CN111868628B - Alkali-developable photocurable and thermosetting resin composition - Google Patents

Abstract

[ Problem ] to provide: a resin composition which is excellent in resolution, sensitivity and the like even when stored for a long period of time and has excellent adhesion. [ solution ] an alkali-developable photocurable/thermosetting resin composition composed of at least a two-component system, which contains at least: the alkali-soluble resin, the photopolymerization initiator having an oxime bond, the reactive diluent, the thermosetting resin, and the solvent are mixed in different compositions, and the solvent mixed with the photopolymerization initiator having an oxime bond contains 50 mass% or more of the ketone-based solvent in the solvent.

Description

Alkali-developable photocurable and thermosetting resin composition

Technical Field

The present invention relates to an alkali-developable photocurable and thermosetting resin composition composed of at least two components.

Background

As one of the components of a curable resin composition that can be used in an alkali-developable liquid resist composition, an alkali-developable photosensitive masking agent, or the like, a photopolymerization initiator having an oxime bond has been conventionally used (for example, patent document 1).

Prior art literature

Patent literature

Patent document 1: japanese patent application laid-open No. 2011-022328

Patent document 2: international publication No. 2012/043001

Disclosure of Invention

Problems to be solved by the invention

The photopolymerization initiator having an oxime bond is a component that can be used for curable resin compositions for high-definition materials requiring high sensitivity, and on the other hand, the optical characteristics such as sensitivity and resolution of a curable resin composition containing the photopolymerization initiator having an oxime bond gradually decrease when stored. Therefore, it is difficult to provide a curable resin composition excellent in light characteristics and the like even after long-term storage.

For such a problem, for example, patent document 2 proposes the following: the photopolymerization initiator having an oxime bond and the carboxyl group-containing resin are separated into two components for storage, thereby reducing the deactivation.

However, since a composition having high black or the like such as an alkali-developable photosensitive masking agent has poor light transmission, if the compounding amount of a photopolymerization initiator having an oxime bond with high sensitivity is increased for the purpose of improving sensitivity in such a composition, the deactivation may be reduced by forming two components as described above, but it is not complete, and in addition, the photopolymerization initiator having an oxime bond may recrystallize to generate coarse particles. In particular, in the case of a masking agent, pinholes are generated in the region where coarse particles of a cured coating film of the masking agent are generated due to the generation of coarse particles, and there is a concern that the appearance is poor.

In view of the above, an object of the present invention is to provide: a resin composition which is excellent in resolution, sensitivity and the like even when stored for a long period of time, has excellent adhesion, and can prevent recrystallization.

Solution for solving the problem

The present inventors have conducted intensive studies and as a result found that: the photopolymerization initiator having an oxime bond is excellent in solubility in a specific solvent, can reduce deactivation of the photopolymerization initiator having an oxime bond, and can also prevent recrystallization.

The present invention is an alkali-developable photocurable and thermosetting resin composition comprising at least a two-component system, characterized by comprising at least: an alkali-soluble resin, a photopolymerization initiator having an oxime bond, a reactive diluent, a thermosetting resin, a solvent,

The photopolymerization initiator having an oxime bond and the alkali-soluble resin are mixed in different compositions, and a solvent mixed with the photopolymerization initiator having an oxime bond contains 50 mass% or more of a ketone solvent in the solvent.

The solvent to be compounded with the photopolymerization initiator having an oxime bond is preferably an ether-based solvent.

Preferably, the alkali-developable photocurable and thermosetting resin composition further contains a colorant.

The colorant preferably contains carbon black and a mixed-color black-based colorant, and the content of the carbon black is preferably 4 to 10 mass% and the content of the mixed-color black-based colorant is preferably 8 to 20 mass% in terms of solid content conversion relative to the total amount of the alkali-developable photocurable and thermosetting resin composition.

Preferably, the reactive diluent contains a (meth) acrylate having a 2-or more function modified with either one of an alkylene oxide and a lactone.

The alkali-developable photocurable and thermosetting resin composition is preferably used for a glass substrate.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there may be provided: the resin composition is excellent in resolution, sensitivity and adhesion even when stored for a long period of time, and can prevent recrystallization.

