KR102115817B1 - Thermosetting resin composition for forming cured film, negative radiation-sensitive resin composition, positive radiation-sensitive resin composition, cured film, method for forming the same, semiconductor device and display device - Google Patents

Abstract

화학식 (1) 중, R¹ 및 R²는 수소 원자, 탄소수 1 내지 4의 알킬기 또는 탄소수 1 내지 4의 불소화 알킬기이다. 화학식 (2) 중, R³ 및 R⁴는 수소 원자, 할로겐 원자, 탄소수 1 내지 4의 알킬기 또는 탄소수 1 내지 4의 불소화 알킬기이다. 상기 가교성 기(a1)는 옥시라닐기 및 옥세타닐기로 이루어지는 군에서 선택되는 적어도 1종인 것이 바람직하다.The present invention, while having excellent surface hardness, can form a cured film capable of satisfactorily satisfying general characteristics such as sensitivity, developing adhesion, chemical resistance, heat resistance, transmittance, and relative dielectric constant, and also has excellent storage stability. It aims at provision of the thermosetting resin composition for formation, a negative radiation sensitive resin composition, and a positive radiation sensitive resin composition.
The solution of the present invention is [A1] a structural unit (I) containing at least one member selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2), and a crosslinkable group It is a thermosetting resin composition for forming a cured film containing a polymer having a structural unit (II-1) containing (a1).
In addition, the solution means of the present invention, [A2] a structural unit (I) comprising at least one member selected from the group consisting of groups represented by the following formula (1) and the following formula (2), and crosslinking Negative radiation-sensitive resin containing a polymer having a structural unit (II-2) containing a radical (a2), [B] a polymerizable compound having an ethylenically unsaturated bond, and [C] a radiation-sensitive polymerization initiator It is a composition.
In addition, the solving means of the present invention, [A3] a structural unit (I) containing at least one member selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2), cyclic It is a positive radiation sensitive resin composition containing a polymer having a structural unit (II-3) containing an ether structure or a cyclic carbonate structure, and an acid generator [G].

In the formula (1), R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms. In the formula (2), R ³ and R ⁴ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms. It is preferable that the crosslinkable group (a1) is at least one selected from the group consisting of an oxiranyl group and an oxetanyl group.

Description

Thermosetting resin composition for forming a cured film, negative radiation sensitive resin composition, positive radiation sensitive resin composition, cured film, formation method thereof, semiconductor device and display device {THERMOSETTING RESIN COMPOSITION FOR FORMING CURED FILM, NEGATIVE RADIATION-SENSITIVE RESIN COMPOSITION, POSITIVE RADIATION-SENSITIVE RESIN COMPOSITION, CURED FILM, METHOD FOR FORMING THE SAME, SEMICONDUCTOR DEVICE AND DISPLAY DEVICE}

The present invention relates to a thermosetting resin composition for forming a cured film, a negative-type radiation-sensitive resin composition, a positive-type radiation-sensitive resin composition, a cured film, a method for forming the same, a semiconductor element, and a display element.

In recent years, as a flexible display substrate such as electronic paper has attracted attention, a substrate made of plastic using polyethylene terephthalate or the like has been studied as a substrate for the flexible display. Since this substrate causes elongation or shrinkage upon heating, lowering of the manufacturing process is considered, and among these, lowering of the firing temperature in the process of forming a cured film such as an interlayer insulating film that becomes the highest in the manufacturing process is required.

As a material for such a curable film capable of lowering temperature, a radiation-sensitive resin composition having a small number of steps at the time of pattern formation and obtaining a high surface hardness is used, for example, a radiation-sensitive resin composition containing a copolymer containing a carboxyl group and an epoxy group. This is known, and the surface hardness as a cured film is obtained by reacting the carboxyl group and the epoxy group (see Japanese Patent Laid-Open No. 2001-354822).

However, in the radiation-sensitive resin composition containing the above-mentioned copolymer, the carboxyl group and the epoxy group react even during storage of the radiation-sensitive resin composition, and as a result, there is a concern that the storage stability may be lowered.

Therefore, while having excellent surface hardness, it is possible to form a cured film capable of satisfactorily satisfying general characteristics such as sensitivity, developing adhesion, chemical resistance, heat resistance, transmittance and relative dielectric constant, and a resin for forming a cured film having excellent storage stability. A composition, a negative radiation sensitive resin composition, and a positive radiation sensitive resin composition are required.

Japanese Patent Publication No. 2001-354822

The present invention was made on the basis of the above circumstances, the purpose of which is to have an excellent surface hardness, and at the same time, a sensitivity, development adhesion, chemical resistance, heat resistance, transmittance and relative dielectric constant sufficient to satisfy the cured film It is to provide a resin composition for forming a cured film that can be formed and has excellent storage stability, a negative radiation-sensitive resin composition, and a positive radiation-sensitive resin composition.

The invention made to solve the above problems,

[A1] A structural unit (I) containing at least one member selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2), and a structure comprising a crosslinkable group (a1) It is a thermosetting resin composition for forming a cured film containing a polymer (hereinafter also referred to as "[A1] polymer") having a unit (II-1) (hereinafter also referred to as "a resin composition for forming a cured film (1)").

In Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms, provided that at least one of R ¹ and R ² is 1 to 4 carbon atoms. Is a fluorinated alkyl group,

In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms, provided that at least one of R ³ and R ⁴ is a halogen atom Or a fluorinated alkyl group having 1 to 4 carbon atoms)

In addition, another invention made to solve the above problems,

(1) a step of forming a coating film on a substrate by using the resin composition for forming a cured film (1), and

(2) Process of heating the coating film

It is a method of forming a cured film having (hereinafter, also referred to as "the method of forming a cured film (1)").

In addition, another invention made to solve the above problems,

[A2] A structural unit (I) containing at least one member selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2), and a structure comprising a crosslinkable group (a2) A polymer having units (II-2) (hereinafter also referred to as "[A2] polymer"),

[B] a polymerizable compound having an ethylenically unsaturated bond (hereinafter also referred to as "[B] polymerizable compound"), and

[C] radiation-sensitive polymerization initiator

It is a negative radiation-sensitive resin composition containing (hereinafter also referred to as "negative radiation-sensitive resin composition (2)").

In Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms, provided that at least one of R ¹ and R ² is 1 to 4 carbon atoms. Is a fluorinated alkyl group,

In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms, provided that at least one of R ³ and R ⁴ is a halogen atom Or a fluorinated alkyl group having 1 to 4 carbon atoms)

In addition, another invention made to solve the above problems,

(1) a step of forming a coating film on the substrate using the negative radiation-sensitive resin composition (2),

(2) a step of irradiating a portion of the coating film with radiation,

(3) a process of developing the coated film irradiated with the radiation, and

(4) Process of heating the developed coating film

It is a method of forming a cured film having (hereinafter, also referred to as "the method of forming a cured film (2)").

In addition, another invention made to solve the above problems,

Cured film formed from the resin composition for forming a cured film (1) (hereinafter also referred to as "cured film (1)"),

Cured film formed from the negative radiation-sensitive resin composition (2) (hereinafter, also referred to as "cured film (2)"),

A semiconductor device having the cured film, and

Display element including the semiconductor element

It includes.

In addition, "crosslinkable group" refers to a group capable of forming a covalent bond between the same or different molecules.

Another invention made to solve the above problem,

[A3] A structural unit (I) containing at least one member selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2), and a cyclic ether structure or a cyclic carbonate structure A polymer having a structural unit (II-3) (hereinafter also referred to as "[A3] polymer"), and

[G] acid generator

It is a positive radiation sensitive resin composition containing.

In Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms, provided that at least one of R ¹ and R ² is 1 to 4 carbon atoms. It is a fluorinated alkyl group.

In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms, provided that at least one of R ³ and R ⁴ is a halogen atom Or a fluorinated alkyl group having 1 to 4 carbon atoms)

In addition, another invention made to solve the above problems,

Cured film formed from the positive radiation-sensitive resin composition (hereinafter also referred to as "cured film (3)"),

A semiconductor device having the cured film, and

Display element including the semiconductor element

It includes.

In addition, another invention made to solve the above problems,

(1) a step of forming a coating film on the substrate using the positive radiation-sensitive resin composition,

(2) a step of irradiating a portion of the coating film with radiation,

(3) a process of developing the coated film irradiated with the radiation, and

(4) Process of heating the developed coating film

It is a method of forming a cured film having (hereinafter, also referred to as "the method of forming a cured film (3)").

The present invention has excellent surface hardness, and at the same time, it is possible to form a cured film capable of satisfactorily satisfying general characteristics such as sensitivity, developing adhesion, chemical resistance, heat resistance, transmittance and relative dielectric constant, and for forming a cured film having excellent storage stability. A thermosetting resin composition, a negative-type radiation-sensitive resin composition, and a positive-type radiation-sensitive resin composition can be provided. Therefore, the thermosetting resin composition for forming a cured film, a negative radiation-sensitive resin composition, a positive radiation-sensitive resin composition, a thermosetting resin composition for forming the cured film, a negative radiation-sensitive resin composition, a positive radiation-sensitive resin The cured film formed from the composition, a semiconductor element and a display element, and the method for forming the cured film can be preferably used in manufacturing processes such as flexible displays and other electronic devices.

<Resin composition for curing film formation (1)>

The resin composition (1) for forming a cured film of the present invention contains the [A1] polymer. Moreover, the said resin composition for cured film formation (1) may contain other components other than a [A1] polymer in the range which does not impair the effect of this invention.

Since the resin composition for forming a cured film (1) contains the [A1] polymer, it is a so-called thermosetting resin composition that is cured by crosslinking by heating. Hereinafter, each component is explained in full detail.

<[A1] polymer>

[A1] The polymer is a polymer having a structural unit (I) and a structural unit (II-1). Further, the polymer [A1] may have a structural unit (III) and a structural unit (IV) within a range that does not impair the effects of the present invention. [A1] As the polymer has a structural unit (I) and a structural unit (II-1), the resin composition for forming a cured film (1) has excellent surface hardness and chemical resistance, heat resistance, transmittance, relative dielectric constant, etc. It is possible to form a cured film capable of satisfactorily satisfying the general characteristics of, and has excellent storage stability. This is a hydroxyl group in the group represented by formulas (1) and / or (2) contained in this structural unit (I) during heating, and a crosslinkable group (a1) contained in the structural unit (II-1). It is presumed that by reacting and forming a strong crosslinked structure, the cured film can obtain excellent surface hardness, and at the same time, the reaction is difficult to proceed at room temperature, and as a result, thickening is suppressed during storage to obtain good storage stability. . Further, the [A1] polymer may have two or more types of each structural unit.

[Structural Unit (I)]

The structural unit (I) is a structural unit comprising at least one member selected from the group consisting of groups represented by the formula (1) and groups represented by the formula (2).

In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms. However, at least one of R ¹ and R ² is a fluorinated alkyl group having 1 to 4 carbon atoms.

In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms. However, at least one of R ³ and R ⁴ is a halogen atom or a fluorinated alkyl group having 1 to 4 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ include, for example, a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t -Butyl group etc. are mentioned.

The fluorinated alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ is a group in which part or all of the hydrogen atoms of the alkyl group having 1 to 4 carbon atoms are substituted with fluorine atoms. Examples of the fluorinated alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ include, for example, difluoromethyl group, trifluoromethyl group, 2,2-difluoroethyl group, and 2,2,2-trifluoroethyl group. , Perfluoroethyl group, 2,2,3,3-tetrafluoropropyl group, perfluoroethylmethyl group, perfluoropropyl group, 2,2,3,3,4,4-hexafluorobutyl group, Perfluorobutyl group, 1,1-dimethyl-2,2,3,3-tetrafluoropropyl group, etc. are mentioned. Among these, a trifluoromethyl group is preferable as the fluorinated alkyl group having 1 to 4 carbon atoms.

Examples of the halogen atom represented by R ³ and R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, the halogen atom is preferably a fluorine atom.

As the structural unit (I) containing the group represented by the formula (1), structural units represented by the following formulas (1a) and (1b) are preferable.

In the formulas (1a) and (1b), R is each independently a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. R ¹ and R ² are as defined in the above formula (1). R ⁵ and R ⁶ are each independently an (n + 1) valent organic group. n is an integer of 1-5 each independently. When n is 2 or more, a plurality of R ¹ and R ² may be the same or different, respectively.

Examples of the (n + 1) valent organic group represented by R ⁵ and R ⁶ include, for example, a (n + 1) valent chain hydrocarbon group having 1 to 20 carbon atoms and a (n + 1) valent alicyclic hydrocarbon having 3 to 20 carbon atoms. 2 or more of a (n + 1) valent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a linear hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms And (n + 1) valent groups. However, some or all of the hydrogen atoms of these groups may be substituted.

Examples of the (n + 1) -valent chain hydrocarbon group having 1 to 20 carbon atoms include, for example, a group in which n hydrogen atoms are removed from a straight or branched alkyl group having 1 to 20 carbon atoms.

Examples of the linear or branched alkyl group having 1 to 20 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t -Butyl group etc. are mentioned.

Examples of the (n + 1) -valent alicyclic hydrocarbon group having 3 to 20 carbon atoms include, for example, a group in which n hydrogen atoms are removed from a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group and the like.

Examples of the (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms include, for example, a group in which n hydrogen atoms are removed from a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group.

Examples of R ⁵ include propylene groups such as methylene group, ethylene group, 1,3-propylene group, and 1,2-propylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, and nona Methylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group, heptadecamethylene group, octadecamethylene group, nonadecamethylene group Group, insarene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl-1,4-butylene group, 2 Saturated chain hydrocarbon groups such as -methyl-1,4-butylene group, methylidene group, ethylidene group, propylidene group, and 2-propylidene group; Cyclobutylene groups such as 1,3-cyclobutylene groups, cyclopentylene groups such as 1,3-cyclopentylene groups, cyclohexylene groups such as 1,4-cyclohexylene groups, and 1,5-cyclooctylene groups Monocyclic hydrocarbon ring groups such as cycloalkylene groups such as cyclooctylene groups; Norbornylene groups such as 1,4-norbornylene group, 2,5-norbornylene group or 2,6-norbornylene group, 1,5-adamantylene group or 2,6-adamantylene group Polycyclic hydrocarbon groups, such as cyclohexane triyl group, such as adamantylene group and 1,3,5-cyclohexane triyl group; Aromatic hydrocarbon groups such as 1,3-phenylene group or 1,4-phenylene group, or groups in combination thereof are preferable, and ethylene group, 1,2-propylene group, 2,5-norbornylene group, 1,4- The phenylene group and 1,3,5-cyclohexanetriyl group are more preferable. Moreover, as said R <^6> , bivalent aromatic hydrocarbon groups, such as a 1,3-phenylene group or 1,4-phenylene group, are preferable, and a 1,4-phenylene group is more preferable.

As the structural unit (I) containing the group represented by the formula (2), structural units represented by the following formulas (2a) and (2b) are preferable.

In the formulas (2a) and (2b), R is synonymous with the formulas (1a) and (1b). R ³ and R ⁴ are as defined in the above formula (2).

Examples of the structural unit (I) include structural units represented by the following formulas (I-1) to (I-15).

In the above formula, R is synonymous with the above formulas (1a), (1b), (2a) and (2b). Among them, as the structural unit (I), structural units represented by the formulas (I-1) to (I-6), (I-9) and (I-11) to (I-13) are preferable, and alkali development The structural units represented by the formulas (I-1) to (I-6) are more preferred from the viewpoints of sex and / or thermosetting properties.

