KR20210062068A - Ethylene unsaturated resin composition and photosensitive resin composition - Google Patents

Abstract

There is provided a resin composition having a small amount of residual polymerization inhibitor and high in transparency, heat yellowing resistance, and fine particle dispersibility including a colorant. The ethylenically unsaturated resin composition of the present invention contains an ethylenically unsaturated resin (A), a carbon cluster (c), and a solvent (B), and the carbon cluster (c) is at least one of fullerene and a soot-like substance. , The content thereof is 0.00001 to 10 parts by mass per 100 parts by mass of the ethylenically unsaturated resin (A).

Description

Ethylene unsaturated resin composition and photosensitive resin composition

The present invention relates to an ethylenically unsaturated resin composition and a photosensitive resin composition.

This application claims priority based on Japanese Patent Application No. 2018-222730 for which it applied to Japan on November 28, 2018, and uses the content here.

Acrylic resins are used in various fields because of their excellent transparency, weather resistance, and mechanical properties with a balance. Recently, by using a photosensitive resin composition containing a resin into which an ethylenically unsaturated group is introduced, it has been disclosed to form a black column spacer or the like as a display member through coating, exposure, and development processes (Patent Document 1). . As a method of introducing an ethylenically unsaturated group into a resin, a method of reacting a resin containing an epoxy group and an ethylenically unsaturated compound containing a carboxyl group in the presence of a polymerization inhibitor and a catalyst is disclosed.

International Publication No. 2017/204079

In recent years, performances such as high heat resistance and yellowing resistance and dispersion of design materials have been important in acrylic resins due to the improvement of performance required for displays. Therefore, it is desired to reduce the amount of the polymerization inhibitor required for storage or the amount of the inhibitor and the residual catalyst.

The present invention has been made in order to solve the above problems, and even if a small amount of carbon clusters is used, the synthesis is efficiently performed to obtain an ethylenically unsaturated resin composition. That is, the present invention aims to provide an ethylenically unsaturated resin composition containing a small amount of carbon clusters, and has high heat yellowing resistance, high dispersibility of fine particles containing a colorant, and photosensitive resists having excellent pattern shapes. It aims to provide a resin composition.

That is, the present invention is represented by the following [1] to [13].

[1] ethylenically unsaturated resin (A),

Carbon cluster (c) and,

Solvent (B)

Contains,

The carbon cluster (c) is at least one of fullerene and a soot-like substance, and the content thereof is 0.00001 to 10 parts by mass per 100 parts by mass of the ethylenically unsaturated resin (A).

[2] The ethylenically unsaturated resin (A) is a polybasic acid anhydride to the epoxy group containing the epoxy group (P1) by ring-opening addition to the ethylenically unsaturated compound (m-2) containing a carboxyl group, and to the hydroxy group generated by the ring opening of the epoxy group. It is an ethylenically unsaturated resin (A1) obtained by adding (d),

The epoxy group-containing copolymer (P1) is

Constituent units derived from epoxy group-containing (meth)acrylate (m-1) and

At least 1 selected from the group consisting of a structural unit derived from a polymerizable monomer (m-3) having a C10 to C20 interchangeable hydrocarbon group and a structural unit derived from a polymerizable monomer (m-4) represented by the following formula (1) Bell

The ethylenically unsaturated resin composition according to [1], which is a copolymer containing.

(X and X'in formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R1 and R2 are each independently a hydrogen atom, a carboxyl group, or a carbon number which may have a substituent. It is a hydrocarbon group of 1 to 20, and may have a cyclic structure connecting R1 and R2.)

[3] The ethylenically unsaturated resin (A) is an unsaturated group-containing ethylenically unsaturated resin having a hydroxy group formed by ring-opening addition of a carboxy group-containing copolymer (P2) to the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1) ( A2), and

The carboxy group-containing copolymer (P2) is

A structural unit derived from an ethylenically unsaturated compound (m-2) containing a carboxyl group, and

At least 1 selected from the group consisting of a structural unit derived from a polymerizable monomer (m-3) having a C10 to C20 interchangeable hydrocarbon group and a structural unit derived from a polymerizable monomer (m-4) represented by the following formula (1) Bell

The ethylenically unsaturated resin composition according to [1], which is a copolymer containing.

(X and X'in formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R1 and R2 are each independently a hydrogen atom, a carboxyl group, or a carbon number which may have a substituent. It is a hydrocarbon group of 1 to 20, and may have a cyclic structure connecting R1 and R2.)

[4] The ethylenically unsaturated resin (A) is a polybasic acid anhydride (d ) Is added to the ethylenically unsaturated resin (A3),

The epoxy resin (P3) is

In [1], which is at least one selected from the group consisting of a novolak type epoxy resin (P3-1), a bisphenol type epoxy resin (P3-2), and a bifunctional epoxy resin having a biphenyl skeleton (P3-3) The described ethylenically unsaturated resin composition.

[5] The ethylenically unsaturated resin (A) is an ethylenically unsaturated resin (A4) having a hydroxy group formed by ring-opening addition of a carboxy group-containing resin (P4) to the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1),

The carboxyl group-containing resin (P4) is a resin having a carboxyl group formed by reacting an epoxy resin (P3) with a polyfunctional carboxylic acid (e),

The epoxy resin (P3) is

In [1], which is at least one selected from the group consisting of a novolak type epoxy resin (P3-1), a bisphenol type epoxy resin (P3-2), and a bifunctional epoxy resin having a biphenyl skeleton (P3-3) The described ethylenically unsaturated resin composition.

[6] The ethylenically unsaturated resin (A) is

An ethylenically unsaturated resin (A5) obtained by adding a polybasic acid anhydride (d) to the hydroxy group of the ethylenically unsaturated resin (A2) described in [3], or

The ethylenically unsaturated resin composition according to [1], which is an ethylenically unsaturated resin (A6) obtained by adding a polybasic acid anhydride (d) to the hydroxy group of the ethylenically unsaturated resin (A4) according to [5].

[7] The ethylenically unsaturated resin composition according to any one of [1] to [6], wherein the carbon cluster (c) is an unsubstituted fullerene.

[8] The ethylenically unsaturated resin composition according to any one of [1] to [7], which substantially does not contain a polymerization inhibitor other than the carbon cluster (c).

[9] The ethylenically unsaturated resin composition according to any one of [1] to [8], further containing a reactive diluent (D).

[10] A photosensitive resin composition containing the ethylenically unsaturated resin composition according to any one of [1] to [9] and a photopolymerization initiator (E).

[11] further containing a colorant (F),

The photosensitive resin composition according to [10], wherein the colorant (F) is at least one selected from the group consisting of dyes and pigments.

[12] The photosensitive resin composition according to [10] or [11], which substantially does not contain a polymerization inhibitor other than the carbon cluster (c).

[13] A resist using the photosensitive resin composition according to any one of [10] to [12].

According to the present invention, there is provided an ethylenically unsaturated resin composition containing a small amount of carbon clusters, high transparency, high heat yellowing resistance, and high fine particle dispersibility including a colorant, and a photosensitive resin composition using the same.

Hereinafter, the present invention will be described in detail.

[Ethylenically unsaturated resin composition]

The ethylenically unsaturated resin composition of the present invention contains an ethylenically unsaturated resin (A), a carbon cluster (c), and a solvent (B). The carbon cluster (c) is at least one of fullerene and soot-like substances. The content of the carbon cluster (c) is 0.00001 to 10 parts by mass per 100 parts by mass of the ethylenically unsaturated resin (A). It is preferable that the carbon cluster (c) is an unsubstituted fullerene. Further, the ethylenically unsaturated resin composition of the present invention does not have to substantially contain a polymerization inhibitor other than the carbon cluster (c). "Substantially not included" means, with respect to 100 parts by mass of the ethylenically unsaturated resin (A), a polymerization inhibitor other than the carbon cluster (c) is preferably 0.05 parts by mass or less, more preferably 0.01 parts by mass or less. It is meant to include.

The resin composition of the present invention may further contain a reactive diluent (D).

[Carbon cluster (c)]

When the ethylenically unsaturated resin composition of the present invention contains the carbon cluster (c), gelation due to polymerization of the double bonds of the ethylenically unsaturated resin (A) can be prevented and storage stability can be improved. In addition, by using the carbon cluster (c) in the photosensitive resin composition containing the photopolymerization initiator (E) described later, the curability is not adversely affected, the heat yellowing resistance and the dispersibility of fine particles including a colorant are excellent, and the pattern shape is A photosensitive resin composition from which an excellent resist is obtained is obtained.

The carbon cluster (c) is a group or fine particles formed by aggregation of several to hundreds of atoms or molecules. The size of the carbon cluster (c) preferably has a maximum diameter of 300 nm or less, and more preferably 100 nm or less. The carbon cluster (c) may have agglomerated primary particles. Since the size of the primary particles affects the dispersion of the carbon cluster (c), the maximum diameter referred to herein is the maximum diameter of the primary particles.

The carbon cluster (c) of the present invention is a fullerene or soot substance.

As the fullerene used in the present invention, those having about 60 to 120 carbon atoms, such as 60, 70, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96, are known. In the present invention, the number of carbon atoms is not particularly limited, but since it is easy to obtain and has excellent dispersibility, 60 (C60) and 70 (C70) carbon atoms are preferable. Further, fullerenes containing heterogeneous atoms such as scandium (Sc), lanthanum (La), cerium (Ce), titanium (Ti), and nitrogen (N) can also be used. _{Further, an oxide of fullerene, (C60) 2} O to which oxides of fullerene are added, and an adduct of fullerenes (C60-C60, C70-C60, C70-C70, etc.) can also be used.

The soot-like material used in the present invention is preferably soot produced by-products during fullerene production. It is included in the crude fullerene produced in the manufacturing process of fullerene. After solvent extraction and removal of the fullerene from the crude fullerene, the soot-like substance is more contained in the residue. This soot-like carbon material has a structure in which a five-membered ring and a six-membered ring are bonded, like fullerene, and contains amorphous carbon molecules that are not enclosed.

As a method for producing a fullerene that produces a soot-like substance, for example, a resistance heating method, an arc discharge method, a microwave method, a high-frequency heating method, a CVD method, a thermal plasma method, a combustion method, a laser method, and a thermal decomposition method are exemplified. All are manufactured under an environment under pressure of 800 hPa or less. In the case of a gas combustion method, for example, the soot-like carbon material can be obtained by firing a hydrocarbon raw material and an oxygen-containing gas in a reduced pressure environment. As the hydrocarbon raw material, for example, aromatic hydrocarbons such as toluene and benzene can be used. The decompression condition is preferably 3 to 800 hPa, and the heating condition is 1600 to 2000°C.

When the hydrocarbon raw material and the oxygen-containing gas are calcined under the above-described reduced pressure environment, hydrogen is released from the hydrocarbon raw material. Here, the mixing ratio of the hydrocarbon raw material and the oxygen-containing gas is preferably 2.5 to 3.5 in terms of an equivalent ratio, and the amount of the hydrocarbon raw material is increased. Thereby, the reaction can be made into incomplete combustion. When the reaction is completely burned, there is a possibility that carbon in the hydrocarbon raw material is bonded to oxygen and is discharged as carbon monoxide or carbon dioxide, making it difficult for carbon to bond with each other. In addition, as for the equivalent ratio, the ratio of the amount of the hydrocarbon raw material to be completely burned and the amount of oxygen is set to 1.

Hydrocarbon raw materials from which hydrogen has been omitted are unstable and tend to aggregate with surrounding carbons. At this time, some react and chemically bond. Carbon compounds obtained in this process include soot-like substances and other carbon compounds.

The soot-like substance includes amorphous carbon molecules that cannot reach a predetermined spherical molecular structure, such as fullerenes, although a plurality of carbons are bound by bonding between molecules. Examples of such amorphous carbon molecules include carbon molecules having the same structure as the partial structure of fullerene, intermediates generated in the production process of fullerene, and structures in which part of the spherical fullerene is not deleted or abolished. This amorphous carbon molecule may form a cluster structure in which a plurality of these carbon molecules are gathered. The cluster structure includes a box-shaped structure in which carbon molecules having a large sized non-enclosed structure contain carbon molecules having a small sized non-enclosed structure.

The carbon cluster (c) may have a substituent as long as effects such as dispersibility and radical replenishment ability are not impaired. Examples of the substituent include indene, malonic acid, methyl phenylbutyrate, and the like, and derivatives of fullerene include ICBA (inden bis adduct), ICMA (indene adduct), PCBM (phenyl-C61-butyric acid methyl ester, etc.), and SAM (1-methyl-1H-pyrrolobenzoic acid adduct) etc. can be illustrated.