Detailed Description

Hereinafter, the alkali-developable photocurable and thermosetting resin composition (hereinafter, may be simply referred to as "curable resin composition") of the present invention will be specifically described, but the present invention is not limited to these.

In the case where an isomer exists in the compound described above, all possible isomers may be used in the present invention as long as they are not particularly limited.

In the present specification, (meth) acrylate is a term generically referring to acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions.

The solid component means, unless otherwise specified, a component constituting the composition other than a solvent (in particular, an organic solvent), or a mass or a volume thereof.

The curable resin composition of the present invention is an alkali-developable photocurable and thermosetting resin composition comprising at least a two-component system, and comprises at least: an alkali-soluble resin, a photopolymerization initiator having an oxime bond, a reactive diluent, a thermosetting resin, and a solvent, wherein the photopolymerization initiator having an oxime bond is compounded in at least a composition different from the alkali-soluble resin, and the solvent compounded with the photopolymerization initiator having an oxime bond is a ketone solvent.

The curable resin composition of the present invention is, in other words, a photocurable and thermosetting composition (photocurable and thermosetting material) containing at least (a) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a reactive diluent, (D) a thermosetting resin and (E) a solvent, and is an alkali-developable photocurable and thermosetting resin composition (alkali-developable photocurable and thermosetting material) composed of at least two components (3 or more) of a 1 st composition containing at least (a) an alkali-soluble resin and a2 nd composition containing (B-1) a photopolymerization initiator { below called "oxime-type photopolymerization initiator" }) as (B) a photopolymerization initiator and (E-1) a ketone-type solvent as (E) in an amount of 50 mass% or more in a solvent.

The curable resin composition of the present invention may contain other component (F) within a range that does not hinder the effects of the present invention.

The components of the curable resin composition of the present invention are classified as follows.

(As essential components, the components contained in the composition 1)

(A) Alkali-soluble resin

(As an essential component, a component contained in the composition of item 2)

(B-1) an oxime-based photopolymerization initiator

(E-1) Ketone solvent

(Optional ingredients included in any or all of the compositions as essential ingredients)

(C) Reactive diluents

(D) Thermosetting resin

(Optional component)

(E) Solvent(s)

(B-2) photopolymerization initiator other than oxime system

(F) Other ingredients

The components of the curable resin composition of the present invention will be described below.

Here, as the other component (F), a colorant is particularly preferably contained. Hereinafter, the components (a) to (E) and the colorant will be described, and the components (F) other than the colorant will be described.

[ (A) alkali-soluble resin ]

As the alkali-soluble resin, a known one can be used, and a carboxyl group-containing resin or a phenolic hydroxyl group-containing resin is preferably used. In particular, if a carboxyl group-containing resin is used, it is more preferable in view of developability. The alkali-soluble resin may be used alone or in combination of 2 or more.

As the carboxyl group-containing resin, particularly, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in a molecule is more preferable as a composition for alkali development from the viewpoints of photocurability and development resistance. Furthermore, the unsaturated double bond thereof is preferably derived from acrylic acid or methacrylic acid, or derivatives thereof.

(I) Carboxyl group-containing resins obtained by copolymerizing unsaturated carboxylic acids such as (meth) acrylic acid with unsaturated group-containing compounds such as styrene, α -methylstyrene, lower alkyl (meth) acrylate, isobutylene and the like.

(II) a carboxyl group-containing polyurethane resin obtained by polyaddition reaction of a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate, a carboxyl group-containing diol compound such as dimethylolpropionic acid or dimethylolbutyric acid, and a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(III) carboxyl group-containing photosensitive polyurethane resins obtained by addition polymerization of diisocyanates, (meth) acrylic acid esters or partial anhydride modifications thereof with 2-functional epoxy resins such as bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, xylenol (bixylenol) type epoxy resins, bisphenol type epoxy resins, and the like, carboxyl group-containing diol compounds and glycol compounds.

(IV) in the synthesis of the resin of the above (II) or (III), a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups in the molecule, such as hydroxyalkyl (meth) acrylate, is added, and the carboxyl group-containing photosensitive polyurethane resin is terminally (meth) acrylated.