The content ratio of the structural unit (I) is preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 80 mol% or less, more preferably 30 mol% with respect to the total structural units constituting the polymer [A1]. More than 70 mol% or less is more preferable. When the content ratio of the structural unit (I) is within the above range, storage stability and the like can be effectively improved.

[Structural Unit (II-1)]

The structural unit (II-1) is a structural unit containing a crosslinkable group (a1).

As said crosslinkable group (a1), an oxiranyl group (1,2-epoxy structure), an oxetanyl group (1,3-epoxy structure), a cyclic carbonate group, (meth) acryloyl group etc. are mentioned, for example. have.

As a structural unit (II-1) containing an oxiranyl group, the structural unit etc. which are represented by following formula (II-1)-(II-5) are mentioned, for example.

As a structural unit (II-1) containing an oxetanyl group, the structural unit etc. which are represented by following formula (II-6)-(II-9) are mentioned, for example.

As a structural unit (II-1) containing a cyclic carbonate group, the structural unit etc. which are represented by following formula (II-10)-(II-14) are mentioned, for example.

In the formulas (II-1) to (II-14), R ⁷ is a hydrogen atom, a methyl group or a trifluoromethyl group.

Moreover, as a structural unit (II-1) containing a (meth) acryloyl group, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylic Rate, propylene glycol di (meth) acrylate, dipropylene di (meth) acrylate, tripropylene di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di ( Di (meth) acrylate compounds such as meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and tripropylene glycol diacrylate; Tri (meth) acrylate compounds such as tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate; Tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; And structural units derived from monomeric compounds such as penta (meth) acrylate compounds such as dipentaerythritol penta (meth) acrylate.

Among them, the crosslinkable group (a1) is preferably at least one selected from the group consisting of an oxiranyl group and an oxetanyl group. Accordingly, the chemical resistance of the formed cured film can be further improved.

The content ratio of the structural unit (II-1) is preferably 1 mol% or more and 70 mol% or less, more preferably 5 mol% or more and 50 mol% or less, more preferably 10 with respect to the total structural units constituting the polymer [A1]. More preferably, it is more than 30% by mole. When the content ratio of the structural unit (II-1) is within the above range, storage stability and the like can be effectively improved.

[Structural Unit (III)]

[A1] The polymer may have a structural unit (III) described later. The content ratio of the structural unit (III) can be appropriately determined within a range that does not impair the effects of the present invention.

[Structural Unit (IV)]

[A1] The polymer may have a structural unit (IV) described later. [A1] As the polymer has a structural unit (IV), the resin composition for forming a cured film (1) adjusts the glass transition temperature of the resin, so that the melt flow during heat curing or the mechanical properties of the cured film obtained Strength and chemical resistance can be improved.

The content ratio of the structural unit (IV) is preferably 0 mol% or more and 90 mol% or less, more preferably 1 mol% or more and 70 mol% or less, and more preferably 3 mol% with respect to the total structural units constituting the polymer [A1]. More than 60 mol% or less is more preferable. By setting the content ratio of the structural unit (IV) to the above range, chemical resistance can be effectively improved.

<Synthesis method of [A1] polymer>

[A1] The polymer can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical initiator. For example, a solution containing a monomer and a radical initiator is added dropwise to a reaction solvent or a solution containing a monomer to perform polymerization reaction, a solution containing a monomer and a solution containing a radical initiator are each separately, a reaction solvent or A method of polymerization by dropping a solution containing a monomer, and a plurality of types of solutions containing each monomer and a solution containing a radical initiator are separately added to a reaction solvent or a solution containing a monomer to perform polymerization reaction. It is preferable to synthesize by a method such as.

The reaction temperature in these methods may be appropriately determined depending on the initiator type. Usually 30 to 180 ° C, 40 to 160 ° C is preferred, and 50 to 140 ° C is more preferred. The dropping time varies depending on the reaction temperature, the type of initiator, and conditions such as a monomer to be reacted, but is usually 30 minutes to 8 hours, preferably 45 minutes to 6 hours, and more preferably 1 hour to 5 hours. In addition, the total reaction time including the dropping time varies depending on the conditions as in the dropping time, but is usually 30 minutes to 8 hours, preferably 45 minutes to 7 hours, and more preferably 1 hour to 6 hours.

As the radical initiator used in the polymerization, azobisisobutyronitrile (AIBN), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis ( 2-cyclopropyl propionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile), and the like. These initiators may be used alone or in combination of two or more.

The polymerization solvent is a solvent other than a solvent that inhibits polymerization (nitrobenzene having a polymerization inhibitory effect, a mercapto compound having a chain transfer effect, etc.), and is not limited as long as it is a solvent capable of dissolving the monomer. Examples of the polymerization solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-lactone-based solvents, and nitrile-based solvents. These solvents may be used alone or in combination of two or more.

The polymer obtained by the polymerization reaction can be recovered by reprecipitation. That is, after completion of the polymerization reaction, the target polymer is recovered as a powder by adding the polymer solution to the reprecipitation solvent. As the reprecipitation solvent, alcohols, alkanes, or the like can be used alone or in combination of two or more. In addition to the reprecipitation method, a polymer may be recovered by removing small-molecular components such as monomers and oligomers by separating operation, column operation, ultrafiltration operation, or the like. In addition, when the polymerization solvent is the same as the solvent of the resin composition for forming a cured film 1 to be produced, the obtained polymer solution is used as it is, or by adding a solvent to the obtained polymer solution, the production of the resin composition for forming a cured film 1 It can also be provided.

[A1] In the polymerization reaction for producing the polymer, a molecular weight modifier can be used to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexylmercaptan, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, and thioglycolic acid; Xanthogens such as dimethyl xanthogen sulfide and diisopropyl xanthogen disulfide; Terpineolene, alpha-methylstyrene dimer, etc. are mentioned.

[A1] The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is not particularly limited, but is preferably 1,000 or more and 30,000 or less, more preferably 5,000 or more and 20,000 or less. Moreover, as ratio (Mw / Mn) of the number average molecular weight (Mn) of [A1] polymer by polystyrene conversion by Mw and GPC, 1 or more and 3 or less are preferable, and 1.5 or more and 2.5 or less are more preferable.

<Other ingredients>

As other components which may be contained in the resin composition for forming a cured film (1), for example, [D] antioxidant, [E] surfactant, [F] adhesion aid, etc. may be mentioned in addition to the solvent described below. . Moreover, the said resin composition for cured film formation (1) can also use each said component individually or in combination of 2 or more types.

<[D] Antioxidant>

[D] Antioxidants are components that can decompose radicals generated by exposure or heating, or peroxides produced by oxidation, to prevent the antipyretic bonds of polymer molecules. As a result, the resulting cured film is prevented from deteriorating oxidation over time, for example, it is possible to suppress a change in the film thickness of the cured film.

[D] Examples of the antioxidant include a compound having a hindered phenol structure, a compound having a hindered amine structure, a compound having an alkylphosphite structure, and a compound having a thioether structure. Among them, a compound having a hindered phenol structure is preferable as the [D] antioxidant.

Examples of the compound having the hindered phenol structure include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4 -Hydroxybenzyl) benzene, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 3,3 ', 3' , 5 ', 5'-hexa-tert-butyl-a, a', a '-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate , Hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy-2 , 6-Xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6 -Bis (octylthio) -1,3,5-triazine-2-ylamine) phenol, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4 -Hydroxybenzyl) benzene, 2,6-di-t-butyl-4-cresol, and the like.

As a commercial item of the compound having the hindered phenol structure, for example, Adekastab AO-20, copper AO-30, copper AO-40, copper AO-50, copper AO-60, copper AO-70, copper AO- 80, copper AO-330 (above, manufactured by ADEKA), sumilizer GM, copper GS, copper MDP-S, copper BBM-S, copper WX-R, copper GA-80 (above, manufactured by Sumitomo Chemicals), IRGANOX 1010 , East 1035, East 1076, East 1098, East 1135, East 1330, East 1726, East 1425WL, East 1520L, East 245, East 259, East 3114, East 565, IRGAMOD 295 (above, manufactured by BASF), Yoshinox BHT, Copper BB, copper 2246G, copper 425, copper 250, copper 930, copper SS, copper TT, copper 917, copper 314 (above, manufactured by API Corporation).

Among them, as a compound having a hindered phenol structure, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl- 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,6-di-t-butyl-4-cresol is more preferable.

[D1] The content of the antioxidant is preferably 0.001 parts by mass or more and 5 parts by mass or less, more preferably 0.01 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the polymer [A1]. [D] By setting the content of the antioxidant in the above range, it is possible to effectively prevent aging deterioration over time of the cured film obtained.

<[E] surfactant>

[E] The surfactant is a component that improves film formability. [E] Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, and other surfactants.

As the fluorine-based surfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group on at least one of the terminal, main and side chains is preferable, for example, 1,1,2,2-tetrafluoro- n-octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycoldi (1 , 1,2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1 , 1,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, perfluoro-n- Sodium dodecanesulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n -Dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkyl phosphate, sodium fluoroalkyl carboxylate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkyl Betaine, other fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethanols, perfluoroalkyl alkoxylates, fluoroalkyl carboxylic acids, and the like.

As a commercial product of the fluorine-based surfactant, for example, BM-1000, BM-1100 (above, manufactured by BM CHEMIE), Megaface F142D, Copper F172, Copper F173, Copper F183, Copper F178, Copper F191, Copper F471, copper F476 (above, manufactured by Dai Nippon Ink Chemical Co., Ltd.), Fluorad FC-170C, copper-171, copper-430, copper-431 (above, manufactured by Sumitomo 3M), suplon S-112, copper- 113, copper-131, copper-141, copper-145, copper-382, suplon SC-101, copper-102, copper-103, copper-104, copper-105, copper-106 (above, manufactured by Asahi Glass) , F-top EF301, Copper 303, Copper 352 (above, manufactured by Shin-Akita Kasei), Gift FT-100, Copper-110, Copper-140A, Copper-150, Copper-250, Copper-251, Copper-300, Copper -310, copper-400S, FTX-218, copper-251 (above, manufactured by Neos), and the like.

Commercially available products of the silicone surfactants include, for example, Toray Silicone DC3PA, Copper DC7PA, Copper SH11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH-190, Copper SH-193, Copper SZ-6032, Copper SF -8428, Copper DC-57, Copper DC-190 (above, manufactured by Toray Dow Corning and Silicon), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, GE Toshiba Silicon Co., Ltd., organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.) and the like.

Examples of the other surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene-n-octylphenyl ether and polyoxyethylene-n-nonylphenyl ether; And nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate.

Examples of commercially available products of the other surfactants include (meth) acrylic acid copolymer polyflow No.57, copper No.95 (above, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

[E1] The content of the surfactant is preferably 0.01 parts by mass or more and 3 parts by mass or less, more preferably 0.05 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the polymer [A1]. When the content of the surfactant [E] is within the above range, film-forming properties can be effectively improved.

<[F] adhesion aid>

[F] The adhesion aid is a component that improves the adhesion between the resulting cured film and the substrate. [F] As the adhesion aid, a functional silane coupling agent having a reactive functional group such as a carboxyl group, methacryloyl group, vinyl group, isocyanate group, or oxiranyl group is preferable.

Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ -Glycidoxypropyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, and the like.

[F1] As the content of the adhesion aid, 0.01 parts by mass or more and 20 parts by mass or less are preferable, and more preferably 0.1 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the polymer [A1].

<The manufacturing method of the resin composition for hardening film formation (1)>

The resin composition (1) for forming a cured film of the present invention can be produced by mixing the [A1] polymer and other components, if necessary, in a predetermined ratio, and preferably dissolving in a suitable solvent. It is preferable to filter the produced resin composition (1) for forming a cured film with a filter having a pore size of about 0.2 µm, for example.

As a solvent used in the preparation of the resin composition for forming a cured film (1), one that uniformly dissolves or disperses each component contained in the resin composition for forming a cured film (1) and does not react with each of the components is used do. Examples of such a solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, and hydrocarbon solvents.

As said alcohol solvent, for example

As a mono alcohol solvent, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec -Pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol , 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec -Heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, etc .;

As a polyhydric alcohol solvent, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2 , 4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, etc .;

As a polyalcohol partial ether-based solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2- Ethyl butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and the like.

Examples of the ether-based solvent include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, and the like. Can be lifted.

Examples of the ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, and ethyl-n -Butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, And acetonyl acetone, acetophenone, and the like.

Examples of the amide solvents include N, N'-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, and N-methylacetate Amide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, and the like.

Examples of the ester solvent include methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate , Methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether acetate , Diethylene glycol monoethyl ether acetate, diethylene glycol monoacetate-n-propyl ether, diethylene glycol monoacetate-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate acetate, propylene glycol monopropyl acetate Ether, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxy triglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, di oxalate And ethyl, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate and the like.

As the hydrocarbon-based solvent, for example

As an aliphatic hydrocarbon-based solvent, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, Methyl cyclohexane, etc .;

As aromatic hydrocarbon solvent, benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di- and i-propylbenzene, n-amylnaphthalene, and the like.

In addition, the solvent may further contain a high boiling point solvent such as caproic acid, caprylic acid, ethylene carbonate, propylene carbonate.

<Method of forming a cured film (1)>

The method (1) of forming the cured film of the present invention,

(1) A step of forming a coating film on the substrate using the resin composition for forming a cured film (1) (hereinafter also referred to as "step (A1)"), and

(2) Step of heating the coating film (hereinafter also referred to as "step (A2)")

Have

Since the resin composition for forming a cured film (1) has the above properties, according to the method (1) for forming a cured film of the present invention, it satisfies general characteristics such as heat resistance, chemical resistance, transmittance, and relative dielectric constant, and is excellent. A cured film having a surface hardness can be formed. Hereinafter, each process is explained in full detail.

[Process (A1)]

In this step, a coating film is formed on the substrate by using the resin composition for forming a cured film (1). Specifically, the solution of the resin composition for forming a cured film (1) is applied to the surface of the substrate, and preferably pre-baking to remove the solvent to form a coating film. Examples of the substrate include glass substrates, silicon substrates, plastic substrates, and substrates on which various metal thin films are formed. As said plastic substrate, the resin substrate containing plastics, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyether sulfone, polycarbonate, polyimide, is mentioned, for example.

As the coating method, suitable methods such as a spray method, a roll coating method, a rotation coating method (spin coating method), a slit die coating method, a bar coating method, and an inkjet method can be adopted, for example. Of these, spin coating, bar coating or slit die coating is preferred as the coating method. The conditions of the pre-baking vary depending on the type of each component, the use ratio, and the like, but can be, for example, from 60 ° C to 130 ° C for about 30 seconds to 10 minutes. The film thickness of the formed coating film is preferably 0.1 µm to 8 µm, more preferably 0.1 µm to 6 µm, and even more preferably 0.1 µm to 4 µm as a value after pre-baking.