The added amount of the carbon cluster (c) is 0.00001 to 10 parts by mass, preferably 0.0001 to 5 parts by mass, and more preferably 0.005 to 1 part by mass, based on 100 parts by mass of the ethylenically unsaturated resin (A). If it is 0.00001 parts by mass or more, the double bond of the ethylenically unsaturated resin (A) is polymerized to prevent the composition from gelling. If it is 10 parts by mass or less, even when photo-cured as a photosensitive resin composition described later, the curability is not adversely affected.

When the carbon cluster (c) is finally contained in the ethylenically unsaturated resin composition, the effect of the present invention can be obtained. Further, by adding the carbon cluster (c) from the step of synthesizing the ethylenically unsaturated resin (A), the carbon cluster (c) can be more efficiently dispersed in the ethylenically unsaturated resin composition.

The addition amount of the carbon cluster (c) used in the synthesis of the ethylenically unsaturated resin (A) is preferably 0.0001 to 0.1 parts by mass, more preferably 0.005 to 0.05 parts by mass based on 100 parts by mass of the total of the polymer and the monomer used as the material. Do.

If the amount of carbon clusters (c) added during the reaction is 0.1 parts by mass or less, the reaction is not inhibited even when radically curing the ethylenically unsaturated resin (A). If it is 0.0001 parts by mass or more, radicals generated during the reaction when obtaining the ethylenically unsaturated resin (A) can be sufficiently captured and gelation of the ethylenically unsaturated resin (A) can be prevented.

Since the amount of carbon cluster (c) is small, it is preferable to use unsubstituted fullerene as the carbon cluster (c), and mixed unsubstituted fullerene containing C60 and C70 and other higher order fullerenes is used from the viewpoint of ease of availability. It is more preferable to do it.

As the carbon cluster (c), for example, nanom mix ST (C60 is about 60%, C70 is about 25%, and other high-order fullerenes) made by Frontier Carbon, which is a fullerene mixture, can be used.

[Polymerization inhibitors other than carbon cluster (c)]

Polymerization inhibitors other than the carbon cluster (c), except for the carbon cluster (c) according to the present invention, are usually added to prevent gelation due to polymerization of the double bond introduced into the ethylenically unsaturated resin (A). The type of ramen noodles is not particularly limited, but specifically, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, dibutylhydroxytoluene, and the like are exemplified.

[Ethylenically unsaturated resin (A)]

The ethylenically unsaturated resin (A) of the present invention is not particularly limited as long as it is a resin containing an ethylenically unsaturated group, but is preferably a resin obtained by reacting an epoxy group-containing compound (a) with a carboxy group-containing compound (b), and contains the epoxy group. At least one of the compound (a) and the carboxyl group-containing compound (b) contains an ethylenically unsaturated group. For example, it is obtained by a method of reacting a resin containing an epoxy group and an unsaturated compound containing a carboxy group as a polymerization inhibitor in the presence of a carbon cluster (c) and a catalyst. Alternatively, for example, it can be obtained by reacting an unsaturated compound containing an epoxy group and a resin containing a carboxy group as a polymerization inhibitor in the presence of a carbon cluster (c) and a catalyst.

The epoxy group-containing compound (a) according to the present invention is not particularly limited as long as it is a compound having an epoxy group. Preferably, the epoxy group-containing copolymer (P1) in the first embodiment described later, the epoxy group-containing ethylenically unsaturated compound (m-1) in the second and fourth embodiments described later, and the agent described later. Epoxy resin (P3) in 3rd embodiment is mentioned.

The carboxyl group-containing compound (b) according to the present invention is not particularly limited as long as it is a compound having a carboxyl group. Preferably, the carboxyl group-containing ethylenically unsaturated compound (m-2) in the first and third embodiments described later, the carboxy group-containing copolymer (P2) in the second embodiment described later, and the agent described later. Carboxy group-containing resin (P4) in 4 embodiment is mentioned.

When the amount of carbon cluster (c) is, for example, 0.00001 to 10 parts by mass per 100 parts by mass of the total of the epoxy group-containing compound and the carboxy group-containing compound, the finally obtained ethylenically unsaturated resin composition is an ethylenically unsaturated resin (A) It contains 0.00001 to 10 parts by mass of carbon clusters (c) per 100 parts by mass.

[First Embodiment]

[Ethylenically unsaturated resin (A1)]

In the ethylenically unsaturated resin (A1) of the present embodiment, a carboxyl group-containing ethylenically unsaturated compound (m-2), which is a carboxy group-containing compound (b), is in the epoxy group of the epoxy group-containing copolymer (P1), which is the epoxy group-containing compound (a). It is a resin having an ethylenically unsaturated group obtained by adding a ring-opening and adding a polybasic acid anhydride (d) to a hydroxy group generated by the ring-opening of the epoxy group, if necessary. The epoxy group-containing copolymer (P1) is a constitutional unit derived from an ethylenically unsaturated compound containing an epoxy group (m-1), a constitutional unit derived from a polymerizable monomer (m-3) having a interchangeable hydrocarbon group having 10 to 20 carbon atoms, and the above It is a copolymer containing at least one type selected from the group consisting of structural units derived from the polymerizable monomer (m-4) represented by the general formula (1). The ethylenically unsaturated resin (A1) may further contain a structural unit derived from an aromatic ring-containing polymerizable monomer (m-5), and the like.

The ethylenically unsaturated resin (A1) according to the present embodiment contains a structural unit derived from the addition reaction of the carboxy group-containing ethylenically unsaturated compound (m-2), thereby introducing a double bond having excellent photosensitivity and ring opening of the epoxy group. Thereby, a hydroxy group excellent in alkali developability can be obtained. Further, when carboxylic acid is introduced by adding polybasic acid anhydride (d) to the obtained hydroxy group, alkali developability can be improved. With this structural unit, the cured product exhibits sufficient hardness and high solvent resistance.

Further, by leaving a part of the epoxy group without reacting with the carboxy group-containing ethylenically unsaturated compound (m-2), curing by heat can also be simultaneously expressed.

[Copolymer containing an epoxy group (P1)]

The monomer (M1) forming the epoxy group-containing copolymer (P1) (hereinafter, simply referred to as “copolymer (P1)”) of the ethylenically unsaturated resin (A1) of the present embodiment is an epoxy group-containing ethylene. Selected from the group consisting of a sexually unsaturated compound (m-1), a polymerizable monomer (m-3) having a interchangeable hydrocarbon group having 10 to 20 carbon atoms, and a polymerizable monomer (m-4) represented by the above formula (1). It contains at least one kind. The monomer (M1) may further contain an aromatic ring-containing polymerizable monomer (m-5) or other polymerizable monomer (m-6). By further having an aromatic ring-containing polymerizable monomer (m-5), an epoxy group-containing copolymer (P1) having more excellent dispersibility of the colorant can be obtained.

[Ethylenically unsaturated compound containing an epoxy group (m-1)]

The epoxy group-containing ethylenically unsaturated compound (m-1) (hereinafter, simply referred to as "monomer (m-1)" in some cases) is not particularly limited as long as it does not have a carboxy group and is a monomer having an epoxy group and an ethylenically unsaturated group. Specific examples include glycidyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) Acrylate, lactone adducts thereof (e.g., Cyclomer (registered trademark) A200, M100 manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane The mono(meth)acrylic acid ester of carboxylate, the epoxidation product of dicyclopentenyl (meth)acrylate, the epoxidation product of dicyclopentenyloxyethyl (meth)acrylate, etc. are mentioned. These epoxy group-containing ethylenically unsaturated compounds (m-1) may be used alone or in combination of two or more. In particular, glycidyl (meth)acrylate is suitable from the viewpoint of ease of availability and good reactivity.

Since the structural unit derived from the epoxy group-containing ethylenically unsaturated compound (m-1) and the carboxy group-containing ethylenically unsaturated compound (m-2) described later impart a photosensitive group that exhibits photocurability, the ethylenic It is an essential derived constitution in an unsaturated resin (A1).

By introducing a photosensitive group that exhibits photocurability, the cured film exhibits sufficient hardness and exhibits high solvent resistance.

[Polymerizable monomer (m-3)]

The polymerizable monomer (m-3) (hereinafter, simply referred to as "monomer (m-3)" in some cases) has a crosslinkable hydrocarbon group having 10 to 20 carbon atoms. Here, the interchangeable hydrocarbon group means having a structure represented by the following formula (2) or (3) typified by adamantane and norbornane, and the interchangeable hydrocarbon group excludes some hydrogen in the structure. It refers to the flag equivalent to the rest of the part. In addition, it is assumed that the polymerizable monomer (m-3) does not contain the polymerizable monomer (m-4) described later.

(In formula (2), A and B each represent a linear or branched alkylene group (including a cyclic), and R 3 represents a hydrogen atom or a methyl group. A and B may be the same or different, and A and B Branches of may be connected to each other to form an illusion.)

(In formula (3), A', B'and D each represent a linear or branched alkylene group (including a cyclic), and R4 represents a hydrogen atom or a methyl group. A', B'and D may be the same. They may be different, and branches of A', B', and D may be connected to each other to form an annular shape.)

As the monomer (m-3), (meth)acrylate having a interchangeable hydrocarbon group having 10 to 20 carbon atoms is preferable, and adamantyl (meth)acrylate or (meth) having a structure represented by the following formula (4) Acrylate is more preferred.

(In formula (4), R5 to R7 each represents a hydrogen atom or a methyl group. R8 and R9 may be a hydrogen atom or a methyl group, or may be connected to each other to form a saturated or unsaturated ring, and the ring is preferably a 5-membered ring. Or a 6-membered ring, * represents a bond hand connected to a (meth)acryloyloxy group.)

Examples of the (m-3) include dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate. . These can be used alone or in combination of two or more.

[Polymerizable monomer (m-4)]

The polymerizable monomer (m-4) (hereinafter, simply referred to as "monomer (m-4)" in some cases) is a monomer represented by the following general formula (1).

(X and X'in the formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R1 and R2 are each independently a hydrogen atom or a substituent having 1 to carbon atoms. It is a hydrocarbon group of 20 and may have a cyclic structure connecting R1 and R2.)

The monomer (m-4) is not particularly limited as long as it has a chemical structure represented by General Formula (1). In the general formula (1), examples of X and X'representing a linear or branched hydrocarbon group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, etc. are mentioned. Further, examples of the substituent in the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent represented by R1 and R2 include an alkoxy group and an aryl group. Examples of R1 and R2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl group, 2-ethylhex A linear or branched alkyl group such as an actual group; Alicyclic groups such as cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, and 2-methyl-2-adamantyl group; An alkyl group substituted with an alkoxy group such as 1-methoxyethyl group and 1-ethoxyethyl group; And an alkyl group substituted with an aryl group such as a phenyl aralkyl group.

Examples of the monomer (m-4) having a chemical structure represented by the general formula (1) include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept- 2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-methyltetracyclo[4.4. 0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-ethyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, dicyclopentadiene, tricyclo[ 5.2.1.0 ^2,6 ]dec-8-ene, tricyclo[5.2.1.0 ^2,6 ]dec-3-ene, tricyclo[4.4.0.1 ^2,5 ]undec-3-ene, tricyclo[6.2 .1.0 ^1,8 ]undec-9-ene, tricyclo[6.2.1.0 ^1,8 ]undec-4-ene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] Dodec-3-ene, 8-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ]Dodec-3-ene, 8-ethylidenetetracyclo[4.4.0.1 ^2,5 .1 ^7,12 ]dodec-3-ene, 8-ethylidenetetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ]dodec-3-ene, pentacyclo[6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ]pentadec-4-ene, pentacyclo[7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ]pentadec-3-ene, etc. I can. These can be used alone or in combination of two or more.

By using the monomer (m-3) and/or the monomer (m-4), it contributes to smooth coating properties, high thermal decomposition resistance, and high heat yellowing resistance of the cured film. In addition, as for the monomer (m-3) and the monomer (m-4), one or both may be used.

[Aromatic Ring-Containing Polymerizable Monomer (m-5)]

The aromatic ring-containing polymerizable monomer (m-5) (hereinafter, simply referred to as “monomer (m-5)” in some cases) is a monomer having no carboxyl group or epoxy group, and having an aromatic ring. For example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxy Aromatic vinyl compounds such as oxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanostyrene, and p-acetylaminostyrene; Benzyl (meth)acrylate, rosin (meth)acrylate, phenyl (meth)acrylate, cumyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy-polyethylene glycol (meth)acrylate (trade name: Light acrylate P-200A, Kyoei Chemical Co., Ltd.), nonylphenoxy polyethylene glycol mono(meth)acrylate, o-phenoxybenzyl(meth)acrylate, m-phenoxybenzyl(meth)acrylate, p- Phenoxybenzyl (meth)acrylate, 4-phenoxyphenyl (meth)acrylate, biphenyloxyethyl (meth)acrylate, ethoxylated o-phenylphenol (meth)acrylate, naphthalene (meth)acrylate, anthracene (Meth)acrylate, etc. are mentioned. Among these, from the viewpoint of elastic recovery rate, the ethylenically unsaturated resin (A1) used in the present invention contains at least one selected from the group consisting of benzyl (meth)acrylate, styrene, biphenyl skeleton, naphthalene skeleton, and anthracene skeleton. It is more preferable to introduce a structural unit to have.