(V) in the synthesis of the resin of the above (II) or (III), a carboxyl group-containing photosensitive polyurethane resin having been (meth) acrylated at the end thereof is obtained by adding a compound having 1 isocyanate group and 1 or more (meth) acryloyl groups in the molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate.

(VI) a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional (solid) epoxy resin having a 2-function or more with (meth) acrylic acid, and adding a dibasic acid anhydride to a hydroxyl group present in a side chain.

(VII) a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a 2-functional (solid) epoxy resin with epichlorohydrin with (meth) acrylic acid, and adding a dibasic acid anhydride to the hydroxyl group thus formed.

(VIII) a carboxyl group-containing polyester resin obtained by reacting a 2-functional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid, and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the primary hydroxyl group formed.

(IX) a carboxyl group-containing resin obtained by reacting an epoxy compound having a plurality of epoxy groups in the 1-molecule with a compound having at least 1 alcoholic hydroxyl group and 1 phenolic hydroxyl group in the 1-molecule, such as p-hydroxyphenylethanol, with an unsaturated group-containing monocarboxylic acid, such as (meth) acrylic acid, and reacting the alcoholic hydroxyl groups of the obtained reaction product with a polybasic acid anhydride, such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, and the like.

(X) a carboxyl group-containing photosensitive resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule with an alkylene oxide such as ethylene oxide or propylene oxide to obtain a reaction product, reacting the obtained reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the obtained reaction product with a polybasic acid anhydride.

(XI) a carboxyl group-containing photosensitive resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate to obtain a reaction product, reacting the obtained reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the obtained reaction product with a polybasic acid anhydride.

(XII) A carboxyl group-containing photosensitive resin obtained by adding a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in 1 molecule to the resins of the above (I) to (XI).

The acid value of the carboxyl group-containing resin is preferably in the range of 20 to 200mgKOH/g, more preferably in the range of 40 to 150 mgKOH/g. When the acid value of the carboxyl group-containing resin is 20mgKOH/g or more, the adhesiveness of the coating film becomes good, and alkali development becomes good. On the other hand, when the acid value is 200mgKOH/g or less, dissolution of the exposed portion by the developer can be suppressed, and therefore, narrowing of the line to a desired level or dissolution and peeling of the exposed portion and the unexposed portion in the developer can be suppressed as the case may be, and a resist pattern can be favorably drawn.

The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, and is preferably in the range of 2000 to 150000, more preferably 5000 to 100000. When the weight average molecular weight is 2000 or more, the tack-free performance is good, the moisture resistance of the coating film after exposure is good, the film loss can be suppressed during development, and the resolution can be suppressed from decreasing. On the other hand, when the weight average molecular weight is 150000 or less, the developability is good and the storage stability is also excellent.

The carboxyl group-containing resin may be used alone or in combination of 2 or more. When the curable resin composition of the present invention contains 2 or more carboxyl group-containing resins, it is preferable that the curable resin composition contains the carboxyl group-containing photosensitive resin (A1) described above, for example.

In another embodiment, the curable resin composition of the present invention may contain, as the carboxyl group-containing resin, the carboxyl group-containing photosensitive resin (A1) and the carboxyl group-containing acrylic copolymer having no alicyclic skeleton. The carboxyl group-containing acrylic copolymer having no alicyclic skeleton includes (1) a styrene-copolymerized carboxyl group-containing resin exemplified as the specific example of the above carboxyl group-containing resin. The ratio of the carboxyl group-containing resin to be blended is, for example, 10 to 95 parts by mass, preferably 10 to 80 parts by mass, based on 100 parts by mass of the entire carboxyl group-containing resin.

The phenolic hydroxyl group-containing resin is not particularly limited as long as it has a phenolic hydroxyl group in the main chain or side chain, that is, a hydroxyl group bonded to a benzene ring. Preferably, the compound has 2 or more phenolic hydroxyl groups in 1 molecule. Examples of the compound having 2 or more phenolic hydroxyl groups in 1 molecule include: catechol, resorcinol, hydroquinone, dihydroxytoluene, naphthalene diol, t-butylcatechol, t-butylhydroquinone, pyrogallol, phloroglucinol, bisphenol a, bisphenol F, bisphenol S, biphenol, bixylenol, novolak type phenol resins, novolak type alkylphenol resins, novolak type resins of bisphenol a, dicyclopentadiene type phenol resins, xylok type phenol resins, terpene modified phenol resins, polyvinyl phenols, condensates of phenols with aromatic aldehydes having phenolic hydroxyl groups, condensates of 1-naphthol or 2-naphthol with aromatic aldehydes, and the like, but are not limited thereto. The phenolic hydroxyl group-containing compound may be used alone or in combination of 2 or more.