[Process (A2)]

In this step, the coating film is cured by heating. Although it does not specifically limit as a heating method, For example, it can heat using a heating apparatus, such as an oven and a hot plate. The heating temperature in this step is preferably 200 ° C or lower. By heating at such a low temperature, the method (1) of forming the cured film can be preferably used for forming a cured film such as an interlayer insulating film on a plastic substrate of a flexible display. The heating temperature is more preferably 120 ° C to 180 ° C, and even more preferably 120 ° C to 150 ° C. The heating time varies depending on the type of the heating device, but may be, for example, 5 minutes to 40 minutes when heat treatment is performed on a hot plate, and 30 minutes to 80 minutes when heat treatment is performed in an oven, more preferably Is within 30 minutes when performing heat treatment on a hot plate, and within 60 minutes when performing heat treatment in an oven. In this way, a cured film 1 such as a target interlayer insulating film can be formed on a substrate.

<Curing film (1)>

The cured film 1 of the present invention is formed from the resin composition 1 for forming the cured film. Although it does not specifically limit as a formation method of the said cured film 1, Preferably, it can form using the formation method (1) of the said cured film mentioned above. Since the cured film 1 is formed from the resin composition 1 for forming a cured film, it has excellent surface hardness and can satisfactorily satisfy general characteristics such as chemical resistance, heat resistance, transmittance, and relative dielectric constant. Since the cured film 1 has the above characteristics, it is preferable as, for example, an interlayer insulating film of a display element, a spacer, a protective film, a coloring pattern for a color filter, or the like.

<Negative radiation sensitive resin composition (2)>

The negative radiation-sensitive resin composition (2) of the present invention contains the [A2] polymer, [B] polymerizable compound, and [C] radiation-sensitive polymerization initiator. Moreover, the said negative radiation sensitive resin composition (2) may contain [D] antioxidant as a suitable component. Moreover, the said negative radiation sensitive resin composition (2) may contain other arbitrary components other than [A] component-[D] component in the range which does not impair the effect of this invention.

Since the negative-type radiation-sensitive resin composition (2) contains a [A2] polymer, a [B] polymerizable compound, and a [C] radiation-sensitive polymerization initiator, a region (exposed part) irradiated with radiation is polymerized. It is a negative radiation sensitive resin composition having so-called negative characteristics that can be cured by, and a part other than the exposed portion (unexposed portion) is dissolved and removed by development with an alkali developer to form a pattern. Therefore, the said negative radiation sensitive resin composition 2 can form a patterned cured film. Hereinafter, each component is explained in full detail.

<[A2] polymer>

[A2] The polymer is a polymer having a structural unit (I) and a structural unit (II-2). Further, the polymer [A2] may have a structural unit (III) and a structural unit (IV) within a range that does not impair the effects of the present invention. [A2] As the polymer has a structural unit (I) and a structural unit (II-2), the negative radiation-sensitive resin composition (2) has an excellent surface similar to the resin composition (1) for forming a cured film. At the same time as having hardness, a cured film capable of satisfactorily satisfying general characteristics such as sensitivity, developing adhesion, chemical resistance, heat resistance, transmittance, and relative dielectric constant can be formed, and storage stability is excellent. In addition, the negative-type radiation-sensitive resin composition (2), the ease of leaving the hydrogen atom of the alcoholic hydroxyl group by the electron withdrawing of the fluorinated alkyl group of the group represented by the formula (1), and the group represented by the formula (2) The phenolic hydroxyl group by the electron withdrawing property of the halogen atom and / or the fluorinated alkyl group exhibits acidity due to the ease of leaving the hydrogen atom, and as a result, the development residue by the alkali developer in the unexposed portion can be reduced. Further, the [A2] polymer may have two or more types of each structural unit.

[Structural Unit (I)]

The structural unit (I) is a structural unit comprising at least one member selected from the group consisting of groups represented by the formula (1) and groups represented by the formula (2).

Since this structural unit (I) is the same as the structural unit (I) in the above-mentioned [A1] polymer, detailed description thereof is omitted.

The content ratio of the structural unit (I) is preferably 5 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 80 mol% or less, more preferably 30 mol% with respect to the total structural units constituting the polymer [A2]. More than 70 mol% or less is more preferable. When the content ratio of the structural unit (I) is within the above range, storage stability and the like can be effectively improved.

[Structural Unit (II-2)]

The structural unit (II-2) is a structural unit containing a crosslinkable group (a2).

As a structural unit (II-2), the structural unit similar to the structural unit illustrated by the structural unit (II-1) mentioned above, etc. are mentioned, for example.

It is preferable that it is at least 1 sort (s) selected from the group which consists of an oxiranyl group, an oxetanyl group, a cyclic carbonate group, and a (meth) acryloyl group as said crosslinkable group (a2). Accordingly, the chemical resistance of the formed cured film can be further improved.

The content ratio of the structural unit (II-2) is preferably 1 mol% or more and 70 mol% or less, more preferably 5 mol% or more and 50 mol% or less, more preferably 10 with respect to the total structural units constituting the polymer [A2]. More preferably, it is more than 30% by mole. When the content ratio of the structural unit (II-2) is within the above range, storage stability and the like can be effectively improved.

[Structural Unit (III)]

The structural unit (III) is a structural unit other than the structural unit (I), and is a structural unit derived from a (meth) acrylic acid ester having a hydroxyl group, or a structural unit derived from a compound represented by the following formula (3). [A2] When the polymer has a structural unit (III), it is possible to control alkali developability and suppress residue.

In the formula (3), R 'is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a fluorine atom. R ^L1 to R ^L5 are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. Y is a single bond, -COO- or -CONH-. p is an integer from 0 to 3. However, at least 1 of R ^L1 to R ^L5 is a hydroxyl group.

As the alkyl group having 1 to 4 carbon atoms represented by R ^L1 to R ^L5 , for example, the same groups as those exemplified as the alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ can be applied.

Examples of the structural unit (III) include structural units represented by the following formulas (III-1) to (III-11).

In the formulas (III-1) to (III-11), R ⁸ is a hydrogen atom, a methyl group or a trifluoromethyl group. p is synonymous with the said Formula (3). Among them, as the structural unit (III), structural units represented by the formulas (III-1), (III-4) and (III-10) are preferable.

As a monomer compound providing the structural unit (III), 2-hydroxyethyl methacrylate, 4-hydroxyphenyl methacrylate, o-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxy Styrene is preferable, 2-hydroxyethyl methacrylate, 4-hydroxyphenylmethacrylate, and α-methyl-p-hydroxystyrene are more preferable.

The content ratio of the structural unit (III) is preferably 0 mol% or more and 50 mol% or less, more preferably 1 mol% or more and 30 mol% or less, and more preferably 3 mol% with respect to the total structural units constituting the polymer [A2]. More than 20 mol% or less is more preferable.

[Structural Unit (IV)]

The structural unit (IV) is a structural unit other than the structural units (I) to (III). The structural unit (IV) is not particularly limited as long as it is a structural unit other than the structural units (I) to (III). [A2] As the polymer has a structural unit (IV), the negative radiation-sensitive resin composition (2) adjusts the glass transition temperature of the resin, so that alkali developability, melt flow during thermal curing, or mechanical properties of the cured film Strength and chemical resistance can be improved.

Examples of the structural unit (IV) include structural units represented by the following formulas (IV-1) to (IV-11).

In the formulas (IV-1) to (IV-11), R ⁹ is a hydrogen atom, a methyl group or a trifluoromethyl group. R ^M is a hydrogen atom or a methyl group. s is an integer from 1 to 10. Among them, as the structural unit (IV), structural units represented by formulas (IV-1), (IV-2), (IV-7) to (IV-9), and (IV-11) are preferable.

Examples of the monomer compound that provides the structural unit (IV) include (meth) acrylic acid, (meth) acrylic acid chain alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester, Bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds and conjugated diene compounds, and tetrahydrofuran skeletons, furan skeletons, tetrahydropyran skeletons, pyran skeletons, or unsaturated compounds having a skeleton represented by the following formula (4), other And structural units derived from unsaturated compounds and the like.

In the formula (4), R ^M and s are synonymous with the formulas (IV-1) to (IV-11).

Examples of the (meth) acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, n-lauryl acrylate, Acrylic acid chain alkyl esters such as tridecyl acrylate and n-stearyl acrylate; Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-methacrylate And methacrylic acid chain alkyl esters such as lauryl, tridecyl methacrylate, and n-stearyl methacrylate.

Examples of the (meth) acrylic acid cyclic alkyl ester include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo acrylate [5.2.1.0 ^2,6 ] decan-8-yl, and tricyclo acrylate [5.2.1.0 ^{2, 6} ] acrylic acid cyclic alkyl esters such as decan-8-yloxyethyl and isobornyl acrylate; Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl, tricyclomethacrylate [5.2.1.0 ^2,6 ] decane-8 -Cyclic alkyl esters of methacrylic acid such as monooxyethyl and isobornyl methacrylate.

Examples of the (meth) acrylic acid aryl ester include acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; And methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate.

As said unsaturated dicarboxylic acid diester, diethyl maleate, diethyl fumarate, diethyl itaconic acid, etc. are mentioned, for example.

Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1] hept -2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] Hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohex Siloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [ 2.2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2 .1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2- Yen, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, etc. are mentioned.

Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, and N- (4-hydroxybenzyl) maleimide Mid, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimidecaproate, N-succinimidyl-3-maleimide Propionate, N- (9-acridinyl) maleimide, and the like.

Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and α-methyl-p-hydroxystyrene.

As said conjugated diene compound, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc. are mentioned, for example.

As the unsaturated compound having a tetrahydrofuran skeleton, for example, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, (meth) acrylic acid Tetrahydrofurfuryl, tetrahydro (meth) acrylate, and the like.

Examples of the unsaturated compound having a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, and 1-furan-2-butyl-3-ene -2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan- 2-yl-hexy-1-en-3-one, acrylic acid-2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-hepten-3-one And the like.

Examples of the unsaturated compound containing the tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct- And 1-en-3-one, 2-methacrylic acid tetrahydropyran-2-yl ester, and 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one.

Examples of the unsaturated compound having a pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran, 4- (1,5-dioxa- And 6-oxo-7-octenyl) -6-methyl-2-pyran.

As the unsaturated compound having a skeleton represented by the formula (4), for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and the like.

As said other unsaturated compound, (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate etc. are mentioned, for example.

Among these, as the monomer compound providing the structural unit (IV), methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, maleimide compound, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, An unsaturated compound having a skeleton represented by the formula (4), an unsaturated aromatic compound, and an acrylic acid cyclic alkyl ester are preferred, and in view of copolymerization reactivity and solubility in an aqueous alkali solution, styrene, methacrylic acid, methyl methacrylate, and meta T-butyl acrylate, n-lauryl methacrylate, tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleate Mid, N-cyclohexylmaleimide, (meth) acrylic acid tetrahydrofurfuryl, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydrofuran-2-one It is more preferable.

The content ratio of the structural unit (IV) is preferably 0 mol% or more and 90 mol% or less, more preferably 1 mol% or more and 70 mol% or less, and more preferably 3 mol% with respect to the total structural units constituting the polymer [A2]. More than 60 mol% or less is more preferable. The chemical resistance can be effectively improved by making the content rate of the structural unit (IV) into the said range.

<Synthesis method of [A2] polymer>

The method for synthesizing the polymer [A2] is not particularly limited, and for example, the same method as for the method for synthesizing the polymer [A1] described above can be applied.

[A2] As the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer, 1,000 or more and 30,000 or less are preferable, and 5,000 or more and 20,000 or less are more preferable. [A2] By setting the Mw of the polymer to the above range, the sensitivity and developability of the negative radiation-sensitive resin composition 2 can be further improved. Moreover, as ratio (Mw / Mn) of the number average molecular weight (Mn) in polystyrene conversion by Mw and GPC of [A2] polymer, 1 or more and 3 or less are preferable, and 1.5 or more and 2.5 or less are more preferable.

<[B] polymerizable compound>

[B] The polymerizable compound is a compound having an ethylenically unsaturated bond. Further, the polymerizable compound [B] may be used alone or in combination of two or more.

[B] The polymerizable compound is not particularly limited as long as it is a polymerizable compound having an ethylenically unsaturated bond, for example, ω-carboxypolycaprolactone mono (meth) acrylate, 2- (2'-vinyloxyethoxy) ethyl Monofunctional (meth) acrylate compounds such as (meth) acrylate; Ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) ) Acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanolfluorenedi (meth) acrylate, dimethyloltricyclodecanedi (meth) acrylate, 2-hydroxy-3- (meth) Acryloyloxypropyl methacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol triacrylate, straight chain alkylene group And urethane (meth) acrylates obtained by reacting a compound having an alicyclic structure, two or more isocyanate groups, and one or more hydroxyl groups in the molecule, and three to five (meth) acryloyloxy groups. And polyfunctional (meth) acrylate compounds such as compounds.

[B] As a commercial product of the polymerizable compound, for example

Aaronix M-400, East M-402, East M-405, East M-450, East M-1310, East M-1600, East M-1960, East M-7100, East M-8030, East M-8060 , Copper M-8100, Copper M-8530, Copper M-8560, Copper M-9050, Aaronix TO-1450, Copper TO-1382 (above, manufactured by Toa Kosei);

KAYARAD DPHA, copper DPCA-20, copper DPCA-30, copper DPCA-60, copper DPCA-120, copper MAX-3510 (above, manufactured by Nippon Kayaku);

Biscot 295, Copper 300, Copper 360, Copper GPT, Copper 3PA, Copper 400 (above, manufactured by Osaka Yuki Kagaku High School);

As a urethane acrylate type compound, New Frontier R-1150 (made by Daiichi Kogyo Seiyaku);

KAYARAD DPHA-40H, UX-5000 (above, manufactured by Nippon Kayaku);

UN-9000H (manufactured by Negami High School);

Aaronix M-5300, Copper M-5600, Copper M-5700, M-210, Copper M-220, Copper M-240, Copper M-270, Copper M-6200, Copper M-305, Copper M-309, Copper M-310, Copper M-315 (above, manufactured by Toa Kosei);

KAYARAD HDDA, KAYARAD HX-220, East HX-620, East R-526, East R-167, East R-604, East R-684, East R-551, East R-712, UX-2201, UX-2301 , UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (above, manufactured by Nippon Kayaku);

Art resin UN-9000PEP, copper UN-9200A, copper UN-7600, copper UN-333, copper UN-1003, copper UN-1255, copper UN-6060PTM, copper UN-6060P (above, manufactured by Negami High School);

And SH-500B biscoat 260, copper 312, copper 335HP (above, manufactured by Osaka Yuki Chemical Industries).

[B] It is preferable that the polymerizable compound has at least one carboxy group in the same molecule. Accordingly, it is possible to improve the crosslinking property and reduce the development residue in the unexposed portion. As the [B] polymerizable compound having at least one carboxyl group in the same molecule, ω-carboxypolycaprolactone mono (meth) acrylate and succinic acid-modified pentaerythritol triacrylate are preferable.

[B2] The content of the polymerizable compound is preferably 20 parts by mass or more and 200 parts by mass or less, more preferably 40 parts by mass or more and 160 parts by mass or less with respect to 100 parts by mass of the polymer [A2]. [B] By setting the content of the polymerizable compound in the above range, the negative radiation-sensitive resin composition (2) has excellent adhesion and can form a cured film having a sufficient surface hardness even at a low exposure amount.

<[C] radiation-sensitive polymerization initiator>

[C] The radiation-sensitive polymerization initiator is a component that generates an active species capable of initiating polymerization of the polymerizable compound [B] in response to radiation. [C] As a radiation-sensitive polymerization initiator, an oxime ester compound, an acetophenone compound, a biimidazole compound, etc. are mentioned, for example. Further, the radiation-sensitive polymerization initiator [C] may be used alone or in combination of two or more.