[Other polymerizable monomers (m-6)]

The epoxy group-containing copolymer (P1) according to the present embodiment is a polymerizable monomer (m-6) other than the monomers (m-1) to (m-5) (hereinafter, simply referred to as ``monomer (m-6)''). In some cases) may be copolymerized. Other polymerizable monomers (m-6) are copolymerizations other than those shown in the above monomers (m-1), (m-3), (m-4), (m-5), and monomers (m-2) described below. It is a possible monomer. This monomer (m-6) is generally a radically polymerizable compound having an ethylenically unsaturated group. For example, as this monomer (m-6), dienes, such as (meth)acrylic acid ester, (meth)acrylic acid amide, maleimide, unsaturated dicarboxylic acid diester, butadiene, etc. are mentioned. Specific examples of (meth)acrylic acid esters are methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate. , sec-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, benzyl (meth)acrylate, Isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclo Hexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, rosin (meth)acrylate, allyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tri Phenylmethyl (meth)acrylate, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate, and the like. Specific examples of (meth)acrylic acid amide include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (Meth)acrylic acid N,N-di-iso-propylamide, (meth)acrylic acid anthracenylamide, and the like. Specific examples of maleimides include vinyl compounds such as anilide (meth)acrylate, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, and vinyl acetate. ; And N-cyclohexylmaleimide, N-laurylmaleimide, and the like. Specific examples of the unsaturated dicarboxylic acid diester include diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconic acid, and the like. These may be used alone or in combination of two or more as necessary.

[Ratio of structures derived from each monomer of the copolymer (P1) containing an epoxy group]

In the copolymer (P1) according to the present invention, the monomer (M1) contains a monomer (m-1), and if necessary, for example, a monomer (m-3), a monomer (m-4), or a monomer ( When m-5) is included, the ratio of the structure derived from each monomer uses the value of the molar ratio of each polymerizable monomer added for the copolymerization reaction. There is no particular limitation on the blending ratio (molar ratio) of each monomer, but the blending ratio of the monomer (m-1) is preferably 9 to 70 mol%, more preferably 13 to 65 mol%. When the blending ratio of the monomer (m-1) is 9 mol% or more, sufficient curability can be expressed when it is set as a photosensitive resin composition. When the blending ratio of the monomer (m-1) is 70 mol% or less, the blending ratio of the monomer (m-3) and/or the monomer (m-4) is sufficiently large, and an ethylenically unsaturated resin having a desired thermal decomposition resistance or refractive index (A1) is obtained.

In the case of using the monomer (m-3) and/or the monomer (m-4), the blending ratio thereof is greater than 0 mol% to 40% based on 100 mol% of the total amount of the monomer (M1) of the epoxy group-containing copolymer (P1). It is preferable that it is mol%, and it is more preferable that it is more than 0 mol%-30 mol%. If the blending ratio is more than 0 mol%, desired heat decomposition resistance, heat yellowing resistance, and good solubility in a solvent can be obtained.

When using the monomer (m-5), the blending ratio thereof is preferably more than 0 mol% to 50 mol% with respect to 100 mol% of the total amount of the monomer (M1) of the epoxy group-containing copolymer (P1), and is 0 mol. It is more preferable that it is more than%-40 mol%.

In the case of using the monomer (m-6), the blending ratio thereof is preferably more than 0 mol% to 10 mol% with respect to 100 mol% of the total amount of the monomer (M1) of the epoxy group-containing copolymer (P1), and is 0 mol. It is more preferable that it is more than 5 mol%.

[Copolymerization Reaction (Method for Producing Epoxy Group-Containing Copolymer (P1))]

The epoxy group-containing copolymer (P1) according to the present invention can be produced using a copolymerization reaction of the monomer (M1). The copolymerization reaction performed in the present invention can be performed according to a radical polymerization method known in the art. For example, after dissolving a monomer used for copolymerization in a solvent, a polymerization initiator is added to the solution, and then at 50 to 140°C, more preferably at 60 to 130°C for 1 to 20 hours, more preferably 1 to 12 Just react with time. Moreover, you may make it react while dropping the monomer used for copolymerization and a polymerization initiator to the solvent adjusted to 50-140 degreeC.

The solvent that can be used for this copolymerization reaction is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.

As the copolymerization reaction solvent, a solvent for addition reaction described later can be used.

The amount of the solvent used for this copolymerization reaction is not particularly limited, but when the total of the monomers used for the copolymerization is 100 parts by mass, it is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass. In particular, by setting the amount of the solvent to 1000 parts by mass or less, a decrease in the molecular weight of the copolymer (P1) due to a chain transfer action can be suppressed, and the viscosity of the copolymer (P1) can be controlled in an appropriate range. In addition, by setting the amount of the solvent to 30 parts by mass or more, an abnormal polymerization reaction can be prevented, the polymerization reaction can be stably performed, and coloration or gelation of the copolymer (P1) can be prevented.

The polymerization initiator that can be used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and an organic peroxide catalyst or an azo compound that is usually used can be used. Specifically, azobisisobutyronitrile, azobisisovaleronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), azobis (2-methylpropionic acid) dimethyl, benzoyl peroxide, di Cumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, t-hexylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-hex Silperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, etc. are mentioned.

These may be used alone or in combination of two or more, and it is preferable to select a radical polymerization initiator having an appropriate half-life according to the polymerization temperature.

The amount of the polymerization initiator used in the copolymerization reaction is not particularly limited, but when the total of the monomers used for the copolymerization is 100 parts by mass, it is generally 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass.

[Ethylenically unsaturated compound containing carboxyl group (m-2)]

The ethylenically unsaturated compound (m-2) containing a carboxyl group (hereinafter, simply referred to as "monomer (m-2)" in some cases) does not have an epoxy group, and among the acid groups, a carboxy group and an ethylenically unsaturated group having particularly good reactivity with an epoxy group and an ethylenically unsaturated group have no epoxy group. It does not specifically limit as long as it has a monomer. For example, an unsaturated monobasic acid or an unsaturated dibasic acid monoester is mentioned. Examples of unsaturated monobasic acids include (meth)acrylic acid, itaconic acid, crotonic acid, cinnamic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylphthalic acid, and 2-(meth)acrylic. Royloxyethylhexahydrophthalic acid, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid, monomethyl maleate, monoethyl maleate, And unsaturated carboxylic acids such as monoisopropyl maleate, monomethyl fumarate, and monoethyl itaconic acid. Examples of the unsaturated dibasic acid monoester include monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, monoethyl itaconic acid, and the like. These carboxy group-containing ethylenically unsaturated compounds (m-2) may be used alone or in combination of two or more. Among these, (meth)acrylic acid is preferable from the viewpoint of availability and reactivity.

The reaction ratio of the carboxy group-containing ethylenically unsaturated compound (m-2) is preferably 10 to 70 mol%, more preferably when the total of the monomers (M1) of the epoxy group-containing copolymer (P1) is 100 mol%. It is 15 to 65 mol%. When the blending ratio of the carboxyl group-containing ethylenically unsaturated compound (m-2) is 10 mol% or more, sufficient curability can be expressed when it is set as a photosensitive resin composition. In addition, when it is 70 mol% or less, the blending ratio of the monomer (M1) is sufficiently ensured, and an ethylenically unsaturated resin (A1) having desired thermal decomposition resistance and the like is obtained. In addition, as a ratio of adding the carboxy group-containing ethylenically unsaturated compound (m-2) to the number of moles of the epoxy group of the epoxy group-containing copolymer (P1), it is preferably 90 to 100%, more preferably 95 to 100%. to be. When the addition ratio of the carboxy group-containing ethylenically unsaturated compound (m-2) is 90% or more, sufficient curability can be expressed when it is set as a photosensitive resin composition.

[Polybasic acid anhydride (d)]

The polybasic acid anhydride (d) is not particularly limited as long as it has an acid anhydride structure having good reactivity with a hydroxy group, but it is preferable that it has a ring structure in which no by-products are generated after the reaction. Specifically, 1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, methyl ratio Cyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, succinic anhydride, octenylsuccinic anhydride, and the like.

The reaction ratio of the polybasic acid anhydride (d) is preferably 10 to 70 mol%, more preferably 15 to 65 mol% when the total of the monomers (M1) of the epoxy group-containing copolymer (P1) is 100 mol%. to be. The number of moles to which the carboxyl group-containing ethylenically unsaturated compound (m-2) is added is preferably 20 to 100 mol%, more preferably 30 to 90 mol%.

[Method for producing ethylenically unsaturated resin (A1)]

In the ethylenically unsaturated resin (A1) according to the present embodiment, for example, after adding a polymerization inhibitor and a catalyst to a solution of the epoxy group-containing copolymer (P1), a carboxy group-containing ethylenically unsaturated compound (m-2) is added. Then, the epoxy group is subjected to a ring-opening addition reaction under conditions of 50 to 150°C, preferably 80 to 130°C, and then polybasic acid anhydride (d) is added as necessary, followed by addition reaction. It is preferable to use carbon clusters (c) as polymerization inhibitors.

When reacting the carboxy group-containing ethylenically unsaturated compound (m-2), even if the solvent used for the copolymerization reaction is contained, there is no particular problem, and thus the reaction can be carried out without removing the solvent after the copolymerization reaction is completed. Here, the polymerization inhibitor is added to prevent gelation due to polymerization of the introduced double bond.

[catalyst]

Examples of the catalyst used in this embodiment include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzyl ammonium chloride, phosphorus compounds such as triphenylphosphine, chelate compounds of chromium, and the like. Can be lifted. These catalysts may be used alone or in combination of two or more.

The amount of the catalyst used in this embodiment is not particularly limited, but when the resin precursor (epoxy group-containing copolymer (P1)) is 100 parts by mass, it is generally 0.01 to 5 parts by mass, preferably 0.1 to It is 2 parts by mass, more preferably 0.2 to 1 part by mass.

[Solvent used in addition reaction]

It does not specifically limit as a solvent used in this embodiment, A well-known thing can be used suitably. As the solvent, an ether compound, a ketone compound, an ester compound, an aromatic hydrocarbon compound, and a carboxylic acid amide compound can be used. As an ether compound, (poly) alkylene glycol monoalkyl ether; (Poly) alkylene glycol monoalkyl ether acetate; Other ether compounds, such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran, etc. are mentioned. Specific examples of the (poly) alkylene glycol monoalkyl ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, and diethylene glycol monomethyl ether. Ethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, di Propylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and the like. Specific examples of the (poly) alkylene glycol monoalkyl ether acetate include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Specific examples of the ketone compound include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and the like. Specific examples of the ester compound are 2-hydroxypropionate methyl, 2-hydroxypropionate ethyl, 2-hydroxy-2-methylpropionate methyl, 2-hydroxy-2-methylpropionate ethyl, 3-methoxypropionate methyl, 3 -Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyrate methyl, 3-methyl-3-methoxybutyl Acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i acetate -Amyl, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate And the like. Specific examples of the aromatic hydrocarbon compound include toluene, xylene, and the like. Specific examples of the carboxylic acid amide compound include N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and the like. These solvents may be used alone or in combination of two or more.

Among the above solvents, glycol ether solvents are preferred. That is, as the solvent, it is preferable to use (poly) alkylene glycol monoalkyl ether such as propylene glycol monomethyl ether, and (poly) alkylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate.

The amount of the solvent used to produce the resin of the present embodiment is not particularly limited, but when the resin precursor is 100 parts by mass, it is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass. When the amount of the solvent is 1000 parts by mass or less, it is preferable because the viscosity of the resin can be controlled within an appropriate range. On the other hand, if the amount of the solvent is 30 parts by mass or more, it is preferable because it is possible to prevent seizure from occurring during the reaction, and because the synthesis reaction can be stably performed. In addition, when the amount of the solvent is 30 parts by mass or more, coloring or gelation of the resin can be prevented.

[Second Embodiment]

[Ethylenically unsaturated resin (A2)]

The ethylenically unsaturated resin (A2) according to the present embodiment is a carboxy group-containing copolymer (P2), which is a carboxy group-containing compound (b), in the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1), which is an epoxy group-containing compound (a). Is a resin containing a hydroxy group and an ethylenically unsaturated group obtained by ring-opening addition. The carboxyl group-containing copolymer (P2) contains at least a structural unit derived from the carboxy group-containing ethylenically unsaturated compound (m-2), and, if necessary, a polymerizable monomer (m-3) having a interchangeable hydrocarbon group having 10 to 20 carbon atoms. ) Derived constituent units, the constituent units derived from the polymerizable monomer (m-4) represented by the general formula (1), or the constituent units derived from the aromatic ring-containing polymerizable monomer (m-5), etc. to be.