The content of the alkali-soluble resin is not particularly limited, and may be 10 to 95 mass%, preferably 10 to 80 mass%, based on the solid content of the curable resin composition.

[ (B) photopolymerization initiator ]

(B-1) oxime-based photopolymerization initiator

As the oxime photopolymerization initiator, a known one can be used. The oxime photopolymerization initiator may be used alone or in combination of 2 or more.

The oxime-based photopolymerization initiator is preferably an oxime-ester-based photopolymerization initiator including a structural moiety represented by the following general formula (I), and more preferably an oxime-ester-based photopolymerization initiator further having a carbazole structure. As the oxime ester-based photopolymerization initiator having a carbazole structure, a dimer oxime ester-based photopolymerization initiator may be used.

In the general formula (I), R1 represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group. R2 represents phenyl, alkyl, cycloalkyl, alkanoyl or benzoyl.

The phenyl group represented by R1 and R2 may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, and the like.

The alkyl group represented by R1 and R2 is preferably an alkyl group having 1 to 20 carbon atoms, and may contain 1 or more oxygen atoms in the alkyl chain. In addition, the hydroxyl group may be substituted with 1 or more hydroxyl groups.

Cycloalkyl groups represented by R1 and R2 are preferably cycloalkyl groups having 5 to 8 carbon atoms.

The alkanoyl group represented by R1 and R2 is preferably an alkanoyl group having 2 to 20 carbon atoms.

The benzoyl group represented by R1 and R2 may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like.

Examples of the oxime ester photopolymerization initiator including a structural moiety represented by the general formula (I) include: and oxime ester compounds having a carbazole skeleton such as 1, 2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime) ], compounds represented by the following formula (I-1), 2- (acetoxyiminomethyl) thioxanthen-9-one, and 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyloxime) and compounds represented by the following formula (I-2).

In the general formula (I-2), R11 has the same meaning as R1 in the general formula (I), and R12 and R14 each independently have the same meaning as R2 in the general formula (I). R13 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms (in the case where the carbon number of the alkyl group constituting the alkoxy group is 2 or more, the alkyl group is optionally substituted with 1 or more hydroxyl groups, and optionally has 1 or more oxygen atoms in the middle of the alkyl chain) or a phenoxycarboxyl group.

Such an oxime ester photopolymerization initiator is preferable because it can improve the sensitivity and resolution of the curable resin composition of the present invention with respect to, for example, exposure for direct imaging. In addition, the oxime ester-based photopolymerization initiator may be a dimer.

The oxime ester-based photopolymerization initiator of the dimer is more preferably a compound represented by the following general formula (I-3).

In the general formula (I-3), R23 represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group, or a naphthyl group. R21 and R22 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen group, a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, a benzofuranyl group, or a benzothienyl group.

Ar represents a single bond, or an alkylene group having 1 to 10 carbon atoms, a vinylidene group, a phenylene group, a biphenylene group, a pyridylene group, a naphthylene group, an anthrylene group, a thienylene group (thienylene), a furanylene group (furylene), a2, 5-pyrrolediyl group, a 4,4 '-stilbene-diyl group, or a 4,2' -styrene-diyl group.

N represents an integer of 0 to 1.

As the alkyl group represented by R23, an alkyl group having 1 to 17 carbon atoms is preferable.

The alkoxy group represented by R23 is preferably an alkoxy group having 1 to 8 carbon atoms.

The phenyl group represented by R23 may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), an amino group, an alkylamino group (preferably having 1 to 8 carbon atoms in the alkyl group), and a dialkylamino group (preferably having 1 to 8 carbon atoms in the alkyl group).

The naphthyl group represented by R23 may have a substituent, and examples of the substituent include the same substituents as those that the phenyl group represented by R23 may have.