Examples of the oxime ester compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1,2 -Octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octan-1-one Oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethan-1-one oxime-O-benzoate, 1- [9-n -Butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethan-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl -4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydro Pyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl)- 9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-diox) And o-acyloxime compounds such as solanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime). Among them, as the oxime ester compound, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1,2-octane Dione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxosol) Neil) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.

Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.

Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4-methylbenzyl). -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and the like. have.

Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane. -1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, and the like.

As the acetophenone compound, an α-aminoketone compound is preferable, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one is more preferable.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'- Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4- Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5 And 5'-tetraphenyl-1,2'-biimidazole. Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichloro Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole is preferred, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2' -Biimidazole is more preferred.

[C] As a commercial product of the radiation-sensitive polymerization initiator, for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907), 2-dimethylamino -2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (Irgacure 379), 1,2-octandione-1- [4- ( Phenylthio) -2- (O-benzoyloxime)] (Irgacure OXE01), Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1 -(O-acetyloxime) (Irgacure OXE02) (above, manufactured by Ciba Specialty Chemicals) and the like.

[C2] The content of the radiation-sensitive polymerization initiator is preferably 0.1 parts by mass or more and 40 parts by mass or less, more preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymer [A2]. By setting the content of the radiation-sensitive polymerization initiator in the above range, the negative radiation-sensitive resin composition 2 can form a cured film having sufficient surface hardness and adhesion even in the case of a low exposure amount.

In addition, the radiation-sensitive polymerization initiator [C] is an oxime ester compound, and the content of the oxime ester compound is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymer [A2], and 1 part by mass or more and 5 parts by mass or less It is more preferably less than or equal to parts. Accordingly, a cured film having sufficient surface hardness and adhesion can be efficiently formed even in the case of a low exposure amount.

<[D] Antioxidant>

[D] Antioxidants are components that can decompose radicals generated by exposure or heating, or peroxides produced by oxidation, to prevent the deterioration of the binding of polymer molecules. [D] As the antioxidant, the antioxidant described in the above section of <Resin composition for curing film formation (1)> can be applied. By containing the antioxidant [D], the negative radiation-sensitive resin composition (2) can prevent aging deterioration of the cured film obtained over time, for example, to suppress a change in the film thickness of the cured film. In addition, [D] antioxidants may be used alone or in combination of two or more.

[D2] The content of the antioxidant is preferably 0 parts by mass or more and 5 parts by mass or less, more preferably 0.01 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the polymer [A2]. [D] By setting the content of the antioxidant in the above range, it is possible to effectively prevent aging deterioration over time of the cured film obtained.

<Other optional ingredients>

As other arbitrary components which the said negative radiation sensitive resin composition (2) may contain, for example, [E] surfactant, [F] adhesion aid, etc. are mentioned besides a solvent. Moreover, what was demonstrated by the term of the above-mentioned <resin composition for hardening film formation (1)> can be applied to each other arbitrary component.

<The manufacturing method of a negative radiation sensitive resin composition (2)>

The negative radiation-sensitive resin composition (2) of the present invention can be produced by mixing the [A2] polymer and other components, if necessary, in a predetermined ratio, and preferably dissolving in a suitable solvent. As a solvent used for the production of the negative-type radiation-sensitive resin composition 2, for example, the same solvent as the solvent exemplified in the above-described <Method for producing the resin composition for forming a cured film 1> is applied. can do. It is preferable to filter the produced negative radiation-sensitive resin composition 2 with a filter having a pore size of about 0.2 µm, for example.

<Method of forming a cured film (2)>

The method (2) of forming the cured film of the present invention is

(1) A step of forming a coating film on the substrate using the negative radiation-sensitive resin composition (2) (hereinafter also referred to as "step (B1)"),

(2) A step of irradiating a portion of the coating film with radiation (hereinafter also referred to as "step (B2)"),

(3) a process of developing the coated film irradiated with the radiation (hereinafter also referred to as "process (B3)"), and

(4) Process of heating the developed coating film (hereinafter also referred to as "process (B4)")

Have

Since the negative radiation-sensitive resin composition (2) has the above properties, according to the method (2) of forming the cured film of the present invention, it satisfies general characteristics such as heat resistance, chemical resistance, transmittance, and relative dielectric constant. A cured film having excellent surface hardness can be formed. Hereinafter, each process is explained in full detail.

[Process (B1)]

In this step, a coating film is formed on the substrate using the negative radiation-sensitive resin composition (2). Specifically, the solution of the negative radiation-sensitive resin composition (2) is applied to the surface of the substrate, and preferably pre-baking to remove the solvent to form a coating film. Examples of the substrate include glass substrates, silicon wafers, plastic substrates, and substrates on which various metal thin films are formed. As said plastic substrate, the resin substrate containing plastics, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyether sulfone, polycarbonate, and polyimide, is mentioned, for example.

As the coating method, suitable methods such as a spray method, a roll coating method, a rotation coating method (spin coating method), a slit die coating method, a bar coating method, and an inkjet method can be adopted, for example. Of these, spin coating, bar coating or slit die coating is preferred as the coating method. The conditions of the pre-baking vary depending on the type of each component, the use ratio, and the like, but can be, for example, from 60 ° C to 130 ° C for about 30 seconds to 10 minutes. The film thickness of the formed coating film is preferably 0.1 µm to 8 µm, more preferably 0.1 µm to 6 µm, and even more preferably 0.1 µm to 4 µm as a value after pre-baking.

[Process (B2)]

In this process, a part of the coating film is irradiated with radiation. Specifically, the coating film formed in step (B1) is irradiated with radiation through a mask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle rays.

Examples of the ultraviolet rays include g-rays (wavelength 436 nm), i-rays (wavelength 365 nm), and the like. Examples of the far ultraviolet rays include KrF excimer laser light and the like. As X-rays, synchrotron radiation etc. are mentioned, for example. As a charged particle beam, an electron beam etc. are mentioned, for example. Among these radiations, ultraviolet rays are preferred, and among the ultraviolet rays, radiations including g rays, h rays and / or i rays are more preferable. Examples of radiation exposure dose, 0.1J / m ² to 10,000J / m ² is preferred.

[Process (B3)]

In this step, the coated film irradiated with the radiation is developed. Specifically, in the step (B2), the coated film irradiated with radiation is developed with a developer to remove the irradiated portion of the radiation. Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethyl Amines, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0 And an aqueous solution of an alkali (basic compound) such as 7-undecene and 1,5-diazabicyclo [4,3,0] -5-nonane. Further, an aqueous solution in which an appropriate amount of a water-soluble organic solvent or surfactant, such as methanol or ethanol, is added to the aqueous solution of the alkali, or an aqueous alkali solution containing a small amount of various organic solvents capable of dissolving the negative radiation-sensitive resin composition (2) is a developer. It can also be used as.

As the developing method, suitable methods such as a liquid accumulating method, a dipping method, a rocking dipping method, and a shower method can be adopted, for example. As development time, although it differs depending on the composition of the said negative radiation sensitive resin composition (2), it can be made into 30 to 120 seconds, for example. In addition, after the development process, the patterned coating film is subjected to rinsing treatment by flowing water washing, followed by irradiation (post-exposure) of radiation by a high-pressure mercury lamp or the like, followed by exposure to (C) radiation remaining in the coating film. It is preferable to decompose the polymerization initiator. As the exposure amount in the subsequent exposure, 2,000 J / m ² to 5,000 J / m ² is preferable.

[Process (B4)]

In this step, the developed coating film is heated. Specifically, the coating film is cured by heating (post baking) the coating film using a heating device such as a hot plate or oven for heating the developed film developed in the step (B3). The heating temperature in this step is preferably 200 ° C or lower. In addition to the ability to form fine patterns using radiation-sensitive properties, heating at such a low temperature enables the method (2) of forming the cured film to be preferably used for forming a cured film such as an interlayer insulating film on a plastic substrate of a flexible display. . The heating temperature is more preferably 120 ° C to 180 ° C, and even more preferably 120 ° C to 150 ° C. The heating time varies depending on the type of the heating device, but may be, for example, 5 minutes to 40 minutes when heat treatment is performed on a hot plate, and 30 minutes to 80 minutes when heat treatment is performed in an oven, more preferably Is within 30 minutes when performing heat treatment on a hot plate, and within 60 minutes when performing heat treatment in an oven. In this way, a patterned coating film corresponding to a cured film such as a target interlayer insulating film can be formed on a substrate.

<Curing film (2)>

The cured film 2 of the present invention is formed from the negative radiation sensitive resin composition 2. Although it does not specifically limit as a formation method of the said cured film 2, Preferably, it can form using the formation method (2) of the said cured film mentioned above. Since the cured film 2 is formed from the negative radiation-sensitive resin composition 2, it has excellent surface hardness and can satisfactorily satisfy general characteristics such as chemical resistance, heat resistance, transmittance, and relative dielectric constant. . Since the cured film 2 has the above characteristics, it is preferable, for example, as an interlayer insulating film, a spacer, a protective film of a display element, a coloring pattern for a color filter, and the like.

<Semiconductor element>

The semiconductor device of the present invention is provided with the cured film (cured film 1 or cured film 2 described above). This cured film is used, for example, as an interlayer insulating film that insulates between wirings in the semiconductor element. The semiconductor device can be formed using a known method. Since the semiconductor element is provided with the cured film, it can be suitably used for electronic devices such as display elements, LEDs, and solar cells.

<Display element>

The display element of this invention is equipped with the said semiconductor element. Since the display element is provided with a semiconductor element having the cured film, it satisfies the general characteristics required in practical terms as a display element. As said display element, a liquid crystal display element etc. are mentioned, for example. In the liquid crystal display device, for example, two TFT array substrates having a liquid crystal alignment film formed on the surface thereof are arranged opposite to each other on the liquid crystal alignment film side through a sealing agent provided on the periphery of the TFT array substrate, and between these two TFT array substrates The liquid crystal is charged. The TFT array substrate has wirings arranged in layers and is insulated between the wirings by the cured film as an interlayer insulating film.

<Positive radiation-sensitive resin composition>

The positive radiation-sensitive resin composition of the present invention contains the [A3] polymer and the [G] acid generator. Further, the positive radiation-sensitive resin composition may contain a [H] solvent as a suitable component. Moreover, the said positive radiation sensitive resin composition may contain other arbitrary components in the range which does not impair the effect of this invention. Hereinafter, each component is explained in full detail.

<[A3] polymer>

[A3] The polymer is a polymer having structural units (I) and (II-3). Further, the polymer [A3] may have a structural unit (III) and a structural unit (IV) within a range that does not impair the effects of the present invention. Further, the polymer [A3] may have two or more types of structural units.

[Structural Unit (I)]

The structural unit (I) is a structural unit comprising at least one member selected from the group consisting of groups represented by the formula (1) and groups represented by the formula (2). [A3] The polymer has a structural unit (I) and a structural unit (II-3) to be described later, so that the positive radiation-sensitive resin composition maintains good surface hardness, as well as excellent storage stability, sensitivity, A cured film capable of satisfactorily satisfying general characteristics such as developing adhesion, heat resistance, chemical resistance, transmittance, and relative dielectric constant can be formed. This is the hydroxyl group in the group represented by the formulas (1) and / or (2) contained in this structural unit (I), and the cyclic ether and / or cyclic carbonate contained in the structural unit (II-3) described later. It is presumed that, by reacting, the surface hardness of the cured film can be maintained by forming a strong cross-linked structure, and the reaction is difficult to proceed at room temperature, and as a result, thickening is suppressed during storage to obtain good storage stability.

In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms. However, at least one of R ¹ and R ² is a fluorinated alkyl group having 1 to 4 carbon atoms.

In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms. However, at least one of R ³ and R ⁴ is a halogen atom or a fluorinated alkyl group having 1 to 4 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ include, for example, a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t -Butyl group etc. are mentioned.

The fluorinated alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ is a group in which part or all of the hydrogen atoms of the alkyl group having 1 to 4 carbon atoms are substituted with fluorine atoms. As the alkyl group having 1 to 4 carbon atoms, for example, the same groups as those exemplified as the alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ can be applied.

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom.

Examples of the R ¹ to R ^4, is preferably a fluorinated alkyl group, a halogen atom having 1 to 4 carbon atoms. As the fluorinated alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms is more preferable, and a trifluoromethyl group is more preferable. Moreover, as said halogen atom, a fluorine atom is more preferable.

As the structural unit (I) containing the group represented by the formula (1), structural units represented by the following formulas (1a) and (1b) are preferable.

In the formulas (1a) and (1b), R is each independently a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. R ¹ and R ² are as defined in the above formula (1). R ⁵ and R ⁶ are each independently an (n + 1) valent organic group. n is an integer of 1-5 each independently. When n is 2 or more, a plurality of R ¹ and R ² may be the same or different, respectively.

Examples of the (n + 1) valent organic group represented by R ⁵ and R ⁶ include, for example, a (n + 1) valent chain hydrocarbon group having 1 to 20 carbon atoms and a (n + 1) valent alicyclic hydrocarbon having 3 to 20 carbon atoms. 2 kinds of groups, or (n + 1) valent aromatic hydrocarbon groups having 6 to 20 carbon atoms, or chain hydrocarbon groups having 1 to 20 carbon atoms, alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and aromatic hydrocarbon groups having 6 to 20 carbon atoms And (n + 1) valent groups combining the above. However, some or all of the hydrogen atoms of these groups may be substituted.

Examples of the (n + 1) -valent chain hydrocarbon group having 1 to 20 carbon atoms include, for example, a group in which n hydrogen atoms are removed from a straight or branched alkyl group having 1 to 20 carbon atoms.

Examples of the linear or branched alkyl group having 1 to 20 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t -Butyl group etc. are mentioned.

Examples of the (n + 1) -valent alicyclic hydrocarbon group having 3 to 20 carbon atoms include, for example, a group in which n hydrogen atoms are removed from a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group and the like.

Examples of the (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms include, for example, a group in which n hydrogen atoms are removed from a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group.

Of these, R ⁵ is preferably a chain hydrocarbon group, an alicyclic hydrocarbon group, or a group combining these groups, and is preferably an ethylene group, a 1,2-propylene group, a 2,5-norbornylene group, or a 2,6-norbornylene group. The hydrocarbon group containing a group is more preferable. Moreover, as R ⁶ , a divalent aromatic hydrocarbon group is preferable, and a phenylene group is more preferable.

As the structural unit (I) containing the group represented by the formula (2), structural units represented by the following formulas (2a) and (2b) are preferable.

In the formulas (2a) and (2b), R is synonymous with the formulas (1a) and (1b). R ³ and R ⁴ are as defined in the above formula (2).

Examples of the structural unit (I) include structural units represented by the following formulas (I-1) to (I-15).

In the above formula, R is synonymous with the above formulas (1a), (1b), (2a) and (2b). Among them, as the structural unit (I), structural units represented by the formulas (I-1) to (I-6), (I-9) and (I-11) to (I-13) are preferable, and alkali development The structural units represented by the formulas (I-1) to (I-6) are more preferable from the viewpoints of sex and thermosetting properties.

The content ratio of the structural unit (I) is preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 80 mol% or less, more preferably 30 mol% with respect to the total structural units constituting the polymer [A3]. More than 70 mol% or less is more preferable. When the content ratio of the structural unit (I) is within the above range, storage stability and the like can be effectively improved.