The ethylenically unsaturated resin (A2) according to the present embodiment contains a structural unit derived from the addition reaction of the epoxy group-containing ethylenically unsaturated compound (m-1), thereby introducing a double bond excellent in photosensitivity, and at the same time, in the ring opening of the epoxy group. Thus, a hydroxy group can be obtained. Thereby, curability by light or heat can be expressed, and alkali developability can be expressed. With this structural unit, the cured product exhibits sufficient hardness and high solvent resistance. In addition, carboxylic acid can be introduced at the same time by leaving a part of the carboxyl group in the carboxyl group-containing copolymer (P2) without reacting with the epoxy group of the monomer (m-1).

The epoxy group-containing ethylenically unsaturated compound (m-1) according to the present embodiment can be used according to the first embodiment.

The addition ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) to the number of moles of carboxy contained in the carboxy group-containing copolymer (P2) is preferably 90 to 100% by mole, more preferably 95 to 100% by mole. . When the addition ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) is 90 mol% or more, sufficient curability can be expressed when it is set as a photosensitive resin composition.

In addition, the reaction ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) is preferably 10 to 70 when the total of all monomers (M2) used in the epoxy group-containing copolymer (P2) is 100 mol%. It is mol%, more preferably 15 to 65 mol%. When the compounding ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) is 10 mol% or more, sufficient curability can be expressed when it is set as a photosensitive resin composition.

[Copolymer containing carboxyl group (P2)]

All monomers (M2) of the carboxy group-containing copolymer (P2) (hereinafter, simply referred to as “copolymer (P2)”) relating to the ethylenically unsaturated resin (A2) of the present embodiment are at least carboxy group-containing ethylene. A polymerizable monomer (m-3) containing a sexually unsaturated compound (m-2) and further having a interchangeable hydrocarbon group having 10 to 20 carbon atoms as necessary, or a polymerizable monomer represented by the above formula (1) (m- 4) or an aromatic ring-containing polymerizable monomer (m-5) or other polymerizable monomer (m-6).

Carboxy group-containing ethylenically unsaturated compound (m-2), polymerizable monomer (m-3), polymerizable monomer (m-4), aromatic ring-containing polymerizable monomer (m-5), and other polymerizable compounds according to the present embodiment The monomer (m-6) is the same as that described in the first embodiment, and a description thereof is omitted.

[Ratio of the structure derived from each monomer of the carboxy group-containing copolymer (P2)]

In the copolymer (P2) according to the present invention, the total monomer (M2) contains a carboxyl group-containing ethylenically unsaturated compound (m-2), and additionally has a C10 to C20 interchangeable hydrocarbon group as required. When a monomer (m-3), a polymerizable monomer (m-4) represented by the general formula (1), or an aromatic ring-containing polymerizable monomer (m-5) is contained, the ratio of the structure derived from each monomer is , The value of the molar ratio of each polymerizable monomer added for the copolymerization reaction is used. There is no particular limitation on the blending ratio (molar ratio) of each monomer, but when the total of all monomers (M2) is 100 mol%, the blending ratio of the monomer (m-2) is preferably 9 to 70 mol%, More preferably, it is 13 to 65 mol%. When the blending ratio of the monomer (m-2) is 9 mol% or more, sufficient curability can be expressed when it is set as a photosensitive resin composition. When the blending ratio of the monomer (m-2) is 70 mol% or less, the blending ratio of the monomer (m-3), the monomer (m-4), and the monomer (m-5) is sufficiently increased, and the desired thermal decomposition resistance is obtained. An ethylenically unsaturated resin (A2) is obtained.

When using the monomer (m-3) and/or the monomer (m-4), the blending ratio is 0 mol% in total based on 100 mol% of the total amount of all monomers (M2) of the carboxyl group-containing copolymer (P2). It is preferable that it is more than 40 mol%, and it is more preferable that it is more than 0 mol% and 30 mol%. When the blending ratio is 1 mol% or more, desired heat decomposition resistance, heat yellowing resistance, and good solubility in a solvent can be obtained.

When a monomer (m-5) is used, the blending ratio thereof is preferably more than 0 mol% to 50 mol%, and 0 mol% with respect to 100 mol% of the total amount of the carboxyl group-containing ethylenically unsaturated compound (m-2). It is more preferable that it is more than 40 mol%.

In the case of using the monomer (m-6), the blending ratio thereof is preferably more than 0 mol% to 10 mol% with respect to 100 mol% of the total amount of the monomer (M2) of the epoxy group-containing copolymer (P2), and 0 It is more preferable that it is more than mol%-5 mol%.

[Copolymerization reaction (manufacturing method of carboxy group-containing copolymer (P2))]

The carboxy group-containing copolymer (P2) according to the present invention can be produced using a copolymerization reaction in the same manner as the copolymer (P1) according to the first embodiment.

[Method for producing ethylenically unsaturated resin (A2)]

The method for preparing ethylenically unsaturated resin (A2) is to prepare an ethylenically unsaturated resin (A2) by reacting an epoxy group-containing ethylenically unsaturated compound (m-1) and a carboxy group-containing copolymer (P2) in the presence of a polymerization inhibitor and a catalyst. And the polymerization inhibitor is preferably the carbon cluster (c) described above.

As an example of the present embodiment, the ethylenically unsaturated resin (A2) according to the present embodiment is, after adding a carbon cluster (c) as a polymerization inhibitor to the solution of the above-described carboxy group-containing copolymer (P2), an epoxy group-containing ethylene It can be produced by adding a sexually unsaturated compound (m-1) and reacting the epoxy group of the first embodiment under the same conditions as in the ring-opening addition reaction. The carbon cluster (c) and the solvent to be used are the same as in the first embodiment.

[Third Embodiment]

[Ethylenically unsaturated resin (A3)]

In the ethylenically unsaturated resin (A3) used in the present embodiment, a carboxyl group-containing ethylenically unsaturated compound (m-2), which is a carboxy group-containing compound (b), is ring-opened in the epoxy group of the epoxy resin (P3), which is the epoxy group-containing compound (a). In addition, it is preferably a resin containing a carboxyl group and an ethylenically unsaturated group obtained by further adding a polybasic acid anhydride (d) to a hydroxy group generated by ring opening of the epoxy group. The epoxy resin (P3) is preferably selected from the group consisting of a novolak type epoxy resin (P3-1), a bisphenol type epoxy resin (P3-2), and a bifunctional epoxy resin having a biphenyl skeleton (P3-3). Do.

That is, as the ethylenically unsaturated resin (A3) used in the present embodiment, a carboxy group-containing ethylenically unsaturated compound (m-2) is added to the novolac-type epoxy resin (P3-1), and if necessary, a polybasic acid anhydride (d ) To the ethylenically unsaturated resin (A3-1) or bisphenol-type epoxy resin (P3-2) to which ethylenically unsaturated compounds containing dibasic acids and carboxyl groups (m-2) are added, and polybasic acid anhydrides as necessary It is necessary for ethylenically unsaturated resin (A3-2) to which (d) is further added or to which ethylenically unsaturated compound (m-2) containing a carboxyl group is added to a bifunctional epoxy resin (P3-3) having a biphenyl skeleton. According to this, an ethylenically unsaturated resin (A3-3) to which a polybasic acid anhydride (d) is further added is mentioned.

The carboxy group-containing ethylenically unsaturated compound (m-2), carbon cluster (c), catalyst, and solvent used in this embodiment can be those of the first embodiment.

[Ethylenically unsaturated resin (A3-1)]

For ethylenically unsaturated resin (A3-1), after adding a carboxyl group-containing ethylenically unsaturated compound (m-2) to introduce a double bond to the novolak type epoxy resin (P3-1), a carboxy group is introduced as necessary. In order to do this, it can be produced by adding a polybasic acid anhydride (d).

As the novolac-type epoxy resin (P3-1), a cresol novolac-type epoxy resin, a phenol novolac-type epoxy resin, or the like can be mentioned. These novolac-type epoxy resins may be used alone, or two or more types may be used.

[Ethylenically unsaturated resin (A3-2)]

In the ethylenically unsaturated resin (A3-2), a carboxyl group-containing ethylenically unsaturated compound (m-2) is added to introduce a double bond to the bisphenol-type epoxy resin (P3-2), and then, if necessary, a carboxyl group is introduced. Hazardous polybasic acid anhydride (d) can be added.

Examples of the bisphenol type epoxy resin (P3-2) include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol S type epoxy resin. These bisphenol type epoxy resins may be used alone, or two or more types may be used. Among these, a bisphenol A type epoxy resin is preferable from the viewpoint of availability and reactivity.

[Ethylenically unsaturated resin (A3-3)]

Ethylene unsaturated resin (A3-3) is, after adding a carboxyl group-containing ethylenically unsaturated compound (m-2) to introduce a double bond to a bifunctional epoxy resin (P3-3) having a biphenyl skeleton, if necessary. Therefore, it can be prepared by adding a polybasic acid anhydride (d) to introduce a carboxy group.

The bifunctional epoxy resin (P3-3) having a biphenyl skeleton is not particularly limited as long as it has a biphenyl skeleton in its molecule and has two epoxy groups. Examples of the biphenyl skeleton include those represented by the following formula (5).

In the formula (5), R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and E and E'each independently represent an organic group having an epoxy group.

As specific examples of the bifunctional epoxy resin having a biphenyl skeleton, YX4000 (R' is CH _{3 in the} following formula (6)), YX4000K (in the following formula (6), R'is CH ₃ ), YX4000H (in the following formula (6), R'is CH ₃ ), YL6121HA (in the following formula (6), a mixture of a compound in which _{R'is H and a compound in which R'is CH 3), etc.} I can.

If necessary, a saturated monobasic acid may be added to the epoxy group of the ethylenically unsaturated resin (A3) together with the carboxy group-containing ethylenically unsaturated compound (m-2). Although it does not specifically limit as a saturated monobasic acid, Formic acid, acetic acid, propionic acid, butyric acid, lauric acid, tridecyl acid, palmitic acid, stearic acid, etc. are mentioned. Saturated monobasic acids may be used alone, or two or more of them may be used. Among these, acetic acid and propionic acid are preferable from the viewpoint of boiling point and reactivity. Flexibility is improved by setting it as the ethylenically unsaturated resin (A3) to which a saturated monobasic acid was added together with the carboxy group-containing ethylenically unsaturated compound (m-2).

As the polybasic acid anhydride (d), the polybasic acid anhydride (d) described in the first embodiment can be used.

The ethylenically unsaturated resin (A) used in the present invention may further add an epoxy group-containing ethylenically unsaturated compound (m-1) to the carboxy group derived from the polybasic acid anhydride (d) in the ethylenically unsaturated resin (A3) of the present embodiment. do. As the epoxy group-containing ethylenically unsaturated compound, the epoxy group-containing ethylenically unsaturated compound (m-1) described in the first embodiment can be used.

The reaction conditions for obtaining the ethylenically unsaturated resin (A3) or epoxy resin (P3) used in the present invention may be appropriately set according to a conventional method.

The addition reaction of the carboxy group-containing ethylenically unsaturated compound (m-2) and the saturated monobasic acid used as necessary is, for example, adding each raw material, a polymerization inhibitor, and an addition reaction catalyst to a solvent, preferably oxygen gas. In an atmosphere with a concentration of 2 to 10% by volume, more preferably 5 to 7% by volume of an oxygen gas concentration, preferably at 100 to 140°C, more preferably at 110 to 130°C for 2 to 12 hours.

The addition reaction of the epoxy group-containing ethylenically unsaturated compound is preferably in an atmosphere having an oxygen gas concentration of 2 to 10% by volume, more preferably an oxygen gas concentration of 5 to 7% by volume, preferably 100 to 140°C, more preferably It is good to perform at 110 to 130°C for 2 to 10 hours.

The preferred structural unit ratio of the ethylenically unsaturated resin (A3) used in the present invention is as follows. In the ethylenically unsaturated resin (A3), the structural unit derived from the epoxy resin (P3) is 40 to 70% by mass, the structural unit derived from the carboxyl group-containing ethylenically unsaturated compound (m-2) is 5 to 35% by mass, The structural unit derived from the polybasic acid anhydride (d) is 10 to 40% by mass. When a saturated monobasic acid is used, the structural unit derived from the saturated monobasic acid is more than 0% by mass to 20% by mass. When using the epoxy group-containing ethylenically unsaturated compound (m-1), the structural unit derived from the epoxy group-containing ethylenically unsaturated compound (m-1) is more than 0% by mass to 10% by mass.