As the alkyl group represented by R21 and R22, an alkyl group having 1 to 17 carbon atoms is preferable.

The alkoxy group represented by R21 and R22 is preferably an alkoxy group having 1 to 8 carbon atoms.

The phenyl group represented by R21 and R22 may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), an amino group, an alkylamino group (preferably having 1 to 8 carbon atoms in the alkyl group), and a dialkylamino group (preferably having 1 to 8 carbon atoms in the alkyl group).

The naphthyl group represented by R21 and R22 may have a substituent, and examples of the substituent include the same substituents as those that the phenyl group represented by R21 and R22 may have.

In the general formula (I-3), R21 and R23 are each independently a methyl group or an ethyl group, R22 is a methyl group or a phenyl group, ar is preferably a single bond, or a phenylene group, a naphthylene group or a thienylene group, and n is preferably 0.

As the compound represented by the general formula (I-3), the following compounds are more preferable.

As the photopolymerization initiator of (B) oxime ester, there may be mentioned, as commercial products: CGI-325, irgacure OXE01 (1- [4- (phenylthio) ] -1, 2-octanedione 2- (O-benzoyloxime), irgacure OXE02 (1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetoxime), N-1919, NCI-831, manufactured by ADEKA, inc., TR-PBG-304, manufactured by Hemsy, kogyo Chemicals, inc., TOE-04-A3, etc. manufactured by Japan chemical industry Co., ltd.

The content of the oxime ester photopolymerization initiator is not particularly limited, and may be set to 0.01 to 20 parts by mass per 100 parts by mass of the alkali-soluble resin.

The curable resin composition of the present invention may contain other photopolymerization initiators. Examples of the other photopolymerization initiator include known and commonly used compounds such as benzophenone-based, acetophenone-based, aminoacetophenone-based, benzoin ether-based, benzil ketal-based, acylphosphine oxide-based, oxime ether-based, and titanocene-based.

In order to improve the sensitivity to exposure, it is preferable to use a combination of an α -aminoacetophenone-based photopolymerization initiator or the like containing a structural moiety represented by the general formula (II).

In the general formula (II), R3 and R4 each independently represent an alkyl group or an arylalkyl group having 1 to 12 carbon atoms, and R5 and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or 2 may be bonded to form a cyclic alkyl ether group.

Examples of the α -aminoacetophenone photopolymerization initiator including a structural moiety represented by the general formula (II) include: 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone, N-dimethylaminoacetophenone, and the like.

[ (B-2) photopolymerization initiator other than oxime System ]

As the photopolymerization initiator other than the oxime system, a known one can be used. The oxime photopolymerization initiator may be used alone or in combination of 2 or more.

Examples of the photopolymerization initiator other than the oxime type include known and commonly used compounds such as benzophenone type, acetophenone type, aminoacetophenone type, benzoin ether type, benzil ketal type, acylphosphine oxide type, oxime ether type, and titanocene type.

[ (C) reactive diluent ]

As the reactive diluent, a known one can be used. The reactive diluent may be used alone or in combination of 2 or more.

The reactive diluent is a compound having multiple bonds (double bonds and triple bonds) between carbons in a molecule, in other words, a photocurable monomer. As such a reactive diluent, there may be mentioned: alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; mono-or di (meth) acrylic acid esters of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol and trihydroxyethyl isocyanurate, and polyvalent (meth) acrylates of ethylene oxide or propylene oxide adducts thereof; (meth) acrylic esters of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A; (meth) acrylic esters of glycidyl ethers such as diglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; and melamine (meth) acrylate; and the like are known (meth) acrylates.

The content of the reactive diluent in the curable resin composition of the present invention is not particularly limited, and may be, for example, 5 to 45 parts by mass (preferably 5 to 40 parts by mass) with respect to 100 parts by mass of the alkali-soluble resin.

Here, the curable resin composition of the present invention can reduce deactivation of the photopolymerization initiator having an oxime bond, and thus can be suitably used for a black mask or the like containing a photopolymerization initiator having high sensitivity.