[Structural Unit (II-3)]

The structural unit (II-3) is a structural unit containing a cyclic ether structure or a cyclic carbonate structure.

Examples of the cyclic ether structure include an oxirane structure (1,2-epoxy structure), an oxetane structure (1,3-epoxy structure), a tetrahydrofuran structure, and the like.

As a structural unit (II-3), for example,

As an oxirane structure, structural units represented by the following formulas (II-1) to (II-5);

As an oxetane structure, structural units represented by the following formulas (II-6) to (II-9), etc .;

As a tetrahydrofuran structure, structural units represented by the following formulas (II-10) and (II-11);

As containing a cyclic carbonate structure, structural units represented by the following formulas (II-12) to (II-16) and the like can be given.

In the formulas (II-1) to (II-16), R ⁷ is a hydrogen atom, a methyl group or a trifluoromethyl group. Among them, the structural unit (II-3) is preferably a structural unit represented by formulas (II-1) to (II-9) and (II-12) to (II-16) from the viewpoints of crosslinkability and chemical resistance. The structural units represented by the formulas (II-1) to (II-9) are more preferable, and the structural units represented by the formulas (II-1) to (II-5) are more preferable, and the formula (II- The structural units represented by 1) to (II-3) are particularly preferred.

The content ratio of the structural unit (II-3) is preferably 1 mol% or more and 70 mol% or less, more preferably 5 mol% or more and 50 mol% or less, more preferably 10 with respect to the total structural units constituting the polymer [A3]. More preferably, it is more than 30% by mole. When the content ratio of the structural unit (II-3) is within the above range, storage stability and the like can be effectively improved.

The said structural unit (II-3) contains a cyclic ether structure, and it is preferable that this cyclic ether structure is at least one of an oxirane structure and an oxetane structure. The structural unit (II-3) can improve crosslinking property by including the structure, and as a result, the positive radiation-sensitive resin composition can increase surface hardness, heat resistance, and the like.

[Structural Unit (III)]

The structural unit (III) is a structural unit derived from a (meth) acrylic acid ester having a hydroxyl group, or a structural unit derived from a compound represented by the following formula (3). [A3] When the polymer has a structural unit (III), it is possible to control alkali developability and suppress residue.

In the formula (3), R 'is a hydrogen atom or alkyl having 1 to 4 carbon atoms which may be substituted with a fluorine atom. R ^L1 to R ^L5 are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. Y is a single bond, -COO- or -CONH-. p is an integer from 0 to 3. However, at least 1 of R ^L1 to R ^L5 is a hydroxyl group.

As the alkyl group having 1 to 4 carbon atoms represented by R ^L1 to R ^L5 , for example, the same groups as those exemplified as the alkyl group having 1 to 4 carbon atoms represented by R ¹ to R ⁴ can be applied.

Examples of the structural unit (III) include structural units represented by the following formulas (III-1) to (III-11).

In the formulas (III-1) to (III-11), R ⁸ is a hydrogen atom, a methyl group or a trifluoromethyl group. p is synonymous with the said Formula (3). Among them, as the structural unit (III), structural units represented by the formulas (III-1), (III-4) and (III-10) are preferable.

As a monomer compound providing the structural unit (III), 2-hydroxyethyl methacrylate, 4-hydroxyphenyl methacrylate, o-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxy Styrene is preferable, 2-hydroxyethyl methacrylate, 4-hydroxyphenylmethacrylate, and α-methyl-p-hydroxystyrene are more preferable.

The content ratio of the structural unit (III) is preferably 0 mol% or more and 50 mol% or less, more preferably 1 mol% or more and 30 mol% or less, and more preferably 3 mol% with respect to the total structural units constituting the polymer [A3]. More than 20 mol% or less is more preferable.

[Structural Unit (IV)]

The structural unit (IV) is a structural unit other than the structural units (I) to (III). The structural unit (IV) is not particularly limited as long as it is a structural unit other than the structural units (I) to (III). [A3] When the polymer has a structural unit (IV), the glass transition temperature of the resin can be adjusted to improve alkali developability, melt flow during heat curing, mechanical strength of the cured film, and chemical resistance, respectively.

Examples of the structural unit (IV) include structural units represented by the following formulas (IV-1) to (IV-11).

In the formulas (IV-1) to (IV-11), R ⁹ is a hydrogen atom, a methyl group or a trifluoromethyl group. R ^M is a hydrogen atom or a methyl group. s is an integer from 1 to 10. Among them, as the structural unit (IV), structural units represented by formulas (IV-1), (IV-2), (IV-7) to (IV-9), and (IV-11) are preferable.

Examples of the monomer compound that provides the structural unit (IV) include (meth) acrylic acid, (meth) acrylic acid chain alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester, Bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds and conjugated diene compounds, and tetrahydrofuran skeletons, furan skeletons, tetrahydropyran skeletons, pyran skeletons, or unsaturated compounds having a skeleton represented by the following formula (4), other And structural units derived from unsaturated compounds and the like.

In the formula (4), R ^M and s are synonymous with the formulas (IV-1) to (IV-11).

Examples of the (meth) acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, n-lauryl acrylate, Acrylic acid chain alkyl esters such as tridecyl acrylate and n-stearyl acrylate; Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-methacrylate And methacrylic acid chain alkyl esters such as lauryl, tridecyl methacrylate, and n-stearyl methacrylate.

Examples of the (meth) acrylic acid cyclic alkyl ester include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo acrylate [5.2.1.0 ^2,6 ] decan-8-yl, and tricyclo acrylate [5.2.1.0 ^{2, 6} ] acrylic acid cyclic alkyl esters such as decan-8-yloxyethyl and isobornyl acrylate; Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl, tricyclomethacrylate [5.2.1.0 ^2,6 ] decane-8 -Cyclic alkyl esters of methacrylic acid such as monooxyethyl and isobornyl methacrylate.

As said (meth) acrylic acid aryl ester, it is phenyl acrylate, for example. Acrylic acid aryl esters such as benzyl acrylate; And methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate.

As said unsaturated dicarboxylic acid diester, diethyl maleate, diethyl fumarate, diethyl itaconic acid, etc. are mentioned, for example.

Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1] hept -2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] Hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohex Siloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [ 2.2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2 .1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2- Yen, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, etc. are mentioned.

Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, and N- (4-hydroxybenzyl) maleimide Mid, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimidecaproate, N-succinimidyl-3-maleimide Propionate, N- (9-acridinyl) maleimide, and the like.

Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and α-methyl-p-hydroxystyrene.

As said conjugated diene compound, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc. are mentioned, for example.

Examples of the unsaturated compound having a tetrahydrofuran skeleton include tetrahydro (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, and 3- (meth) acryloyloxytetrahydrofuran- 2-on, tetrahydrofurfuryl (meth) acrylate, and the like.

Examples of the unsaturated compound having a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, and 1-furan-2-butyl-3-ene -2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan- 2-yl-hexy-1-en-3-one, acrylic acid-2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-hepten-3-one And the like.

Examples of the unsaturated compound containing the tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct- And 1-en-3-one, 2-methacrylic acid tetrahydropyran-2-yl ester, and 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one.

Examples of the unsaturated compound having a pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran, 4- (1,5-dioxa- And 6-oxo-7-octenyl) -6-methyl-2-pyran.

As said other unsaturated compound, (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate etc. are mentioned, for example.

Among these, as the monomer compound providing the structural unit (IV), methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, maleimide compound, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, An unsaturated compound having a skeleton represented by the formula (4), an unsaturated aromatic compound, and an acrylic acid cyclic alkyl ester are preferred, and in view of copolymerization reactivity and solubility in an aqueous alkali solution, styrene, methacrylic acid, methyl methacrylate, and meta T-butyl acrylate, n-lauryl methacrylate, tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleate Mid, N-cyclohexylmaleimide, (meth) acrylic acid tetrahydrofurfuryl, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydrofuran-2-one It is more preferable.

The content ratio of the structural unit (IV) is preferably 0 mol% or more and 90 mol% or less, more preferably 1 mol% or more and 70 mol% or less, and more preferably 3 mol% with respect to the total structural units constituting the polymer [A3]. More than 60 mol% or less is more preferable. By setting the content ratio of the structural unit (IV) to the above range, chemical resistance can be effectively improved.

<Synthesis method of [A3] polymer>

[A3] The polymer can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical initiator. For example, a solution containing a monomer and a radical initiator is added dropwise to a reaction solvent or a solution containing a monomer to perform polymerization reaction, a solution containing a monomer and a solution containing a radical initiator are each separately, a reaction solvent or A method of polymerization by dropping a solution containing a monomer, and a plurality of types of solutions containing each monomer and a solution containing a radical initiator are separately added to a reaction solvent or a solution containing a monomer to perform polymerization reaction. It is preferable to synthesize by a method such as.

The reaction temperature in these methods may be appropriately determined depending on the initiator type. Usually 30 to 180 ° C, 40 to 160 ° C is preferred, and 50 to 140 ° C is more preferred. The dropping time varies depending on the reaction temperature, the type of initiator, and conditions such as a monomer to be reacted, but is usually 30 minutes to 8 hours, preferably 45 minutes to 6 hours, and more preferably 1 hour to 5 hours. In addition, the total reaction time including the dropping time varies depending on the conditions as in the dropping time, but is usually 30 minutes to 8 hours, preferably 45 minutes to 7 hours, and more preferably 1 hour to 6 hours.

As the radical initiator used in the polymerization, azobisisobutyronitrile (AIBN), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis ( 2-cyclopropyl propionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile), and the like. These initiators may be used alone or in combination of two or more.

The polymerization solvent is a solvent other than a solvent that inhibits polymerization (nitrobenzene having a polymerization inhibitory effect, a mercapto compound having a chain transfer effect, etc.), and is not limited as long as it is a solvent capable of dissolving the monomer. Examples of the polymerization solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-lactone-based solvents, and nitrile-based solvents. These solvents may be used alone or in combination of two or more.

It is preferable that the polymer obtained by the polymerization reaction is recovered by a reprecipitation method. That is, after completion of the polymerization reaction, the target polymer is recovered as a powder by adding the polymerization solution to the reprecipitation solvent. As the reprecipitation solvent, alcohols, alkanes, or the like can be used alone or in combination of two or more. In addition to the reprecipitation method, a polymer may be recovered by removing small-molecular components such as monomers and oligomers by separating operation, column operation, ultrafiltration operation, or the like.

[A3] In the polymerization reaction for producing the polymer, a molecular weight modifier can be used to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexylmercaptan, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, and thioglycolic acid; Xanthogens such as dimethyl xanthogen sulfide and diisopropyl xanthogen disulfide; Terpineolene, alpha-methylstyrene dimer, etc. are mentioned.

[A3] The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is not particularly limited, but is preferably 1,000 or more and 30,000 or less, more preferably 5,000 or more and 20,000 or less. [A3] When the Mw of the polymer is within the above range, the sensitivity and developability of the positive radiation sensitive resin composition can be improved.

[A3] The ratio (Mw / Mn) of the number average molecular weight (Mn) in terms of polystyrene by Mw of the polymer and GPC is preferably 1 or more and 3 or less, and more preferably 1.5 or more and 2.5 or less.

<[G] acid generator>

[G] The acid generator generates acid by irradiation with radiation or heating. When the positive radiation-sensitive resin composition contains an acid generator [G], the exposed portion of radiation has a positive radiation-sensitive property that is removed in the development process, and at the same time, the acid generated by heating in a subsequent heating process is generated. By functioning as a crosslinking catalyst, the crosslinking reaction can be promoted to form a cured film having high heat resistance and surface hardness. As the content form of the [G] acid generator in the positive radiation sensitive resin composition, it may be an aspect of the compound as described below (hereinafter, this aspect is also referred to as "[G] acid generator"), or of a polymer. It may be an aspect inserted as a part or both of them. In addition, the radiation is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like.

[G] As an acid generator, an oxime sulfonate compound, a sulfonimide compound, a quinonediazide compound, etc. are mentioned, for example. Moreover, these [G] acid generators may be used alone or in combination of two or more.

As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by following formula (5) is preferable.

In the formula (5), R ^a is an alkyl group having 1 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. However, some or all of the hydrogen atoms of these alkyl groups, alicyclic groups, and aryl groups may be substituted by substituents.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^a include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, and t-butyl group. And the like. Among these, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable.

Examples of the alicyclic group having 3 to 20 carbon atoms represented by R ^a include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the substituent which the alkyl group and the alicyclic group may have include an alkoxy group having 1 to 10 carbon atoms, an alicyclic group having 1 to 10 carbon atoms, and the like.

Examples of the alkoxy group having 1 to 10 carbon atoms as the substituent include a methoxy group, an ethoxy group, and the like.

As the alicyclic group having 1 to 10 carbon atoms as the substituent, for example, an alicyclic group having 3 to 20 carbon atoms represented by R ^a can be used having 1 to 10 carbon atoms.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ^a include phenyl group, tolyl group, xylyl group, naphthyl group, and anthryl group. Among these, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group and a naphthyl group are more preferable.

As a substituent which the said aryl group may have, a C1-C5 alkyl group, a C1-C5 alkoxy group, a halogen atom, etc. are mentioned, for example.

Examples of the alkyl group having 1 to 5 carbon atoms as the substituent include a methyl group, an ethyl group, and the like.

Examples of the alkoxy group having 1 to 5 carbon atoms as the substituent include a methoxy group, an ethoxy group, and the like.

Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As a compound containing an oxime sulfonate group represented by the above formula (5), an oxime sulfonate compound represented by the following formulas (5-1) and (5-2) is preferable.

In the formulas (5-1) and (5-2), R ^a is synonymous with the formula (5). X is a C1-C5 alkyl group, a C1-C5 alkoxy group, or a halogen atom. m is an integer from 0 to 3. When m is 2 or 3, a plurality of Xs may be the same or different.

As the alkyl group having 1 to 5 carbon atoms represented by X, an alkoxy group having 1 to 5 carbon atoms and a halogen atom, for example, groups similar to the respective groups exemplified as the above substituents can be applied. Of these, a linear or branched alkyl group having 1 to 4 carbon atoms is preferable as the alkyl group, a straight chain or branched alkoxy group having 1 to 4 carbon atoms is preferable as the alkoxy group, and a chlorine atom or fluorine as the halogen atom. Atoms are preferred. In addition, m or 0 is preferable. In particular, in the formula (5-1), a compound in which m is 1, X is a methyl group, and the substitution position of X is an ortho position is preferable.

As the oxime sulfonate compound represented by the above formula (5), for example, the following formulas (5-1-i) to (5-1-iv), and (5-2-i) and (5-2- and compounds represented by ii).

Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (campasulfonyloxy) succinimide, and N- (4-methylphenylsulfonyloxy) succinimide , N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) naphthyldicarboxyimide (trifluoromethanesulfonic acid-1,8-naphthalimide ), N- (campasulfonyloxy) naphthyldicarboxylimide, N- (4-methylphenylsulfonyloxy) naphthyldicarboxylimide, N- (phenylsulfonyloxy) naphthyldicarboxylimide, N -(2-trifluoromethylphenylsulfonyloxy) naphthyldicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyldicarboxylimide, N- (pentafluoroethylsulfonyloxy) naph Tildicarboxylimide, N- (heptafluoropropylsulfonyloxy) naphthyldicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyldicarboxylimide, N- (ethylsulfonyloxy) Naphthyldicarboxylimide, N- (propylsulfonyloxy) naphthyldicarboxylimide, N- (butylsulfonyloxy) naphthyldicarboxylimide, N- (pentylsulfonyloxy) naphthyldicarboxyl Mead, N- (hexylsulfonyloxy) naphthyldicarboxylimide, N- (heptylsulfonyloxy) naphthyldicarboxylimide, N- (octylsulfonyloxy) naphthyldicarboxylimide, N- ( And nonylsulfonyloxy) naphthyl dicarboxyimide.