In addition, in setting a preferred structural unit ratio of the ethylenically unsaturated resin (A3) used in the present invention, the ethylenically unsaturated compound containing a carboxyl group to the epoxy group contained in the structural unit derived from the epoxy resin (P3) (m-2 ) And the total addition rate of the constituent units derived from the saturated monobasic acid used as necessary is preferably 90 to 100% in total with respect to the epoxy group, and the ethylenically unsaturated compound (m-2) containing a carboxyl group and used as necessary. The addition ratio of the structural unit derived from the polybasic acid anhydride to the hydroxy group generated by the addition of the constituent unit derived from the saturated monobasic acid is preferably 5 to 80%, and more preferably 10 to 70%. Further, the addition ratio of the structural unit derived from the epoxy group-containing ethylenically unsaturated compound (m-1) to the carboxyl group generated by the addition of the structural unit derived from the polybasic acid anhydride (d) is preferably 10 to 50%.

[Method for producing ethylenically unsaturated resin (A3)]

The method for producing ethylenically unsaturated resin (A3) is a method of preparing an ethylenically unsaturated resin (A3) by reacting an epoxy resin (P3) with an ethylenically unsaturated compound (m-2) containing a carboxyl group in the presence of a polymerization inhibitor and a catalyst. And it is preferable that the polymerization inhibitor is the above-described carbon cluster (c).

[Fourth Embodiment]

[Ethylenically unsaturated resin (A4)]

In the ethylenically unsaturated resin (A4) according to the present embodiment, a carboxy group-containing resin (P4), which is a carboxy group-containing compound (b), is ring-opened in the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1), which is an epoxy group-containing compound (a). It is an ethylenically unsaturated resin having a hydroxy group obtained by adding it.

As the epoxy group-containing ethylenically unsaturated compound (m-1) used in the present embodiment, those of the first embodiment can be used.

It is preferable that the addition amount of the epoxy group-containing ethylenically unsaturated compound (m-1) is more than 0 parts by mass to 10 parts by mass with respect to 100 parts by mass of the carboxy group-containing resin (P4). If the addition amount of the epoxy group-containing ethylenically unsaturated compound (m-1) exceeds 0 parts by mass, since the sensitivity can be improved, it is preferable. On the other hand, when the addition amount of the epoxy group-containing ethylenically unsaturated compound (m-1) is 10 parts by mass or less, it is preferable because the elastic recovery rate and developability can be maintained.

It is preferable that the molar ratio of the added epoxy group-containing ethylenically unsaturated compound (m-1) to the structural unit derived from the carboxyl group-containing resin (P4) in the ethylenically unsaturated resin (A4) is 0.05 to 0.3.

[Carboxy group-containing resin (P4)]

The carboxyl group-containing resin (P4) used in the present embodiment is a resin having a carboxyl group formed by reacting an epoxy resin (P3) with a polyfunctional carboxylic acid (e).

As the epoxy resin (P3), the epoxy resin (P3) used in the third embodiment can be used.

[Polyfunctional carboxylic acid (e)]

It does not specifically limit as a polyfunctional carboxylic acid (e). Any of saturated and unsaturated polyfunctional carboxylic acids may be used. Specific examples include adipic acid, itaconic acid, succinic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, tartaric acid, glutamic acid, sebacic acid, and the like. Dibasic acids may be used alone, or two or more types may be used. Among these, from the viewpoint of reactivity, adipic acid and itaconic acid are preferable.

[Ratio of the structural unit of the carboxy group-containing resin (P4)]

It is preferable that the carboxy group-containing resin (P4) contains 30 to 80 mass% of the structural units derived from the epoxy resin (P3) and 20 to 70 mass% of the structural units derived from the polyfunctional carboxylic acid (e). Here, the molar ratio of the structural unit derived from the polyfunctional carboxylic acid (e) to the structural unit derived from the epoxy resin (P3) in the carboxyl group-containing resin (P4) is preferably 0.1 to 0.8, more preferably 0.15 to 0.7. desirable.

[Production method of carboxy group-containing resin (P4)]

The carboxy group-containing resin (P4) used in this embodiment can be produced by, for example, adding an epoxy resin (P3) and a polyfunctional carboxylic acid (e) in the presence of an addition catalyst.

The conditions of the addition reaction for obtaining the carboxy group-containing resin (P4) used in the present embodiment may be appropriately set according to a conventional method. The addition reaction is carried out, for example, by adding each raw material and an addition catalyst to a solvent, preferably in an atmosphere having an oxygen gas concentration of 2 to 10% by volume, more preferably an oxygen gas concentration of 5 to 7% by volume, and preferably 50 to 150°C, more preferably 60 to 140°C for 1 to 12 hours.

It does not specifically limit as a solvent which can be used for the said addition reaction, A well-known thing can be used suitably. For example, a solvent used in the addition reaction of the first embodiment can be used.

It does not specifically limit as a polycondensation catalyst which can be used for the said addition reaction, A well-known thing can be used suitably. For example, a catalyst used in the addition reaction of the first embodiment can be used.

[Method for producing ethylenically unsaturated resin (A4)]

The method for producing ethylenically unsaturated resin (A4) is to prepare an ethylenically unsaturated resin (A4) by reacting an epoxy group-containing ethylenically unsaturated compound (m-1) and a carboxy group-containing resin (P4) in the presence of a polymerization inhibitor and a catalyst. Method, and it is preferable that the polymerization inhibitor is a carbon cluster (c). The carboxyl group-containing resin (P4) is a resin having a carboxyl group formed by reacting an epoxy resin (P3) with a polyfunctional carboxylic acid (e).

As an example of this embodiment, the ethylenically unsaturated resin (A4) according to this embodiment contains an epoxy group after adding a carbon cluster (c) and a catalyst as a polymerization inhibitor to the solution of the aforementioned carboxy group-containing resin (P4). It can be produced by adding an ethylenically unsaturated compound (m-1) and reacting under the same conditions as the ring-opening addition reaction of the epoxy group of the first embodiment. The carbon cluster (c) and the solvent to be used are the same as in the first embodiment.

[Fifth Embodiment]

[Ethylenically unsaturated resin (A5)]

The ethylenically unsaturated resin (A5) of the present embodiment is a resin containing an ethylenically unsaturated group obtained by adding a polybasic acid anhydride (d) to the hydroxy group of the ethylenically unsaturated resin (A2) in the second embodiment. . The hydroxy group is a hydroxy group generated by ring-opening addition of a carboxy group-containing copolymer (P2) to the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1).

The ethylenically unsaturated resin (A5) of the present embodiment contains a structural unit derived from the addition reaction of an epoxy group-containing ethylenically unsaturated compound (m-1) and a polybasic acid anhydride (d), thereby introducing a double bond having excellent photosensitivity. At the same time, a hydroxy group excellent in alkali developability can be obtained by ring opening of the epoxy group. With this structural unit, the cured product exhibits sufficient hardness and high solvent resistance. In addition, by introducing an acidic group or a hydroxy group as an alkali developable group, the affinity of the copolymer with an alkali developer is increased, a high-precision curing pattern can be formed, and strict dimensional accuracy is realized.

Further, by leaving a part of the carboxyl group in the carboxyl group-containing copolymer (P2) without reacting with the epoxy group, the carboxylic acid can also be introduced at the same time. Further, polybasic acid anhydride may be added to the obtained hydroxyl group to increase the amount of carboxylic acid introduced.

The reaction ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) is the same as the reaction ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) of the ethylenically unsaturated resin (A2) of the second embodiment.

The ratio of the polybasic acid anhydride (d) to the number of moles of the epoxy group-containing ethylenically unsaturated compound (m-1) in the ethylenically unsaturated resin (A2) is preferably 10 to 90 mol%, more preferably 30 to It is 70 mol%. When the ratio of the polybasic acid anhydride (d) is 10 mol% or more, further curability can be expressed when it is set as a photosensitive resin composition. When it is 90 mol% or less, an unreacted product of the polybasic acid anhydride (d) does not remain, and a desired ethylenically unsaturated resin (A5) is obtained.

In addition, the reaction ratio of the polybasic acid anhydride (d) is a monomer (m-1) and a monomer (m-2) constituting the carboxy group-containing copolymer (P2), an optional monomer (m-3) and/or a monomer (m When the total of -4) and the optional monomer (m-5) is 100 mol%, it is preferably 5 to 65 mol%, more preferably 5 to 50 mol%. When the blending ratio of the polybasic acid anhydride (d) is 5 mol% or more, further curability can be expressed when it is set as a photosensitive resin composition. When the blending ratio of the polybasic acid anhydride (d) is 65 mol% or less, a copolymer having a desired refractive index is obtained.

[Method for producing ethylenically unsaturated resin (A5)]

The ethylenically unsaturated resin (A5) is prepared by preparing the ethylenically unsaturated resin (A2), and then polybasic acid anhydride (d) is added, and the hydroxy group and polybasic acid anhydride (d ) Can be produced by reacting.

When reacting the polybasic acid anhydride (d), there is no particular problem even if the solvent used for the preparation of the ethylenically unsaturated resin (A2) is included, so the solvent is removed after the reaction to obtain the ethylenically unsaturated resin (A2) is completed. The reaction can be carried out without doing it.

[Sixth Embodiment]

[Ethylenically unsaturated resin (A6)]

The ethylenically unsaturated resin (A6) of the present embodiment is a resin containing an ethylenically unsaturated group obtained by adding a polybasic acid anhydride (d) to the hydroxyl group of the ethylenically unsaturated resin (A4) in the fourth embodiment. . The hydroxy group is a hydroxy group generated by ring-opening addition of a carboxy group-containing resin (P4) to the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1).

The ethylenically unsaturated resin (A6) of the present embodiment contains a structural unit derived from the addition reaction of an epoxy group-containing ethylenically unsaturated compound (m-1) and a polybasic acid anhydride (d), thereby introducing a double bond having excellent photosensitivity. At the same time, a hydroxy group excellent in alkali developability can be obtained by ring opening of the epoxy group. With this structural unit, the cured product exhibits sufficient hardness and high solvent resistance. In addition, by introducing an acidic group or a hydroxy group as an alkali developable group, the affinity of the copolymer with an alkali developer is increased, a high-precision curing pattern can be formed, and strict dimensional accuracy is realized.

Further, by leaving a part of the carboxyl group of the carboxyl group-containing resin (P4) without reacting with the epoxy group, the carboxylic acid can also be introduced at the same time. Further, polybasic acid anhydride may be added to the obtained hydroxyl group to increase the amount of carboxylic acid introduced.

The reaction ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) is the same as the reaction ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) of the ethylenically unsaturated resin (A4) of the fourth embodiment.

The ratio of the polybasic acid anhydride (d) to the number of moles of the epoxy group-containing ethylenically unsaturated compound (m-1) is preferably 10 to 90 mol%, more preferably 30 to 70 mol%.

When the ratio of the polybasic acid anhydride (d) is 10 mol% or more, further curability can be expressed when it is set as a photosensitive resin composition. When it is 90 mol% or less, an unreacted product of the polybasic acid anhydride (d) does not remain, and a desired ethylenically unsaturated resin (A6) is obtained.

Moreover, it is preferable that the reaction ratio of polybasic acid anhydride (d) is more than 0 mass%-10 mass% with respect to ethylenic unsaturated resin (A6). When the addition amount of the polybasic acid anhydride (d) exceeds 0% by mass, since the sensitivity can be increased, it is preferable. On the other hand, when the addition amount of the polybasic acid anhydride (d) is 10% by mass or less, it is preferable because the elastic recovery rate and developability can be maintained.

[Method for producing ethylenically unsaturated resin (A6)]

The ethylenically unsaturated resin (A6) is, after preparing the ethylenically unsaturated resin (A4), a polybasic acid anhydride (d) is added, and a hydroxyl group and a polybasic acid anhydride ( It can be produced by reacting d).

When reacting the polybasic acid anhydride (d), there is no particular problem even if the solvent used for the preparation of the ethylenically unsaturated resin (A4) is included, so the solvent is removed after the reaction to obtain the ethylenically unsaturated resin (A4) is completed. The reaction can be carried out without doing it.

[Characteristics of ethylenically unsaturated resin (A)]

The molecular weight (weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC)) of the ethylenically unsaturated resin (A) obtained in the first to sixth embodiments of the present invention is preferably 1000 to 50000, more Preferably it is 3000 to 40000. When this molecular weight is 1000 or more, solvent resistance and thermal decomposition resistance of a cured film can be sufficiently ensured. On the other hand, when this molecular weight is 50000 or less, the molecular weight and viscosity can be controlled in an appropriate range, and it is practical. Moreover, it is preferable that the weight average molecular weight is 3000-30000 from a viewpoint of an elastic recovery factor.