When the curable resin composition of the present invention is used as a black shielding agent (alkali-developable photosensitive black shielding agent), the photocurable monomer, which is a reactive diluent of the present invention, preferably contains a (meth) acrylate { hereinafter, referred to as "(meth) acrylate (c)" } having a2 or more functions (preferably 3 or more functions) modified with any one of an alkylene oxide and a lactone. Thus, a black shielding agent having excellent adhesion to a glass substrate can be provided. In the case of containing the (meth) acrylate (c), the alkali-soluble resin (a) is preferably a carboxyl group-containing resin.

Here, the (meth) acrylate (c) may be modified with at least a part of the (meth) acrylate having a 2-functional group or more by alkylene oxide or lactone. The (meth) acrylate (c) may be modified with both alkylene oxide and lactone.

The alkylene oxide is not particularly limited, but ethylene oxide and propylene oxide are preferable.

The lactone is not particularly limited, but caprolactone is preferable.

The modified portion of the alkylene oxide and lactone in the (meth) acrylate (c) may have a repeating structure.

Specific examples of the (meth) acrylic acid ester (c) include (meth) acrylic acid esters obtained by modifying 2 or more functional (meth) acrylic acid esters of the above known (meth) acrylic acid esters with any one of alkylene oxide and lactone, for example, alkylene oxide adduct polyols or lactone adduct polyols. More specifically, the (meth) acrylic acid ester (c) may be: EO-modified trimethylolpropane triacrylate, EO-modified pentaerythritol tetraacrylate, EO-modified di (trimethylolpropane) tetraacrylate, EO-modified dipentaerythritol hexaacrylate, EO-modified triacrylate, EO-modified fluorene diacrylate, EO-modified bisphenol A epoxy diacrylate, EO-modified bisphenol F epoxy diacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol F diacrylate, EO-modified glycerol diglycidyl ether (meth) acrylate, EO-modified trimethylolpropane triglycidyl ether (meth) acrylate, EO-modified triglycidyl isocyanurate (meth) acrylate, caprolactone-modified dipentaerythritol hexaacrylate, caprolactone-modified isocyanurate triacrylate, and the like. Among them, EO-modified trimethylolpropane triacrylate and caprolactone-modified dipentaerythritol hexaacrylate are preferable.

When (meth) acrylate (c) is used as the photocurable monomer, 1 (meth) acrylate (c) may be used alone, and 2 or more (meth) acrylates (c) may be used in combination. Further, the (meth) acrylate (c) may be used in combination with a photocurable monomer other than the (meth) acrylate (c) (hereinafter referred to as "other photocurable monomer").

The other photocurable monomer is not particularly limited, and the above-mentioned known (meth) acrylate and the like can be used.

The content of the (meth) acrylic acid ester (c) is preferably 10 to 45 parts by mass based on 100 parts by mass of the alkali-soluble resin (a) (preferably, carboxyl-containing resin). When the content of the (meth) acrylic acid ester (c) is 10 parts by mass or more, a good resolution can be obtained. In addition, when the amount is 45 parts by mass or less, a coating film having good tackiness (no negative adhesion) can be obtained.

In the case of compounding other photocurable monomer, the total content of the (meth) acrylic acid ester (c) and the other photocurable monomer is preferably 10 to 45 parts by mass with respect to 100 parts by mass of the (a) alkali-soluble resin (preferably carboxyl-containing resin), and the other photocurable monomer is preferably 0 to 50% by weight.

[ (D) Heat-curable resin ]

As the thermosetting resin, a known one can be used. The thermosetting resin may be used alone or in combination of 2 or more.

Examples of the thermosetting resin include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, and benzoguanamine derivatives, isocyanate compounds, blocked isocyanate compounds, cyclic carbonate compounds, epoxy compounds, oxetane compounds, episulfide resins, bismaleimides, and carbodiimide resins.

As the thermosetting resin, a thermosetting resin having a plurality of cyclic ether groups or cyclic thioether groups { hereinafter, referred to as "cyclic (thio) ether groups" } in the molecule is preferable.