As the quinonediazide compound, for example, a phenolic compound or an alcoholic compound (hereinafter also referred to as "mother nucleus") and 1,2-naphthoquinonediazide sulfonic acid halide or 1,2-naphthoquinonediazide sulfonic acid amide Condensate of can be used.

Examples of the parent nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other parent nuclei other than the parent nucleus. have.

As a specific example of the said nucleus, for example

As trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, etc .;

As tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxy Benzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc .;

As pentahydroxybenzophenone, 2,3,4,2 ', 6'-pentahydroxybenzophenone, etc .;

As hexahydroxybenzophenone, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone, etc .;

(Polyhydroxyphenyl) alkanes, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris ( p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris ( 2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] Bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6, 7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavane and the like;

As other parent nuclei, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1 -Methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydrate And hydroxybenzene.

Among these, as the nucleus, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris (p-hydroxyphenyl) ethane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferred.

As said 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-naphtho Quinoniazide-5-sulfonic acid chloride is more preferred, and 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferred.

As the 1,2-naphthoquinone diazide sulfonic acid amide, 2,3,4-triaminobenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid amide is preferable.

In the condensation reaction of the phenolic compound or alcoholic compound (parent nucleus) with 1,2-naphthoquinone diazide sulfonic acid halide, preferably 30 mol% or more and 85 mol% with respect to the number of OH groups in the phenolic compound or alcoholic compound Hereinafter, more preferably, it is possible to use 1,2-naphthoquinone diazide sulfonic acid halide equivalent to 50 mol% or more and 70 mol% or less. In addition, the said condensation reaction can be performed by a well-known method.

[G3] The content of the acid generator is preferably 5 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, more preferably 20 parts by mass or more and 40 parts by mass with respect to 100 parts by mass of the polymer [A3]. Part or less is more preferable. When the content of the acid generator is within the above range, the difference in solubility between the irradiated portion and the unradiated portion of the alkali aqueous solution serving as a developer is large, and as a result, the patterning performance becomes good, and at the same time, the chemical resistance of the resulting cured film It also becomes good.

<[H] solvent>

The [H] solvent dissolves the [A3] polymer, the [G] acid generator, and optional components contained as necessary, and those that do not react with each component are used. Further, the [H] solvent may be used alone or in combination of two or more.

Examples of the [H] solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, and hydrocarbon solvents.

As said alcohol solvent, for example

As a mono alcohol solvent, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec -Pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol , 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec -Heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, etc .;

As a polyhydric alcohol solvent, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2 , 4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, etc .;

As a polyalcohol partial ether-based solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2- Ethyl butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and the like.

Examples of the ether-based solvent include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, and the like. Can be lifted.

Examples of the ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, and ethyl-n -Butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, And acetonyl acetone, acetophenone, and the like.

Examples of the amide solvents include N, N'-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, and N-methylacetate Amide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, and the like.

Examples of the ester solvent include methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate , Methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether acetate , Diethylene glycol monoethyl ether acetate, diethylene glycol monoacetate-n-propyl ether, diethylene glycol monoacetate-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate acetate, propylene glycol monopropyl acetate Ether, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxy triglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, di oxalate And ethyl, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate and the like.

As the hydrocarbon-based solvent, for example

As an aliphatic hydrocarbon-based solvent, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, Methyl cyclohexane, etc .;

As aromatic hydrocarbon solvent, benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di- and i-propylbenzene, n-amylnaphthalene, and the like.

In addition, the [H] solvent may contain a high boiling point solvent such as caproic acid, caprylic acid, ethylene carbonate, or propylene carbonate together with the solvent.

<Other optional ingredients>

Examples of other optional components that the positive radiation-sensitive resin composition may contain include, for example, cyclic ether compounds other than the [A3] polymer (hereinafter also referred to as "Compound X"), antioxidants, surfactants, and adhesion aids. And the like. Moreover, the said positive radiation sensitive resin composition can also use each said component individually or in combination of 2 or more types.

[Compound X]

Compound X is a cyclic ether compound other than the [A3] polymer, and specifically, is a compound having a thermally reactive group such as an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure). When the positive radiation-sensitive resin composition contains compound X, the heat resistance, surface hardness, and the like of the resulting cured film can be improved. As the compound X, a compound having two or more oxiranyl groups or oxetanyl groups in the molecule is preferable.

As the compound X having two or more oxiranyl groups in the molecule, for example

Bisphenol type diglycidyl ethers, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglyc Cidyl ether, hydrogenated bisphenol AD diglycidyl ether, etc .;

As polyglycidyl ethers of polyhydric alcohols, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol Diglycidyl ether, polypropylene glycol diglycidyl ether, and the like;

Polyglycidyl ethers of polyether polyols obtained by adding one or two or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin;

Phenol novolac-type epoxy resins;

Cresol novolac-type epoxy resins;

Polyphenol type epoxy resins;

Diglycidyl esters of aliphatic long-chain dibasic acids;

Glycidyl esters of higher fatty acids;

Aliphatic polyglycidyl ethers;

And epoxidized soybean oil and epoxidized linseed oil.

As a commercial product of the compound X having two or more oxiranyl groups in the molecule, for example

Examples of bisphenol A-type epoxy resins include Epicoat 1001, Copper 1002, Copper 1003, Copper 1004, Copper 1007, Copper 1009, Copper 1010, Copper 828 (above, manufactured by Japan Epoxy Resin);

As bisphenol F-type epoxy resin, Epicoat 807 (made by Japan Epoxy Resin), etc .;

As a phenol novolak-type epoxy resin, Epicoat 152, Copper 154, Copper 157S65 (above, manufactured by Japan Epoxy Resin), EPPN 201, Copper 202 (above, manufactured by Nippon Kayaku), etc .;

As a cresol novolak-type epoxy resin, EOCN 102, copper 103S, copper 104S, 1020, 1025, 1027 (above, manufactured by Nippon Kayaku), Epicoat 180S75 (made by Japan Epoxy Resin), etc .;

As a polyphenol-type epoxy resin, Epicoat 1032H60, Copper XY-4000 (above, Japan Epoxy Resin), etc .;

As a cyclic aliphatic epoxy resin, CY-175, Copper 177, Copper 179, Araldite CY-182, Copper 192, 184 (above, manufactured by Ciba Specialty Chemicals), ERL-4234, 4299, 4221, 4206 (above, UCC Manufacturing), Showdyne 509 (Showa Denko), Epiclone 200, Copper 400 (above, manufactured by Dainippon Ink), Epicoat 871, Copper 872 (above, manufactured by Japan Epoxy Resin), ED-5661, Copper 5662 ( As above, Cellanise coating production), etc .;

Examples of the aliphatic polyglycidyl ether include epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), epiol TMP (manufactured by Nippon Yushi Co., Ltd.) and the like.

As compound X having two or more oxetanyl groups in the molecule, for example, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, di [1-ethyl- (3-oxeta) Neil) methyl] ether (alias: bis (3-ethyl-3-oxetanylmethyl) ether), 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 '-[1 , 3- (2-methylenyl) propanediylbis (oxymethylene)] bis- (3-ethyloxetane), 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1 , 3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3- Oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene ( 3-ethyl-3-oxetanylmethyl) ether, trimethylolpropanetris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, Xylene bisoxetane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3- Ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipenta Erythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3- Ethyl-3-oxetanylmethyl) ether, caprolactone modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanyl Methyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis ( 3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) And ethers.

Among these, as compound X having two or more oxetanyl groups in the molecule, di [1-ethyl- (3-oxetanyl) methyl] ether, 1,4-bis [(3-ethyl-3-oxetanylme Methoxy) methyl] benzene is preferred.

The content of the compound X is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 1 part by mass or more and 50 parts by mass or less, and more preferably 1 part by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the polymer [A3]. desirable. When the content of compound X is within the above range, sensitivity, heat resistance, and the like can be improved.

[Antioxidants]

Antioxidants are components that can decompose radicals generated by exposure or heating, or peroxides produced by oxidation, to prevent the antipyretic bonds of polymer molecules. As a result, the resulting cured film is prevented from deteriorating oxidation over time, for example, it is possible to suppress a change in the film thickness of the cured film.

Examples of the antioxidants include compounds having a hindered phenol structure, compounds having a hindered amine structure, compounds having an alkylphosphite structure, compounds having a thioether structure, and the like. Among them, a compound having a hindered phenol structure is preferable as the antioxidant.

Examples of the compound having the hindered phenol structure include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4 -Hydroxybenzyl) benzene, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 3,3 ', 3' , 5 ', 5'-hexa-tert-butyl-a, a', a '-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate , Hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy-2 , 6-Xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6 -Bis (octylthio) -1,3,5-triazine-2-ylamine) phenol, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4 -Hydroxybenzyl) benzene, 2,6-di-t-butyl-4-cresol, and the like.

As a commercial item of the compound having the hindered phenol structure, for example, Adekastab AO-20, copper AO-30, copper AO-40, copper AO-50, copper AO-60, copper AO-70, copper AO- 80, copper AO-330 (above, manufactured by ADEKA), sumilizer GM, copper GS, copper MDP-S, copper BBM-S, copper WX-R, copper GA-80 (above, manufactured by Sumitomo Chemicals), IRGANOX 1010 , East 1035, East 1076, East 1098, East 1135, East 1330, East 1726, East 1425WL, East 1520L, East 245, East 259, East 3114, East 565, IRGAMOD 295 (above, manufactured by BASF), Yoshinox BHT, Copper BB, copper 2246G, copper 425, copper 250, copper 930, copper SS, copper TT, copper 917, copper 314 (above, manufactured by API Corporation).

Among them, as a compound having a hindered phenol structure, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl- 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,6-di-t-butyl-4-cresol is more preferable.

The content of the antioxidant is preferably 0.001 parts by mass or more and 5 parts by mass or less, more preferably 0.01 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the polymer [A3].

[Surfactants]

The surfactant is a component that improves the film-forming properties of the positive radiation-sensitive resin composition. Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, and other surfactants.

As the fluorine-based surfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group on at least one of the terminal, main and side chains is preferable, for example, 1,1,2,2-tetrafluoro- n-octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycoldi (1 , 1,2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1 , 1,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, perfluoro-n- Sodium dodecanesulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n -Dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkyl phosphate, sodium fluoroalkyl carboxylate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkyl Betaine, other fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethanols, perfluoroalkyl alkoxylates, fluoroalkyl carboxylic acids, and the like.

As commercially available products of the fluorine-based surfactant, for example, BM-1000, BM-1100 (above, manufactured by BM CHEMIE), Megaface F142D, Copper F172, Copper F173, Copper F183, Copper F178, Copper F191, Copper F471, Copper F476 (Above, manufactured by Dani Nippon Ink Chemical Co., Ltd.), Fluorad FC-170C, Dong-171, Dong-430, Dong-431 (above, manufactured by Sumitomo 3M), Sufflon S-112, Dong-113, Dong- 131, copper-141, copper-145, copper-382, suplon SC-101, copper-102, copper-103, copper-104, copper-105, copper-106 (above, manufactured by Asahi Glass), F-top EF301 , Copper 303, Copper 352 (above, manufactured by Shin-Akita Kasei), Pactant FT-100, Copper-110, Copper-140A, Copper-150, Copper-250, Copper-251, Copper-300, Copper-310, Copper -400S, FTX-218, copper-251 (above, manufactured by Neos), and the like.

Commercially available products of the silicone surfactants include, for example, Toray Silicone DC3PA, Copper DC7PA, Copper SH11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH-190, Copper SH-193, Copper SZ-6032, Copper SF -8428, Copper DC-57, Copper DC-190 (above, manufactured by Toray Dow Corning and Silicon), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, GE Toshiba Silicon Co., Ltd., organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.) and the like.

Examples of the other surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene-n-octylphenyl ether and polyoxyethylene-n-nonylphenyl ether; And nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate.

Examples of commercially available products of the other surfactants include (meth) acrylic acid copolymer polyflow No.57, copper No.95 (above, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

As content of the said surfactant, 0.01 mass part or more and 3 mass parts or less are preferable with respect to 100 mass parts of [A3] polymers, and 0.05 mass part or more and 1 mass part or less are more preferable. When the content of the surfactant is within the above range, film formability can be effectively improved.

[Adhesive Aid]

The adhesion aid is a component that improves the adhesion between the resulting cured film and the substrate. As the adhesion aid, a functional silane coupling agent having a reactive functional group such as a carboxyl group, methacryloyl group, vinyl group, isocyanate group, or oxiranyl group is preferable.

Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ -Glycidoxypropyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, and the like.

As content of the said adhesive auxiliary agent, 0.01 mass part or more and 20 mass parts or less are preferable with respect to 100 mass parts of [A3] polymers, and 0.1 mass part or more and 15 mass parts or less are more preferable. When the usage-amount of an adhesive aid exceeds 20 mass parts, there exists a tendency for a development residue to arise easily.

<Production method of positive radiation sensitive resin composition>

In the positive radiation sensitive resin composition of the present invention, optional components such as [A3] polymer, [G] acid generator, and [H] solvent, antioxidant, surfactant, and adhesion aid are mixed in a predetermined ratio, if necessary. Can be produced. It is preferable to filter the produced positive radiation sensitive resin composition with a filter having a pore size of about 0.5 µm.

<Method of forming a cured film (3)>

The method (3) of forming the cured film of the present invention,

(1) a step of forming a coating film on the substrate using the positive radiation-sensitive resin composition,

(2) a step of irradiating a portion of the coating film with radiation,

(3) a process of developing the coated film irradiated with the radiation, and

(4) Process of heating the developed coating film

Have

Since the positive radiation-sensitive resin composition has the above-described properties, according to the method (3) of forming the cured film of the present invention, it has good surface hardness, develop adhesion, heat resistance, chemical resistance, transmittance, and relative dielectric constant. A cured film capable of satisfactorily satisfying general characteristics can also be formed. Hereinafter, each process is explained in full detail.

[Process (C1)]

In this step, a coating film is formed on the substrate using the positive radiation-sensitive resin composition. Specifically, a solution of the positive radiation-sensitive resin composition is applied to the surface of the substrate, and preferably pre-baking, the solvent is removed to form a coating film of the radiation-sensitive resin composition. Examples of the substrate include glass substrates, silicon wafers, plastic substrates, and substrates on which various metal thin films are formed. As said plastic substrate, the resin substrate containing plastics, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyether sulfone, polycarbonate, polyimide, is mentioned, for example.

As the coating method, suitable methods such as a spray method, a roll coating method, a rotation coating method (spin coating method), a slit die coating method, a bar coating method, and an inkjet method can be adopted, for example. Of these, spin coating, bar coating, and slit die coating are preferred as the coating method. The conditions of the pre-baking vary depending on the type of each component, the use ratio, and the like, but can be, for example, from 60 ° C to 130 ° C for about 30 seconds to 10 minutes. The film thickness of the formed coating film is preferably 0.1 µm to 8 µm, more preferably 0.1 µm to 6 µm, and even more preferably 0.1 µm to 4 µm as a value after pre-baking.