The acid value (JIS K6901 5.3) of the ethylenically unsaturated resin (A) is usually 20 to 300 KOHmg/g, preferably 30 to 200KOHmg/g. When the acid value is 20 KOHmg/g or more, developability becomes good, which is preferable. On the other hand, when the acid value is 300 KOHmg/g or less, since the exposed portion (photocured portion) becomes difficult to dissolve in an alkaline developer, it is preferable. In addition, from the viewpoint of the elastic recovery rate, the acid value of the ethylenically unsaturated resin (A) is preferably 30 to 200 KOHmg/g.

The hydroxyl group equivalent of the ethylenically unsaturated resin (A) is usually 200 to 4000 g/mol, preferably 200 to 2500 g/mol. By setting the hydroxyl equivalent weight to 4000 g/mol or less, more preferably 2500 g/mol or less, the water repellency of the alkaline developer can be suppressed, and good developability can be realized. On the other hand, if the hydroxyl equivalent weight is less than 200 g/mol, the introduction amount of other substituents required for the present invention decreases, and desired curability, thermal decomposition resistance, heat yellowing resistance, and refractive index may not be obtained.

In addition, the hydroxyl group equivalent in this specification is the mass of the ethylenically unsaturated resin (A) per mole number of hydroxy groups, and is a theoretical value calculated from the input amount of a raw material as 100% of a reaction rate.

In addition, the unsaturated group equivalent of the ethylenically unsaturated resin (A) is not limited as long as it exhibits the desired effect of the present invention, but is usually 100 to 4000 g/mol, preferably 200 to 2000 g/mol, and more preferably 300 To 500 g/mol. If the unsaturated group equivalent is 100 g/mol or more, it is preferable because it is effective in improving the coating film physical properties and alkali developability. On the other hand, if the unsaturated group equivalent is 4000 g/mol or less, since it is effective for further increasing the sensitivity, it is preferable. In addition, an unsaturated group equivalent of 100 g/mol or more is effective to further increase thermal decomposition resistance and heat yellowing resistance. Moreover, it is preferable that the unsaturated group equivalent of the ethylenic unsaturated resin (A) is 200-2000 g/mol from a viewpoint of an elastic recovery rate.

In addition, in this specification, the unsaturated group equivalent is a theoretical value calculated from the input amount when it is assumed that the raw material used for introducing the unsaturated group has reacted in its entirety.

The epoxy equivalent of the ethylenically unsaturated resin (A) used in the present invention is not limited as long as it exhibits the desired effect of the present invention, but is usually 100 to 4000 g/mol, preferably 200 to 2000 g/mol, more preferably It is 300 to 500 g/mol. When the epoxy equivalent is 100 g/mol or more, it is effective in improving the physical properties and storage stability of the coating film, and thus is preferable. Conversely, when the epoxy equivalent is 4000 g/mol or less, it is effective to further increase the solvent resistance.

In addition, the said epoxy equivalent is the mass of a polymer per 1 mole of the epoxy group of a polymer. This value can be obtained by dividing the mass of the polymer by the amount of epoxy groups in the polymer (g/mol). In the present specification, the "epoxy equivalent" is a theoretical value calculated as 100% of the reaction rate from the input amount of the raw material used to introduce the epoxy group and the amount of the carboxy group-containing compound (b) subjected to addition reaction.

[Solvent (B)]

The solvent (B) of the ethylenically unsaturated resin composition is not particularly limited as long as it is a solvent that does not react with the ethylenically unsaturated resin (A). As the solvent (B), the same solvent as the solvent used when producing the ethylenically unsaturated resin (A) can be used, and the solvent contained after the reaction may be used as it is or may be further added. Moreover, when another component is added, it may coexist there. As a specific example of the solvent (B), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, dipropylene glycol mono Methyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate, etc. Can be mentioned. These can be used alone or in combination of two or more. In addition, among these, glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, which are used when producing the ethylenically unsaturated resin (A), are preferred.

The compounding amount of the solvent (B) in the resin composition of the present embodiment is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, assuming that the total of the components excluding the solvent (B) in the composition is 100 parts by mass. Parts, more preferably 100 to 700 parts by mass. If it is a blending amount in this range, it will be a resin composition which has an appropriate viscosity.

[Reactive diluent (D)]

Although it does not specifically limit as a reactive diluent (D), It is preferable to contain an ethylenically unsaturated double bond, Preferably it is a vinyl group, and (meth)acryloyloxy group. Specific examples include aromatic vinyl monomers such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallylphthalate and diallylbenzenephosphonate; Polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethylene glycol Di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropanedi(meth)acrylate, trimethylolpropanetri( (Meth)acrylic monomers such as meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(hydroxyethyl)isocyanurate tri(meth)acrylate, etc. ; Triallyl cyanurate, etc. are mentioned. These can be used alone or in combination of two or more.

The blending amount of the reactive diluent (D) in the resin composition of the present embodiment is generally 10 to 90 parts by mass, preferably 20 to 80 parts by mass, assuming that the total of the components excluding the solvent (B) in the composition is 100 parts by mass. It is a mass part, More preferably, it is 25 to 70 mass parts. If the blending amount is within this range, a resin composition having an appropriate viscosity is obtained, and the photosensitive resin composition using the same has an appropriate photocurability.

[Photosensitive resin composition]

The photosensitive resin composition of the present invention contains an ethylenically unsaturated resin (A), a carbon cluster (c), a solvent (B), a reactive diluent (D), and a photoinitiator (E). The photosensitive resin composition of this invention may further contain a coloring agent (F).

In addition, the photosensitive resin composition of the present invention does not have to substantially contain a polymerization inhibitor other than the carbon cluster (c). "Substantially not included" means containing 0.010 parts by mass or less, preferably 0.05 parts by mass or less of a polymerization inhibitor other than the carbon cluster (c) with respect to 100 parts by mass of the ethylenically unsaturated resin (A). .

The compounding amount of the solvent (B) in the photosensitive resin composition of the present embodiment is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, assuming that the total of the components excluding the solvent (B) in the composition is 100 parts by mass. It is a mass part, More preferably, it is 100 to 700 mass parts. If it is a blending amount in this range, it will be a photosensitive resin composition which has an appropriate viscosity.

The compounding amount of the reactive diluent (D) in the photosensitive resin composition of the present embodiment is generally 10 to 90% by mass, preferably 20 when the total of the components excluding the solvent (B) in the composition is 100% by mass. It is 80 to 80 mass %, More preferably, it is 25 to 70 mass %. If the blending amount is within this range, a photosensitive resin composition having an appropriate viscosity is obtained, and the photosensitive resin composition has an appropriate photocurability.

[Photopolymerization initiator (E)]

Although it does not specifically limit as a photoinitiator (E), Specific examples include benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and alkyl ethers thereof; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-t-butyldioxy-1-methylethyl)acetophenone; Anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; Thioxanthones, such as 2,4-dimethyl thioxanthone, 2,4-diisopropyl thioxanthone, and 2-chloro thioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones, such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone ; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; Acylphosphine oxides; And xanthones. These can be used alone or in combination of two or more.

The blending amount of the photopolymerization initiator (E) in the photosensitive resin composition of the present embodiment is generally 0.1 to 30 parts by mass, preferably 0.5 when the total of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass. It is -20 mass parts, More preferably, it is 1-15 mass parts. If it is a blending amount within this range, it will be a photosensitive resin composition which has suitable photocurability.

[Coloring agent (F)]

The coloring agent (F) is not particularly limited as long as it is dissolved or dispersed in the solvent (B), and a known dye or pigment can be used. When a dye is used as the colorant (F), a colored pattern of high luminance can be obtained as compared to the case of using a pigment, and a good alkali developability is exhibited. On the other hand, when a pigment is used as the coloring agent (F), the heat resistance of the colored pattern is high compared to when a dye is used. You may use a dye and a pigment together according to the required performance or the color of a target pixel.

"dyes"

As a dye, from the viewpoint of solubility in a solvent (B) or an alkali developer, interaction with other components in the photosensitive resin composition, heat resistance, etc., an acidic dye having an acidic group such as a carboxyl group, a salt of an acidic dye with a nitrogen compound, acidic It is preferable to use a sulfonamide compound of a dye or the like. Specific examples of such dyes include acid alizarin violet N; Acid black 1, 2, 24, 48; Acid Blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; Acid chromium violet K; Acid fuxine; Acid green 1, 3, 5, 25, 27, 50; Acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; Acid violet 6B, 7, 9, 17, 19; Acid Yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; Food Yellow 3 and derivatives thereof, and the like.

Among these, an azo-based, xanthene-based, anthraquinone-based, or phthalocyanine-based acid dye is preferable. These dyes can be used alone or in combination of two or more depending on the color of the target pixel.

「Pigment」

As a specific example of a pigment, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194, 214 and the like yellow pigments; C.I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. ; C.I. Blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, and 60; C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38; C.I. Green pigments such as Pigment Green 7, 36, and 58; C.I. Brown pigments such as Pigment Brown 23 and 25; C.I. Black pigments, such as pigment black 1, 7, carbon black, titanium black, and iron oxide, etc. are mentioned. These pigments may be used singly or in combination of two or more depending on the color of the target pixel.

In the photosensitive resin composition of the present embodiment, when the colorant (F) is blended, the blending amount is generally 5 to 80 parts by mass, preferably when the total of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass. Is 5 to 70 parts by mass, more preferably 10 to 60 parts by mass.

When a pigment is used as the colorant (F), a known dispersant may be blended into the photosensitive resin composition from the viewpoint of improving the dispersibility of the pigment. As the dispersant, it is preferable to use a polymer dispersant having excellent dispersion stability over time. Examples of the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, an aliphatic modified ester dispersant, and the like. As such a polymeric dispersant, what is marketed under brand names such as EFKA (manufactured by EFKA Chemicals BV (EFKA)), Disperbyk (manufactured by Vicchemy), Dispalon (manufactured by Kusumoto Kasei Co., Ltd.), and SOLSPERSE (manufactured by Geneka Corporation). You can use it. The blending amount of the dispersant in the photosensitive resin composition of the present embodiment may be appropriately set according to the kind of pigment to be used.

[Composition of ethylenically unsaturated resin composition]

The blending amount of the ethylenically unsaturated resin (A), the carbon cluster (c), and the solvent (B) in the resin composition of the present embodiment is 100 parts by mass as the total of the components excluding the solvent (B) in the resin composition, It is preferable that the ethylenically unsaturated resin (A) is 50 to 99.9 parts by mass; It is preferable that the carbon cluster (c) is 0.00001 to 10 parts by mass; It is preferable that it is 30-1000 mass parts, it is more preferable that it is 50-800 mass parts, and it is still more preferable that it is 100-700 mass parts of solvent (B).

When the resin composition of the present embodiment contains the reactive diluent (D), the amount of the ethylenically unsaturated resin (A), the carbon cluster (c), the solvent (B), and the reactive diluent (D) is the solvent ( When the total amount of the components excluding B) is 100 parts by mass, the ethylenically unsaturated resin (A) is 10 to 90 parts by mass, the carbon cluster (c) is 0.00001 to 10 parts by mass, and the solvent (B) is 30 to 1000 parts by mass, Reactive diluent (D) is 10 to 90 parts by mass, preferably ethylenically unsaturated resin (A) is 20 to 80 parts by mass, carbon cluster (c) is 0.0001 to 0.10 parts by mass, solvent (B) is 50 to 800 Parts by mass, reactive diluent (D) is 20 to 80 parts by mass, more preferably ethylenically unsaturated resin (A) is 30 to 75 parts by mass, carbon cluster (c) is 0.0005 to 0.05 parts by mass, solvent (B) Is 100 to 700 parts by mass, and the reactive diluent (D) is 25 to 70 parts by mass.

[Composition of photosensitive resin composition]

The amount of the ethylenically unsaturated resin (A), the carbon cluster (c), the solvent (B), the reactive diluent (D), and the photopolymerization initiator (E) of the photosensitive resin composition of the present embodiment is the solvent (B) in the photosensitive resin composition. If the total of the components excluding) is 100 parts by mass, preferably 5 to 80 parts by mass of the ethylenically unsaturated resin (A), 0.00001 to 10 parts by mass of the carbon cluster (c), and 30 to 1000 parts by mass of the solvent (B) Parts, reactive diluent (D) is 10 to 90 parts by mass, photopolymerization initiator (E) is 0.1 to 30 parts by mass, more preferably ethylenically unsaturated resin (A) is 8 to 70 parts by mass, carbon cluster (c) Is 0.0001 to 5 parts by mass, solvent (B) is 50 to 800 parts by mass, reactive diluent (D) is 20 to 80 parts by mass, photopolymerization initiator (E) is 0.5 to 20 parts by mass, more preferably ethylenically unsaturated Resin (A) is 10 to 60 parts by mass, carbon cluster (c) is 0.005 to 1 parts by mass, solvent (B) is 100 to 700 parts by mass, reactive diluent (D) is 25 to 70 parts by mass, photopolymerization initiator (E ) Is 1 to 15 parts by mass.

When the photosensitive resin composition of this embodiment contains a coloring agent (F), an ethylenically unsaturated resin (A), a carbon cluster (c), a solvent (B), a reactive diluent (D), a photoinitiator (E), a coloring agent ( The blending amount of F) is generally 100 parts by mass of the total amount of the components excluding the solvent (B) in the photosensitive resin composition, the ethylenically unsaturated resin (A) is 5 to 80 parts by mass, and the carbon cluster (c) is 0.00001 to 10 Mass parts, solvent (B) is 30 to 1000 parts by mass, reactive diluent (D) is 10 to 89 parts by mass, photopolymerization initiator (E) is 0.1 to 30 parts by mass, colorant (F) is 5 to 80 parts by mass, Preferably, the ethylenically unsaturated resin (A) is 8 to 70 parts by mass, the carbon cluster (c) is 0.0001 to 0.10 parts by mass, the solvent (B) is 50 to 800 parts by mass, and the reactive diluent (D) is 20 to 80 parts by mass. Parts, the photopolymerization initiator (E) is 0.5 to 20 parts by mass, the colorant (F) is 5 to 70 parts by mass, more preferably the ethylenically unsaturated resin (A) is 10 to 60 parts by mass, and the carbon cluster (c) is 0.0005 to 0.5 parts by mass, solvent (B) is 100 to 700 parts by mass, reactive diluent (D) is 25 to 70 parts by mass, photoinitiator (E) is 1 to 15 parts by mass, colorant (F) is 10 to 60 parts by mass It's wealth.

In addition to the above components, the photosensitive resin composition of the present embodiment contains known additives such as a known coupling agent, a leveling agent, and a thermal polymerization inhibitor, and a known colorant, filler, dispersant, etc. You can do it. The blending amount of these additives is not particularly limited as long as the effect of the present invention is not impaired.

[Method for producing photosensitive resin composition]

The photosensitive resin composition of this embodiment can be manufactured by mixing each said component using a well-known mixing apparatus. In addition, the photosensitive resin composition of the present embodiment may be prepared by first preparing a resin composition containing an ethylenically unsaturated resin (A) and a solvent (B), and then mixing a reactive diluent (D) and a photopolymerization initiator (E). It is possible. In addition, the said resin composition can be used not only to prepare the photosensitive resin composition of this embodiment, but can also be used for other uses.

[Resin cured film]

Since the photosensitive resin composition of the present embodiment contains the resin of the present embodiment, a cured film having excellent developability, excellent colorant dispersibility and solvent resistance, and a high elastic recovery rate can be obtained.

Therefore, the photosensitive resin composition of this embodiment is suitable as a material for a black matrix, a color filter, and a black column spacer.

In addition, the photosensitive resin composition of the present embodiment has good dispersibility of the colorant, and even if it sufficiently contains a black colorant, it can sufficiently satisfy general properties such as developability, and has good adhesion to the surface to be formed. A film can be formed. For this reason, according to the photosensitive resin composition of this embodiment, the adhesion to the surface to be formed is good, and a black pattern having sufficient light-shielding property can be formed.

[Method of manufacturing cured resin film]

The cured resin film of this embodiment can be produced, for example, by the method shown below.

First, a photosensitive resin composition is applied on the surface to be formed of a cured resin film, and a resin layer (coating film) is formed. Subsequently, the resin layer is exposed through a mask of a predetermined pattern, and the exposed portion is photocured. Subsequently, the unexposed portion of the resin layer is developed with a developer to obtain a cured resin film having a predetermined pattern. After that, post-baking (heat treatment) of the cured resin film is performed as necessary.

When exposing the resin layer, a halftone mask having a predetermined pattern may be used. In this case, the unexposed portion and the semi-exposed portion are developed with a developer to obtain a cured resin film having a predetermined pattern.

Although it does not specifically limit as a method of coating a photosensitive resin composition, For example, a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, etc. are mentioned.

After applying the photosensitive resin composition, if necessary, the solvent (B) contained in the resin layer may be volatilized by heating using a heating means such as a circulation oven, an infrared heater, or a hot plate. The heating conditions after application are not particularly limited, and may be appropriately set according to the composition of the photosensitive resin composition. For example, the heating temperature after application may be 50°C to 120°C, and the heating time may be 30 seconds to 30 minutes.

Although it does not specifically limit as a method of exposing the resin layer, For example, a method of irradiating an active energy ray, such as ultraviolet rays and excimer laser light, is mentioned.

The energy dose to be irradiated to the resin layer may be appropriately set according to the composition of the photosensitive resin composition. For example, although the energy dose irradiated to the resin layer can be 30 to 2000 mJ/cm ² , it is not limited to this range.

Although it does not specifically limit as a light source used for exposure, A low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. can be arbitrarily selected and used.

As a developer used for development, it is preferable to use an alkaline developer because excellent developability is obtained. Examples of the alkali developer include aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide; Aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine; Tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N -Ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and p-phenyl such as sulfate, hydrochloride or p-toluenesulfonate thereof And an aqueous solution of a rendiamine compound.

The developing solution may contain a defoaming agent, a surfactant, or the like as necessary.

After developing with a developer, it is preferable to wash and dry the cured resin film having a predetermined pattern with water.

Further, after developing with a developer, it is preferable to perform post-baking (heat treatment) of a cured resin film having a predetermined pattern. By performing post-baking, the curing of the cured resin film can be further advanced. The conditions for post-baking are not particularly limited and can be selected arbitrarily, and may be appropriately set according to the composition of the photosensitive resin composition. For example, the heating temperature of the post-baking may be 130°C to 250°C. In addition, the heating time of the post-baking is preferably 10 minutes to 4 hours, more preferably 20 minutes to 2 hours.

[Image display device]

The image display device of this embodiment is provided with the cured resin film of this embodiment. As a specific example of an image display device, a liquid crystal display device, an organic EL display device, etc. are mentioned, for example.

As an image display device, it is preferable that at least one member selected from a black matrix, a color filter, and a black column spacer is formed of the cured resin film of this embodiment, for example.

The material of the substrate forming the surface to be formed of the cured resin film is not particularly limited, but for example, glass, silicone, polycarbonate, polyester, polyamide, polyamideimide, polyimide, aluminum, printed wiring board, etc. And a substrate on which a wiring pattern is formed on the surface of, an array substrate, and the like.

The manufacturing method of the image display device of this embodiment should just include the step of forming the cured resin film of this embodiment by the above-described manufacturing method, and members other than the member formed of the cured resin film can be manufactured according to a conventional method. have.

The cured resin film obtained by curing the photosensitive resin composition of the present embodiment has excellent developability, good colorant dispersibility and solvent resistance, and has a high elastic recovery rate. For this reason, it is suitable as a material for a black matrix, a color filter, and a black column spacer provided in an image display device.

Example

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by these Examples. In addition, parts and percentages in this example are all based on mass unless otherwise noted.

[Example 1]

To a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 137.5 g of propylene glycol monomethyl ether acetate was added, followed by stirring while replacing with nitrogen, and the temperature was raised to 120°C. Then, to a monomer mixture containing 141.7 g (1.00 mol) of glycidyl methacrylate, 4.7 g (0.02 mol) of tricyclodecanyl methacrylate, and 5.0 g (0.05 mol) of styrene, 13.3 g of t-butylper What added oxy-2-ethylhexanoate (polymerization initiator, Nichiyu Corporation, Perbutyl (registered trademark) O) was added dropwise from the dropping funnel to the flask over 2 hours. After completion of the dropwise addition, the mixture was further stirred at 120° C. for 2 hours to perform a copolymerization reaction, thereby producing a solution of the epoxy group-containing copolymer (P1). There was 6.0 g of a trimethylbenzene solution containing 72.0 g of acrylic acid as a monomer (m-2) and 3% by mass of fullerene (manufactured by Frontier Carbon, nanom (registered trademark) mix ST) as a polymerization inhibitor, and triphenylphosphine as a catalyst. 0.67 g (0.3 parts by mass) was added, followed by heating at 110° C. for 10 hours while blowing low-oxygen air into which nitrogen gas was injected so that the oxygen concentration became 4 to 7% by volume.

Thereafter, it was confirmed that the acid value was 1.0 KOHmg/g or less, 15.6 g of tetrahydrophthalic anhydride was added as the polybasic acid anhydride (d) and reacted at 110° C. for 2 hours, and the ethylenically unsaturated resin (A1) having a solid content concentration of 50% by mass The ethylenically unsaturated resin composition (solid acid value 32.4 KOHmg/g, weight average molecular weight 9400) which is a solution containing was obtained. In addition, the solid content means a heating residue when the ethylenically unsaturated resin (A1) solution is heated at 130° C. for 2 hours, and the ethylenically unsaturated resin (A1) is a main component.

It was 99.1% when the addition reaction rate of acrylic acid with respect to an epoxy group was calculated by measuring the acid value (monomer residual rate) in the reaction solution.

[Examples 2 to 4 and Comparative Examples 1 to 3]

In Examples 2 to 3, the addition amount of the fullerene solution was changed, and in Example 4, instead of the fullerene solution, a solution of an indene adduct of fullerene (manufactured by Frontier Carbon, nanom (registered trademark) spectra NPQ3000) (concentration 0.02% by mass) In the comparative example, except having used BHT (di-t-butylhydroxytoluene) instead of the fullerene solution, it carried out similarly to Example 1, and obtained the composition which is a solution containing an ethylenically unsaturated resin. Table 1 shows the results.

[Example 5]

In Example 5, an ethylenically unsaturated resin solution was obtained in the same manner as in Example 1 except that the polymerization inhibitor was changed to 0.02% by mass of the soot-like substance. The soot-like substance was obtained by the following method. Toluene and pure oxygen gas were supplied to the reaction tube at a ratio of 3:1, mixed, and heated under conditions of 67 hPa and 180°C to obtain soot. Subsequently, washing was performed twice with toluene to obtain a soot-like substance. Table 1 shows the results.

[Example 6]

To a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 185.6 g of propylene glycol monomethyl ether acetate was added, followed by stirring while replacing with nitrogen, and the temperature was raised to 120°C.

Subsequently, to a monomer mixture containing 58.5 g (0.68 mol) of methacrylic acid, 33.7 g (0.15 mol) of tricyclodecanyl methacrylate, and 3.0 g (0.02 mol) of benzyl methacrylate, 2.9 g of t-butylper What added oxy-2-ethylhexanoate (polymerization initiator, Nichiyu Corporation, Perbutyl (registered trademark) O) was added dropwise from the dropping funnel to the flask over 2 hours. After completion of the dropwise addition, the mixture was further stirred at 120° C. for 2 hours to perform a copolymerization reaction, thereby producing a solution of the carboxyl group-containing copolymer (P2). 3.5 g of a trimethylbenzene solution containing 35 g of glycidyl methacrylate as a monomer (m-1) and 3% by mass of fullerene (manufactured by Frontier Carbon, nanom (registered trademark) mix ST) as a polymerization inhibitor was added thereto, as a catalyst. 0.39 g (0.3 parts by mass) of triphenylphosphine was added, followed by heating at 110° C. for 10 hours while blowing low-oxygen air injected with nitrogen gas so that the oxygen concentration became 4% by volume to 7% by volume.

Thereafter, it was confirmed that the acid value was 72.0 KOHmg/g or less, and the ethylenically unsaturated resin composition as a solution containing the ethylenically unsaturated resin (A2) having a solid content concentration of 28.6% by mass (solid content acid value 196.8 KOHmg/g, weight average molecular weight 18500) Got it.

By measuring the acid value in the reaction solution, the reaction rate between the acid and the epoxy was calculated and found to be 97.8%.

[Examples 7 to 10 and Comparative Examples 4 to 6]

In Examples 6 to 8, the addition amount of the fullerene solution was changed, in Example 9, the polymerization inhibitor was changed to an indene adduct of fullerene, and in Example 10, the polymerization inhibitor was changed to a soot-like substance, and Comparative Example In the case of, an ethylenically unsaturated resin composition was obtained in the same manner as in Example 1 except that BHT was used instead of the fullerene solution. Table 2 shows the results.