[Process (C2)]

In this process, a part of the coating film is irradiated with radiation. Specifically, radiation is irradiated to the coating film formed in step (C1) through a mask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle rays.

Examples of the ultraviolet rays include g-rays (wavelength 436 nm), i-rays (wavelength 365 nm), and the like. Examples of the far ultraviolet rays include KrF excimer laser light and the like. As X-rays, synchrotron radiation etc. are mentioned, for example. As a charged particle beam, an electron beam etc. are mentioned, for example. Among these radiations, ultraviolet rays are preferred, and among the ultraviolet rays, radiations including g rays, h rays and / or i rays are more preferable. Examples of radiation exposure dose, 0.1J / m ² to 10,000J / m ² is preferred.

[Process (C3)]

In this step, the coated film irradiated with the radiation is developed. Specifically, in the step (C2), the coated film irradiated with radiation is developed with a developer to remove the irradiated portion of the radiation. Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethyl Amines, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0 And an aqueous solution of an alkali (basic compound) such as 7-undecene and 1,5-diazabicyclo [4,3,0] -5-nonane. Further, an aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the aqueous solution of the alkali, or an aqueous alkali solution containing a small amount of various organic solvents for dissolving the positive radiation-sensitive resin composition may be used as the developer. have.

As the developing method, suitable methods such as a liquid accumulating method, a dipping method, a rocking dipping method, and a shower method can be adopted, for example. The development time varies depending on the composition of the positive radiation sensitive resin composition, but can be, for example, 30 seconds to 120 seconds. Further, after the development process, the patterned coating film is subjected to a rinsing treatment by washing with running water, followed by irradiation with high pressure mercury lamp or the like (post exposure) to decompose the acid generator remaining in the coating film. It is preferable to do. As the exposure amount in the subsequent exposure, 2,000 J / m ² to 5,000 J / m ² is preferable.

[Process (C4)]

In this step, the developed coating film is heated. Specifically, the coating film is cured by heating and firing (post baking) the coating film using a heating device such as a hot plate or oven for firing the developed film developed in step (C3). The firing temperature in this step is preferably 200 ° C or lower. In addition to the ability to form a fine pattern using radiation-sensitive properties, by firing at such a low temperature, the forming method (3) can be preferably used for forming a cured film such as an interlayer insulating film on a plastic substrate of a flexible display. As the firing temperature, 120 ° C to 180 ° C is more preferable, and 120 ° C to 150 ° C is more preferable. The calcination time varies depending on the type of the heating device, but may be, for example, 5 minutes to 40 minutes when heat treatment is performed on a hot plate, and 30 minutes to 80 minutes when heat treatment is performed in an oven, more preferably Is within 30 minutes when performing heat treatment on a hot plate, and within 60 minutes when performing heat treatment in an oven. In this way, a patterned coating film corresponding to a cured film such as a target interlayer insulating film can be formed on a substrate.

<Curing film (3)>

The cured film 3 of the present invention is formed by, for example, the method (3) for forming the cured film described above, using the above-mentioned positive radiation sensitive resin composition. Since the cured film 3 is formed using the positive radiation-sensitive resin composition, it has good surface hardness and can sufficiently satisfy general characteristics such as developing adhesion, heat resistance, chemical resistance, transmittance, and relative dielectric constant. have.

<Semiconductor element>

The semiconductor element of the present invention is provided with the cured film 3. Since the semiconductor element is provided with a cured film 3 formed from the positive radiation-sensitive resin composition, it is possible to improve the integration density and recording density of the circuit, and to electronic devices such as display elements, LEDs, and solar cells. It can be preferably used.

<Display element>

The display element of this invention is equipped with the said semiconductor element. This semiconductor element has a cured film 3 formed from the positive radiation-sensitive resin composition. Accordingly, the general characteristics required in practical terms as a display element are satisfied. As said display element, a liquid crystal display element etc. are mentioned, for example. In the liquid crystal display element, for example, two TFT array substrates on which a liquid crystal alignment film is formed on the surface are disposed to face each other on the liquid crystal alignment film side through a sealing agent provided on the periphery of the TFT array substrate, and between these two TFT array substrates The liquid crystal is charged. The TFT array substrate has wirings arranged in layers, and the wirings are insulated by the cured film such as an interlayer insulating film.

[Example]

Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples. The measurement method of each physical property value is shown below.

[Weight average molecular weight (Mw) and number average molecular weight (Mn)]

Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions. In addition, the molecular weight distribution (Mw / Mn) was calculated from the obtained Mw and Mn.

Device: GPC-101 (manufactured by Showa Denko)

GPC column: combines GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (manufactured by Shimadzu GLC)

Mobile phase: Tetrahydrofuran

Column temperature: 40 ° C

Flow rate: 1.0 mL / min

Sample concentration: 1.0% by mass

Sample injection volume: 100 μL

Detector: Differential refractometer

Standard material: monodisperse polystyrene

<Synthesis of [A1] polymer and [A2] polymer>

The monomer compounds used in the synthesis of the polymers of the respective examples and comparative examples are shown below.

[Monomer compound providing structural unit (I)]

Monomer compounds (1-1) to (1-10) represented by the following formulas (1-1) to (1-10)

[Monomer compound providing structural unit (II-1), structural unit (II-2)]

Monomer compounds (2-1) to (2-7) represented by the following formulas (2-1) to (2-7)

[Monomer compound providing structural unit (III)]

(3-1): Methacrylic acid p-hydroxyphenol (4-hydroxyphenyl methacrylate)

(3-2): Hydroxyethyl methacrylate (2-hydroxyethyl methacrylate)

(3-3): α-methyl-p-hydroxystyrene

[Monomer compound providing structural unit (IV)]

(4-1): methacrylic acid

(4-2): Styrene

(4-3): methyl methacrylate

(4-4): N-cyclohexylmaleimide

(4-5): Tetrahydrofurfuryl methacrylate

(4-6): Tricyclo methacrylate [5.2.1.0 ^2,6 ] decan-8-yl

[Synthesis Example 1] (Synthesis of polymer (A-1))

To a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were added. Subsequently, 60 parts by mass of the monomer compound (1-1) providing the structural unit (I), 18 parts by mass of the monomer compound (2-1) providing the structural unit (II-1), and the structural unit (IV) A polymer solution containing polymer (A-1) by adding 22 parts by mass of monomer compound (4-2), purging with nitrogen and slowly stirring, raising the temperature of the solution to 70 ° C, and maintaining the temperature for 4 hours to polymerize. Got The polymer solution had a solid content concentration of 30.4%, a polymer (A-1) had an Mw of 8,000, and a molecular weight distribution (Mw / Mn) of 2.3.

[Synthesis Examples 2 to 46] (Synthesis of polymers (A-2) to (A-42) and (a-1) to (a-4))

Polymers (A-2) to (A-42) and (a-1) to (a-4) were synthesized in the same manner as in Synthesis Example 1, except that the monomer compounds of the types and compounding amounts shown in Table 1 below were used. Did. The solid content concentration of each obtained polymer solution, and Mw and Mw / Mn of each polymer were equivalent to the values of the polymer (A-1). In addition, the blank in Table 1 indicates that the corresponding monomer compound was not blended.

<Production of the resin composition for forming a cured film (1)>

[Example 1]

[A1] To a polymer solution containing 100 parts by mass (solid content) of (A-1) as a polymer, after adding diethylene glycol methyl ethyl ether as a solvent so that the solid content concentration becomes 30 mass%, a membrane filter having a pore diameter of 0.2 µm The resin composition for cured film formation (1) was produced by filtration with.

[Example 2 and Comparative Example 1]

The resin composition (1) for forming each cured film was produced in the same manner as in Example 1, except that the component [A] was used as the type and compounding amount shown in Table 2. In addition, "-" in Table 2 indicates that the corresponding component was not blended, or that evaluation described later was not performed.

<Production of the negative radiation sensitive resin composition (2)>

The [B] polymerizable compound, [C] radiation-sensitive polymerization initiator and [D] antioxidant used in the production of each negative-type radiation-sensitive resin composition (2) are shown below.

[[B] polymerizable compound]

B-1: Dipentaerythritol hexaacrylate

B-2: Mixture of polyfunctional acrylate compounds (KAYARAD DPHA-40H, manufactured by Nippon Kayaku)

B-3: 1,9-nonanediol diacrylate

B-4: ω-carboxy-polycaprolactone monoacrylate (Aronics M-5300 (manufactured by Toagosei)

B-5: Succinic acid-modified pentaerythritol triacrylate

[[C] radiation-sensitive polymerization initiator]

C-1: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02, Ciba Specialty · Chemicals)

C-2: 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (Irgacure OXE01, manufactured by Ciba Specialty Chemicals)

C-3: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907, manufactured by Ciba Specialty Chemicals)

C-4: 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (Irgacure 379, Ciba Specialty Chemicals) Produce)

[[D] Antioxidants]

D-1: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], (Adekast AO-60, manufactured by ADEKA)

D-2: Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate (adekastab AO-20, manufactured by ADEKA)

[Example 3]

[A2] A polymer solution containing 100 parts by mass (A-1) (solid content) as a polymer, [B] 50 parts by mass (B-1) as a polymerizable compound, and [C] (C) as a radiation-sensitive polymerization initiator -1) After mixing 5 parts by mass and further adding diethylene glycol methyl ethyl ether as a solvent so that the solid content concentration becomes 30% by mass, and then filtering with a membrane filter having a pore diameter of 0.2 µm, a negative radiation sensitive resin composition (2 ) Was prepared.

[Examples 4 to 50 and Comparative Examples 2 to 5]

It was operated in the same manner as in Example 3 except that the components [A], [B] the polymerizable compound, [C] the radiation-sensitive polymerization initiator, and [D] the antioxidant were the types and compounding amounts shown in Table 2, and each negative was A type radiation-sensitive resin composition (2) was prepared. In addition, "-" in Table 2 indicates that the corresponding component was not blended.

<Evaluation>

Each of the prepared resin compositions for forming a cured film (1) and (2) was evaluated according to the following evaluation method. Table 2 shows the evaluation results.

[Storage stability]

The resin composition for forming each cured film was left in an oven at 40 ° C. for one week, and the viscosity before and after heating was measured to obtain a rate of change in viscosity (%), and was used as an indicator of storage stability. Viscosity change rate, A: viscosity change rate of less than 5%, B: viscosity change rate of 5% or more and less than 10%, C: viscosity change rate of 10% or more and less than 15%, D: viscosity change rate of 15% or more, and storage for A or B The stability was evaluated as good, and in the case of C or D, it was evaluated as poor. The viscosity was measured at 25 ° C using an E-type viscometer (VISCONIC ELD. R, manufactured by Toki Sangyo).

[Sensitivity]

After the resin composition for forming each cured film was coated on a silicon substrate using a spinner, pre-baking was performed on a hot plate at 90 ° C for 2 minutes to form a coating film having a thickness of 3.0 µm. The obtained coating film was irradiated with a predetermined amount of ultraviolet light by a mercury lamp through a pattern mask having a line-and-space pattern having a width of 10 µm. Subsequently, a developing solution containing a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used for developing for 60 seconds at 25 ° C., followed by washing with running water for 1 minute with ultrapure water. At this time, the minimum ultraviolet irradiation amount capable of forming a line-and-space pattern having a width of 10 µm was measured. If the measurement is 700J / m ² is less than, and the sensitivity can be evaluated as good as, or more defective 700J / m ^2.

[Phenomenon adhesion]

After applying the resin composition for forming each cured film on a silicon substrate using a spinner, pre-baking was performed on a hot plate at 90 ° C for 2 minutes to form a coating film having a thickness of 3.0 µm. The obtained coating film was irradiated with ultraviolet rays of 1,000 J / m ² by a mercury lamp through a pattern mask having a line and space pattern having a width of 10 μm. Subsequently, using a developing solution containing a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development was performed at 25 ° C for 60 seconds, followed by washing with running water with ultrapure water for 1 minute. Then, the presence or absence of peeling of the line-and-space pattern having a width of 10 µm was observed under a microscope to obtain developing adhesion. At this time, depending on the degree of peeling, A: no peeling, B: slightly peeling, C: partially peeling, D: full face peeling, and in the case of A or B, the developing adhesiveness is good, in the case of C or D It was evaluated as bad.

[Chemical resistance]

After the resin composition for forming each cured film was coated on a silicon substrate using a spinner, pre-baking was performed on a hot plate at 90 ° C for 2 minutes to form a coating film having a thickness of 3.0 µm. The obtained coating film was irradiated with ultraviolet light so that the integrated irradiation amount was 1,000 J / m ² by a mercury lamp. Subsequently, the silicon substrate was heated on a hot plate at 200 ° C for 30 minutes to measure the film thickness (T1) of the resulting cured film. Then, after immersing the silicon substrate on which the cured film was formed in dimethyl sulfoxide temperature-controlled at 70 ° C. for 20 minutes, the film thickness (t1) of the cured film after immersion was measured, and the film thickness change rate was calculated from the following formula. This was used as an index of chemical resistance.

Film thickness change rate = {(t1-T1) / T1} × 100 (%)

When the absolute value of this value is less than 5%, it can be evaluated that the chemical resistance is good, and when it is 5% or more, it is poor.

[Heat resistance]

After applying the resin composition for forming each cured film on a silicon substrate using a spinner, pre-baking was performed on a hot plate at 90 ° C for 2 minutes to form a coating film having a thickness of 3.0 µm. The obtained coating film was irradiated with ultraviolet light so that the integrated irradiation amount was 1,000 J / m ² by a mercury lamp. Next, this silicon substrate was heated on a hot plate at 200 ° C for 30 minutes to obtain a cured film. The 5% weight loss temperature of the obtained cured film was measured under air using a measuring device (TG / DTA220U, manufactured by SII · Nano Technology), and used as an index of heat resistance. At this time, it can be evaluated that the heat resistance is good when the 5% weight loss temperature is 300 ° C or higher, and the heat resistance is poor when it is less than 300 ° C.

[Transmittance]

After the resin composition for forming each cured film was coated on a glass substrate using a spinner, pre-baking was performed on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet light so that the integrated irradiation amount was 1,000 J / m ² by a mercury lamp. Subsequently, this glass substrate was heated on a hot plate at 200 ° C for 30 minutes to obtain a cured film. The transmittance of the obtained cured film was measured using an ultraviolet visible spectrophotometer (V-630, manufactured by Nippon Bunko). At this time, the case where the transmittance of light having a wavelength of 400 nm is 95% or more can be evaluated as good (good transparency), and the case where it is less than 95% can be evaluated as poor (bad transparency).

[Surface hardness]

After the resin composition for forming each cured film was coated on a silicon substrate using a spinner, pre-baking was performed on a hot plate at 90 ° C for 2 minutes to form a coating film having a thickness of 3.0 µm. The obtained coating film was irradiated with ultraviolet rays so that the integrated irradiation amount was 1,000 J / m ² by a mercury lamp. Subsequently, this silicon substrate was heated on a hot plate at 200 ° C for 30 minutes to obtain a cured film. And the pencil hardness of the cured film was measured by the 8.4.1 pencil scratching test of JIS K-5400-1990 with respect to the substrate on which the cured film was formed, and this was used as an index of surface hardness. When the pencil hardness is 3H or more, it can be evaluated that the surface hardness of the cured film is good (the resin composition for forming a cured film has sufficient curability), and when it is 2H or less, it is poor.

[Relative permittivity]

After applying the resin composition for forming each cured film on the SUS substrate using a spinner, pre-baking was performed on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Cured on the SUS substrate by exposing the coating film to an integrated irradiation amount of 1,000 J / m ² using an exposure machine (MPA-600FA, manufactured by Canon) and heating the exposed substrate at 200 ° C. for 30 minutes in a clean oven. A film was formed. Subsequently, a Pt / Pd electrode pattern was formed on the cured film by a vapor deposition method to prepare a dielectric constant measurement sample. For the substrate having this electrode pattern, the relative dielectric constant was measured by CV method at a frequency of 10 kHz using an electrode (HP16451B, manufactured by Yokogawa Hewlett-Packard) and a flash zone LCR meter (HP4284A, manufactured by Yokogawa-Hewlett-Packard). Was done. At this time, it can be evaluated that the case where the relative dielectric constant is 3.9 or less is good, and the case where it exceeds 3.9 is defective.

As can be seen from the evaluation results in Table 2, the properties of any of the examples were good, whereas those of the comparative examples were poor.

<Synthesis of [A3] polymer>

The monomer compounds used in the synthesis of the polymers of the respective examples and comparative examples are shown below.

[Monomer compound providing structural unit (I)]

Monomer compounds (1-1) to (1-10) represented by the following formulas (1-1) to (1-10)

[Monomer compound providing structural unit (II-3)]

Monomer compounds (2-1) to (2-7) represented by the following formulas (2-1) to (2-7)

[Monomer compound providing structural unit (III)]

(3-1): Methacrylic acid p-hydroxyphenyl (4-hydroxyphenyl methacrylate)

(3-2): Hydroxyethyl methacrylate (2-hydroxyethyl methacrylate)

(3-3): α-methyl-p-hydroxystyrene

[Monomer compound providing structural unit (IV)]

(4-1): methacrylic acid

(4-2): Styrene

(4-3): methyl methacrylate

(4-4): N-cyclohexylmaleimide

(4-5): Tetrahydrofurfuryl methacrylate

(4-6): Tricyclo methacrylate [5.2.1.0 ^2,6 ] decan-8-yl

[Synthesis Example a1] (Synthesis of polymer (A-a1))

To a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were added. Subsequently, 60 parts by mass of the compound (1-1) providing the structural unit (I), 18 parts by mass of the compound (2-1) providing the structural unit (II-3), and a compound providing the structural unit (IV) ( 4-2) 22 parts by mass was added, and the mixture was nitrogen-stirred and stirred slowly, while raising the temperature of the solution to 70 ° C and maintaining the temperature for 4 hours to polymerize to obtain a polymer solution containing the copolymer (A-a1). . The polymer solution had a solid content concentration of 30.4 mass%, a copolymer (A-a1) had an Mw of 8,000, and a molecular weight distribution (Mw / Mn) of 2.3.

[Synthesis Examples a2 to a45] (Synthesis of polymers (A-a2) to (A-a42) and (a-a1) to (a-a3))

Polymers (A-a2) to (A-a42) and (a-a1) to (a-a3) were synthesized in the same manner as in Synthesis Example a1, except that the monomer compounds of the types and amounts shown in Table 3 below were used. Did. The solid content concentration of each obtained polymer solution, and Mw and Mw / Mn of each polymer were equivalent to the values of the polymer (A-a1). In addition, the blank in Table 3 indicates that the corresponding monomer compound was not blended.

<Preparation of positive radiation sensitive resin composition>

The [G] acid generator used in the production of each positive radiation sensitive resin composition is shown below.

[G] acid generator

G-1: trifluoromethanesulfonic acid-1,8-naphthalimide

G-2: 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonedia Condensate of Zid-5-sulfonic acid chloride (2.0 mol)

G-3: Condensate of 1,1,1-tri (p-hydroxyphenyl) ethane and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol)

G-4: the compound represented by the formula (5-1-i)

[Example a1]

[A3] A polymer solution containing 100 parts by mass of (A-a1) as a polymer (solid content), [G] 30 parts by mass of (G-2) as an acid generator, adhesion aid (γ-glycidoxypropyltrimethoxy Silane) 5 parts by weight, 0.5 parts by weight of surfactant (FTX-218, manufactured by Neos), 0.1 parts by weight of antioxidant (manufactured by IRGANOX1010, manufactured by BASF), and diethylene glycol as a solvent [H] so that the solid content concentration is 30% by mass. After further adding methyl ethyl ether, a positive radiation sensitive resin composition was prepared by filtration through a membrane filter having a pore diameter of 0.2 µm.

[Examples a2 to a58 and Comparative Examples a1 to a6]

Each positive-type radiation-sensitive resin composition was prepared by operating in the same manner as in Example a1, except that the polymers [A3] and [G] were used as the types shown in Table 4.

<Evaluation>

Each positive radiation sensitive resin composition thus prepared was evaluated in accordance with the following evaluation method. Table 4 shows the evaluation results.

[Storage stability]

Each positive radiation sensitive resin composition was left in an oven at 40 ° C. for one week, and the viscosity change rate (%) was measured by measuring the viscosity before and after heating to obtain an index of storage stability. Viscosity change rate, A: viscosity change rate of less than 5%, B: viscosity change rate of 5% or more and less than 10%, C: viscosity change rate of 10% or more and less than 15%, D: viscosity change rate of 15% or more, and storage for A or B The stability was evaluated as good, and in the case of C or D, it was evaluated as poor. The viscosity was measured at 25 ° C using an E-type viscometer (VISCONIC ELD. R, manufactured by Toki Sangyo).

[Sensitivity]

Each positive-type radiation-sensitive resin composition was coated on a silicon substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with a predetermined amount of ultraviolet light by a mercury lamp through a pattern mask having a line-and-space pattern having a width of 10 µm. Subsequently, using a developing solution containing a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development was performed at 25 ° C for 60 seconds, followed by washing with running water with ultrapure water for 1 minute. At this time, the minimum ultraviolet irradiation amount capable of forming a line-and-space pattern having a width of 10 µm was measured. If this measurement is 500J / m ² is less than the sensitivity that can be evaluated as good, bad or more 500J / m ^2.

[Phenomenon adhesion]

Each positive-type radiation-sensitive resin composition was coated on a silicon substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays of 500 J / m ² by a mercury lamp through a pattern mask having a line and space pattern having a width of 10 μm. Subsequently, using a developing solution containing a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development was performed at 25 ° C for 60 seconds, followed by washing with running water with ultrapure water for 1 minute. Then, the presence or absence of peeling of the line-and-space pattern having a width of 10 µm was observed under a microscope to obtain developing adhesion. At this time, depending on the presence or absence of peeling, A: no peeling, B: slightly peeling, C: partially peeling, D: full face peeling, and in the case of A or B, the developing adhesiveness is good, in the case of C or D It was evaluated as bad.

[Chemical resistance]

Each positive-type radiation-sensitive resin composition was coated on a silicon substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays so that the integrated irradiation amount was 3,000 J / m ² by a mercury lamp. Subsequently, the silicon substrate was heated on a hot plate at 200 ° C for 30 minutes to measure the film thickness (T1) of the resulting cured film. Then, after immersing the silicon substrate on which the cured film was formed in dimethyl sulfoxide temperature-controlled at 70 ° C. for 20 minutes, the film thickness (t1) of the cured film after immersion was measured, and the film thickness change rate was calculated from the following calculation formula. It was set as an index of chemical resistance.

Film thickness change rate = {(t1-T1) / T1} × 100 (%)

When the absolute value of this value is less than 5%, it can be evaluated that the chemical resistance is good, and when it is 5% or more, it is poor.

[Heat resistance]

Each positive-type radiation-sensitive resin composition was coated on a silicon substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays so that the integrated irradiation amount was 3,000 J / m ² by a mercury lamp. Next, this silicon substrate was heated on a hot plate at 200 ° C for 30 minutes to obtain a cured film. The 5% weight loss temperature of the obtained cured film was measured under air using a measuring device (TG / DTA220U, manufactured by SII · Nano Technology), and used as an index of heat resistance. At this time, it can be evaluated that the heat resistance is good when the 5% weight loss temperature is 300 ° C or higher, and the heat resistance is poor when it is less than 300 ° C.

[Transmittance]

Each positive-type radiation-sensitive resin composition was coated on a glass substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays so that the integrated irradiation amount was 3,000 J / m ² by a mercury lamp. Subsequently, this glass substrate was heated on a hot plate at 200 ° C for 30 minutes to obtain a cured film. The transmittance of the obtained cured film was measured using an ultraviolet visible spectrophotometer (V-630, manufactured by Nippon Bunko). At this time, the case where the transmittance of light having a wavelength of 400 nm is 95% or more can be evaluated as good (good transparency), and the case where it is less than 95% can be evaluated as poor (bad transparency).

[Surface hardness]

Each positive-type radiation-sensitive resin composition was coated on a silicon substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays so that the integrated irradiation amount was 3,000 J / m ² by a mercury lamp. Subsequently, the silicon substrate was heated on a hot plate at 200 ° C for 30 minutes to obtain a cured film. And the pencil hardness of the cured film was measured about the board | substrate in which the cured film was formed by the 8.4.1 pencil scratching test of JIS K-5400-1990, and this was used as an index of surface hardness. When the pencil hardness is 3H or more, it can be evaluated that the surface hardness of the cured film is good (positive radiation-sensitive resin composition has sufficient curability), and when it is 2H or less, it is poor.

[Relative permittivity]

After applying each positive-type radiation-sensitive resin composition on the SUS substrate using a spinner, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 3.0 μm. Cured on the SUS substrate by exposing the coating film to an integrated irradiation amount of 9,000 J / m ² using an exposure machine (MPA-600FA, manufactured by Canon) and heating the exposed substrate at 200 ° C. for 30 minutes in a clean oven. A film was formed. Subsequently, a Pt / Pd electrode pattern was formed on the cured film by a vapor deposition method to prepare a dielectric constant measurement sample. For the substrate having this electrode pattern, the relative dielectric constant was measured by CV method at a frequency of 10 kHz using an electrode (HP16451B, manufactured by Yokogawa Hewlett-Packard) and a flash zone LCR meter (HP4284A, manufactured by Yokogawa-Hewlett-Packard). Was done. At this time, it can be evaluated that the case where the relative dielectric constant is 3.9 or less is good, and the case where it exceeds 3.9 is defective.

The present invention has excellent surface hardness, and at the same time, it is possible to form a cured film capable of satisfactorily satisfying general characteristics such as sensitivity, developing adhesion, chemical resistance, heat resistance, transmittance and relative dielectric constant, and for forming a cured film having excellent storage stability. A thermosetting resin composition, a negative-type radiation-sensitive resin composition, and a positive-type radiation-sensitive resin composition can be provided. Therefore, the thermosetting resin composition for forming a cured film, a negative radiation-sensitive resin composition, a positive radiation-sensitive resin composition, a thermosetting resin composition for forming the cured film, a negative radiation-sensitive resin composition, a positive radiation-sensitive resin The cured film formed from the composition, a semiconductor element and a display element, and the method for forming the cured film can be preferably used in manufacturing processes such as flexible displays and other electronic devices.

Claims (17)

[A2] A structural unit (I) containing at least one member selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2), and a structure comprising a crosslinkable group (a2) Polymer having unit (II-2),
[B] a polymerizable compound having an ethylenically unsaturated bond, and
[C] radiation-sensitive polymerization initiator
Containing,
[C] A radiation-sensitive resin composition in which the radiation-sensitive polymerization initiator is a component that generates an active species capable of initiating polymerization of the polymerizable compound [B].

In Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms, provided that at least one of R ¹ and R ² is 1 to 4 carbon atoms. Is a fluorinated alkyl group,
In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms, provided that at least one of R ³ and R ⁴ is a halogen atom Or a fluorinated alkyl group having 1 to 4 carbon atoms) The negative radiation-sensitive resin composition according to claim 1, wherein the crosslinkable group (a2) is at least one selected from the group consisting of an oxiranyl group, an oxetanyl group, a cyclic carbonate group, and a (meth) acryloyl group. The negative type according to claim 1 or 2, wherein the radiation-sensitive polymerization initiator [C] is an oxime ester compound, and the content of the oxime ester compound is 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the [A2] polymer. Radiation-sensitive resin composition. The negative radiation sensitive resin composition according to claim 1 or 2, further comprising an antioxidant [D]. The negative-type radiation-sensitive resin composition according to claim 1 or 2, wherein the polymerizable compound has at least one carboxyl group in the same molecule. [A3] A structural unit (I) containing at least one member selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2), and a cyclic ether structure or a cyclic carbonate structure A polymer having a structural unit (II-3), and
[G] acid generator
Containing,
[G] A positive radiation-sensitive resin composition in which the acid generator is an acid generator containing a quinonediazide compound.

In Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms, provided that at least one of R ¹ and R ² is 1 to 4 carbon atoms. Is a fluorinated alkyl group,
In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms, provided that at least one of R ³ and R ⁴ is a halogen atom Or a fluorinated alkyl group having 1 to 4 carbon atoms) The positive radiation-sensitive resin composition according to claim 6, wherein the structural unit (II-3) includes a cyclic ether structure, and the cyclic ether structure is at least one of an oxirane structure and an oxetane structure. (1) [A1] a structural unit (I) and a crosslinkable group (a1) comprising at least one member selected from the group consisting of groups represented by the following formula (1) and groups represented by the following formula (2): A step of forming a coating film on a substrate using a thermosetting resin composition for forming a cured film containing a polymer having a structural unit (II-1) containing the same, and
(2) Process of heating the coating film
A method of forming a cured film having a.

In Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms, provided that at least one of R ¹ and R ² is 1 to 4 carbon atoms. Is a fluorinated alkyl group,
In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms, provided that at least one of R ³ and R ⁴ is a halogen atom Or a fluorinated alkyl group having 1 to 4 carbon atoms) The method for forming a cured film according to claim 8, wherein the crosslinkable group (a1) is at least one selected from the group consisting of an oxiranyl group and an oxetanyl group. (1) The process of forming a coating film on a board | substrate using the negative radiation sensitive resin composition of Claim 1 or 2, or the positive radiation sensitive resin composition of Claim 6 or 7,
(2) a step of irradiating a portion of the coating film with radiation,
(3) a process of developing the coated film irradiated with the radiation, and
(4) Process of heating the developed coating film
A method of forming a cured film having a. [A1] A structural unit (I) containing at least one member selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2), and a structure comprising a crosslinkable group (a1) A cured film formed from a thermosetting resin composition for forming a cured film containing a polymer having a unit (II-1).

In Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms, provided that at least one of R ¹ and R ² is 1 to 4 carbon atoms. Is a fluorinated alkyl group,
In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms, provided that at least one of R ³ and R ⁴ is a halogen atom Or a fluorinated alkyl group having 1 to 4 carbon atoms) The cured film according to claim 11, wherein the crosslinkable group (a1) is at least one selected from the group consisting of an oxiranyl group and an oxetanyl group. A cured film formed from the negative radiation-sensitive resin composition according to claim 1 or 2, or from the positive radiation-sensitive resin composition according to claim 6 or 7. A semiconductor device comprising the cured film according to claim 11 or 12. A semiconductor device comprising the cured film according to claim 13. A display element comprising the semiconductor element according to claim 14. A display element comprising the semiconductor element according to claim 15.