[Example 11]

To a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 224.1 g of cresol novolak-based epoxy N-695 (epoxy equivalent 215) manufactured by DIC Corporation, an epoxy resin (P3), and 94.5 g of PGMEA The temperature was raised to 120°C while blowing low oxygen air injected with nitrogen gas so that the oxygen concentration was 4 to 7% by volume. Thereafter, it was confirmed that the acid value was 42.0 KOHmg/g or less, and a trimethylbenzene solution containing 3% by mass of fullerene (manufactured by Frontier Carbon, nanom (registered trademark) mix ST) in 75.1 g (1.04 mol) of acrylic acid as a monomer (m-2) What dissolved 8 g and 0.9 g of triphenylphosphine was added dropwise over 10 minutes. Thereafter, the reaction was continued until the acid value became 1 or less, and 33.4 g of succinic anhydride was added as the polybasic acid anhydride (d) and reacted at 110° C. for 1 hour, and the ethylenically unsaturated resin (A3-1) having a solid content concentration of 38.5% by weight (A3-1 ) To obtain a solution containing an ethylenically unsaturated resin composition (solid content acid value of 60.8 KOHmg/g, weight average molecular weight of 5900).

It was 99.1% when the reaction rate was calculated by measuring the acid value (monomer residual rate) in the reaction solution.

[Examples 12 to 15 and Comparative Examples 7 to 9]

In Examples 12 to 13, the addition amount of the fullerene solution was changed, in Example 14, the polymerization inhibitor was changed to an indene adduct of fullerene, and in Example 15, the polymerization inhibitor was changed to a soot substance, and Comparative Example In the same manner as in Example 9 except that BHT was used instead of the fullerene solution, an ethylenically unsaturated resin composition was obtained. Table 3 shows the results.

[Example 16]

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 64.3 g (0.30 mol) of 1,2,4-cyclohexanetricarboxylic acid as a polyfunctional carboxylic acid (e) and an epoxy resin as an epoxy resin. Add 67.1 g of AER-2603 (epoxy equivalent 188), 0.54 g of triphenylphosphine, and 88.1 g of PGMEA, manufactured by Asahi Kasei Co., Ltd. while blowing in low-oxygen air injected with nitrogen gas so that the oxygen concentration becomes 4 to 7% by volume. The temperature is raised to. Thereafter, the reaction is carried out until the acid value becomes 138 KOHmg/g or less, and after making the carboxyl group-containing resin (P4), as a monomer (m-1), 50.7 g of glycidyl methacrylate is added with fullerene (manufactured by Frontier Carbon, nanom (registered). Trademark) mix ST) What added 4.9 g of trimethylbenzene solution containing 3 mass% was dripped in 10 minutes. Solution containing ethylenically unsaturated resin (A6) having a solid content concentration of 48.5% by weight by confirming that the acid value is 40 KOHmg/g or less, adding 17.9 g of succinic anhydride as polybasic acid anhydride (d) and reacting at 110° C. for 1 hour Phosphorus ethylenically unsaturated resin composition (solid content acid value 107.8 KOHmg/g, weight average molecular weight 6100) was obtained.

It was 95.4% when the reaction rate was calculated by measuring the acid value (monomer residual rate) in the reaction solution.

[Examples 17 to 20 and Comparative Examples 10 to 12]

In Examples 17 to 18, the addition amount of the fullerene solution was changed, in Example 19, the polymerization inhibitor was changed to an indene adduct of fullerene, and in Example 20, the polymerization inhibitor was changed to a soot-like substance, and Comparative Example In the same manner as in Example 13 except having used BHT instead of the fullerene solution, an ethylenically unsaturated resin composition was obtained. Table 4 shows the results.

As for the ethylenically unsaturated resin contained in the synthesized ethylenically unsaturated resin composition, the acid value and molecular weight were measured by the following method.

[Measurement method of acid value]

In accordance with JIS K6901 5.3.2, it was measured using a mixture indicator of bromothymol blue and phenolet. It refers to the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the solid ethylenically unsaturated resin (A).

In addition, as for the solid content, the heating residue when the sample was heated at 130° C. for 2 hours was measured.

[Measurement method of weight average molecular weight (Mw)]

It measured under the following conditions using gel permeation chromatography (GPC), and converted into standard polystyrene.

Column: Shodex (registered trademark) LF-804+LF-804 (made by Showa Denko Co., Ltd.)

Column temperature: 40°C

Sample: 0.2% tetrahydrofuran solution of the copolymer

Developing solvent: tetrahydrofuran

Detector: Differential refractometer (Shōdex (registered trademark) RI-71S) (made by Showa Denko Corporation)

Flow rate: 1 mL/min

As shown in Tables 1 to 4, synthesis is possible even if the amount of fullerene as an inhibitor is reduced in Examples, but in Comparative Examples, when the amount of BHT is reduced, crosslinking of double bonds is not suppressed and gelation occurs.

[Examples 21 to 52, Comparative Examples 13 to 20]

Using the resins of Examples 1 to 20 and Comparative Examples 1, 4, 7, and 10, respectively, photosensitive resin compositions having the formulations shown in Tables 5 to 8 were prepared. In addition, the blending amount of the resin in the table was described as the value of the solid content, and the solvent contained in the synthesis of the resin was added and described in the item of "solvent" in the table.

[Evaluation of OD value]

On the glass substrate, the photosensitive resin compositions of Examples 21 to 36 and Comparative Examples 13 to 16 were used, and a coating film was produced with a spin coater so as to have a film thickness of 1.5 µm. Then, the produced coating film was heated at 90° C. for 3 minutes to volatilize the solvent in the coating film. ^{Subsequently, the entire surface of the coating film was exposed (exposure amount 200 mJ/cm 2} ) and photocured using Multilite ML-251D/B manufactured by Ushio Electric Co., Ltd. and irradiation optical unit PM25C-100. After irradiation, the film subjected to post-curing at 230°C for 30 minutes was measured for an OD value using an OD meter 361T manufactured by X-rite. Table 9 shows the results. The larger the OD value is, the more light does not pass through, which is better as a black matrix.

[Evaluation of resist pattern shape]

A coating film with a thickness of 2.5 µm was prepared by the same method as for evaluating the OD value, and a mask of a line and space pattern with a line width of 20 µm was covered on the coating film, and the multilite ML-251D/B manufactured by Ushio Denki Co., Ltd. and irradiation optics It exposed (exposure amount 50mJ/cm ² ) using the unit PM25C-100, and was photocured. After irradiation, it developed with 0.2 mass% potassium hydroxide aqueous solution for 120 seconds, and it further post-baked at 230 degreeC for 30 minutes, and obtained the target pattern. The ratio of the area at a height of 5% from the lower part and the upper part to the lower part of the pattern is referred to as T/B, and the results are shown in Table 9. The closer the T/B is to 1, the closer it is to the target pattern shape.

[Evaluation of heat yellowing resistance]

On the glass substrate, the photosensitive resin compositions of Examples 37 to 52 and Comparative Examples 17 to 20 were used, respectively, to prepare a compound having the composition shown in Table 6, and a coating film was prepared so as to have a film thickness of 2.5 µm by a spin coater. Then, the produced coating film was heated at 90° C. for 3 minutes to volatilize the solvent in the coating film. ^{Subsequently, the entire surface of the coating film was exposed (exposure amount 50 mJ/cm 2} ) and photocured using Multilite ML-251D/B manufactured by Ushio Electric Corporation and the irradiation optical unit PM25C-100. After irradiation, the absorbance of the maximum absorption wavelength of the cured resin film was measured for the film subjected to post-curing at 230°C for 30 minutes using a UV spectrum meter UV-1650PC manufactured by SIMAZU.

Table 10 shows the results. The smaller ΔEab, the less yellowing.

[Evaluation of transparency]

In the same manner as in the evaluation of heat yellowing resistance, a coating film was prepared, and the transmittance from a wavelength of 380 nm to 780 nm was measured. The average value of the transmittance at each wavelength was taken as the average transmittance (%).

Table 11 shows the results of Examples 37 to 44 and Comparative Examples 17 and 18. Table 12 shows the results of Examples 45 to 52 and Comparative Examples 19 and 20.

As shown in Tables 9 to 10, it can be seen that the photosensitive resin containing the carbon cluster (c) is excellent in dispersibility of the colorant, and a cured product excellent in pattern shape and heat yellowing resistance is obtained. In addition, as shown in Tables 11 and 12, it can be seen that the photosensitive resin using the ethylenically unsaturated resin synthesized using the carbon cluster (c) has improved transparency.

Claims (13)

Ethylenically unsaturated resin (A),
Carbon clusters (c) and,
Solvent (B)
Contains,
The carbon cluster (c) is at least one of fullerene and a soot-like substance, and the content thereof is 0.00001 to 10 parts by mass based on 100 parts by mass of the ethylenically unsaturated resin (A).
Ethylenically unsaturated resin composition, characterized in that. The hydroxy group according to claim 1, wherein the ethylenically unsaturated resin (A) is a hydroxy group generated by ring-opening addition of a carboxy group-containing ethylenically unsaturated compound (m-2) to the epoxy group of the epoxy group-containing copolymer (P1), and the epoxy group It is an ethylenically unsaturated resin (A1) obtained by adding a polybasic acid anhydride (d) to
The epoxy group-containing copolymer (P1) is
Constituent units derived from epoxy group-containing (meth)acrylate (m-1) and
At least 1 selected from the group consisting of a structural unit derived from a polymerizable monomer (m-3) having a C10 to C20 interchangeable hydrocarbon group and a structural unit derived from a polymerizable monomer (m-4) represented by the following formula (1) Bell
Which is a copolymer containing
Ethylene unsaturated resin composition.

(X and X'in formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R1 and R2 are each independently a hydrogen atom, a carboxyl group, or a carbon number which may have a substituent. It is a hydrocarbon group of 1 to 20, and may have a cyclic structure connecting R1 and R2.) The ethylenic unsaturated group-containing ethylenic resin according to claim 1, wherein the ethylenically unsaturated resin (A) is formed by ring-opening addition of a carboxy group-containing copolymer (P2) to the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1). It is an unsaturated resin (A2),
The carboxy group-containing copolymer (P2) is
A structural unit derived from an ethylenically unsaturated compound (m-2) containing a carboxyl group, and
At least 1 selected from the group consisting of a structural unit derived from a polymerizable monomer (m-3) having a C10 to C20 interchangeable hydrocarbon group and a structural unit derived from a polymerizable monomer (m-4) represented by the following formula (1) Bell
Which is a copolymer containing
Ethylene unsaturated resin composition.

(X and X'in formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R1 and R2 are each independently a hydrogen atom, a carboxyl group, or a carbon number which may have a substituent. It is a hydrocarbon group of 1 to 20, and may have a cyclic structure connecting R1 and R2.) The polybasic acid according to claim 1, wherein the ethylenically unsaturated resin (A) is added to the epoxy group of the epoxy resin (P3) by ring-opening addition of the ethylenically unsaturated compound (m-2) containing a carboxyl group, and the hydroxy group generated by the ring opening of the epoxy group. It is an ethylenically unsaturated resin (A3) obtained by adding an anhydride (d),
The epoxy resin (P3) is
At least one selected from the group consisting of a novolak type epoxy resin (P3-1), a bisphenol type epoxy resin (P3-2), and a bifunctional epoxy resin having a biphenyl skeleton (P3-3)
Ethylene unsaturated resin composition. The ethylenically unsaturated resin (A4) according to claim 1, wherein the ethylenically unsaturated resin (A) is formed by ring-opening addition of a carboxy group-containing resin (P4) to the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1). ),
The carboxyl group-containing resin (P4) is a resin having a carboxyl group formed by reacting an epoxy resin (P3) with a polyfunctional carboxylic acid (e),
The epoxy resin (P3) is
At least one selected from the group consisting of a novolak type epoxy resin (P3-1), a bisphenol type epoxy resin (P3-2), and a bifunctional epoxy resin having a biphenyl skeleton (P3-3)
Ethylene unsaturated resin composition. The method of claim 1, wherein the ethylenically unsaturated resin (A) is
An ethylenically unsaturated resin (A5) obtained by adding a polybasic acid anhydride (d) to the hydroxy group of the ethylenically unsaturated resin (A2) according to claim 3, or
It is an ethylenically unsaturated resin (A6) obtained by adding a polybasic acid anhydride (d) to the hydroxy group of the ethylenically unsaturated resin (A4) according to claim 5,
Ethylene unsaturated resin composition. The method according to any one of claims 1 to 6, wherein the carbon cluster (c) is an unsubstituted fullerene.
Ethylene unsaturated resin composition. The method according to any one of claims 1 to 7, which is substantially free of polymerization inhibitors other than carbon clusters (c).
Ethylene unsaturated resin composition. The method according to any one of claims 1 to 8, further comprising a reactive diluent (D)
Ethylene unsaturated resin composition. The ethylenically unsaturated resin composition according to any one of claims 1 to 9, and
Photopolymerization initiator (E)
Photosensitive resin composition containing. The method according to claim 10, further containing a colorant (F),
The colorant (F) is at least one selected from the group consisting of dyes and pigments
Photosensitive resin composition. The method according to claim 10 or 11, which substantially does not contain a polymerization inhibitor other than carbon cluster (c).
Photosensitive resin composition. A resist using the photosensitive resin composition according to any one of claims 10 to 12.