The thermosetting resin having a plurality of cyclic (thio) ether groups in the molecule is a compound having a plurality of cyclic (thio) ether groups of 3-membered, 4-membered or 5-membered rings in the molecule, and examples thereof include: a compound having a plurality of epoxy groups in the molecule, namely, a polyfunctional epoxy compound; a compound having a plurality of oxetanyl groups in the molecule, namely, a polyfunctional oxetane compound; and a compound having a plurality of thioether groups in the molecule, namely, an episulfide resin.

Examples of the polyfunctional epoxy compound include: epoxidizing vegetable oil; bisphenol a type epoxy resin; hydroquinone-type epoxy resins; bisphenol type epoxy resin; a thioether type epoxy resin; a brominated epoxy resin; novolac type epoxy resin; bisphenol novolac type epoxy resin; bisphenol F type epoxy resin; hydrogenated bisphenol a type epoxy resin; glycidol amine type epoxy resin; hydantoin type epoxy resins; alicyclic epoxy resin; a trihydroxyphenyl methane type epoxy resin; a bixylenol-type or biphenol-type epoxy resin or a mixture thereof; bisphenol S-type epoxy resin; bisphenol a novolac type epoxy resin; a tetrahydroxyphenyl ethane type epoxy resin; a heterocyclic epoxy resin; a diglycidyl phthalate resin; tetraglycidyl ditolyl ethane resin; naphthalene group-containing epoxy resins; an epoxy resin having a dicyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resin; copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate; an epoxy-modified polybutadiene rubber derivative; CTBN modified epoxy resins, etc., but are not limited thereto. These epoxy resins may be used singly or in combination of 2 or more.

Examples of the polyfunctional oxetane compound include polyfunctional oxetanes such as bis [ (3-methyl-3-oxetanylmethoxy) methyl ] ether, bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] ether, 1, 4-bis [ (3-methyl-3-oxetanylmethoxy) methyl ] benzene, 1, 4-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] benzene, (3-methyl-3-oxetanylmethyl) acrylate, (3-ethyl-3-oxetanylmethyl) methyl methacrylate, and oligomer or copolymer thereof, and etherified resins having a hydroxyl group such as oxetane alcohol and a varnish resin, poly (p-hydroxystyrene), cardo-bisphenol, calixarene, resorcinol calixarene, or silsesquioxane. Further, there may be mentioned: copolymers of unsaturated monomers having an oxetane ring with alkyl (meth) acrylates, and the like.

Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol a type episulfide resin and the like. In addition, it is also possible to use: and episulfide resins obtained by substituting an oxygen atom of an epoxy group of a novolak type epoxy resin with a sulfur atom by the same synthesis method.

Examples of the amino resin such as melamine derivative and benzoguanamine derivative include methylolmelamine compound, methylolbenzoguanamine compound, methylolglycourea compound and methylol urea compound.

As the isocyanate compound, a polyisocyanate compound may be compounded. The polyisocyanate compound may be: aromatic polyisocyanates such as 4,4' -diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, naphthylene-1, 5-diisocyanate, phthalene diisocyanate, m-xylylene diisocyanate, and 2, 4-toluene diisocyanate dimers; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; alicyclic polyisocyanates such as bicycloheptane triisocyanate; and adducts, biurets, isocyanurates, and the like of the above-listed isocyanate compounds.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. Examples of the isocyanate compound capable of reacting with the isocyanate blocking agent include the polyisocyanate compound described above. Examples of the isocyanate blocking agent include phenol blocking agents; a lactam-based capping agent; an active methylene-based capping agent; an alcohol-based capping agent; an oxime-based blocking agent; a thiol-based capping agent; an amide-based end-capping agent; an imide-based capping agent; an amine-based capping agent; imidazole-based capping agents; imine-based capping agents, and the like.

The content of the thermosetting resin is not particularly limited, and may be set to 0.6 to 2.8 equivalents or the like relative to 1 equivalent of the alkali-soluble group (carboxyl group, phenolic hydroxyl group) of the alkali-soluble resin.

[ (E) solvent ]

(E) The solvent includes (E-1) a ketone solvent and (E-2) a solvent other than the ketone solvent. Hereinafter, each will be described.

(E-1) Ketone solvent

As the ketone solvent, a known solvent can be used. The ketone solvent may be used alone or in combination of 2 or more.

Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl butyl ketone, and methyl isobutyl ketone. Among them, cyclohexanone is preferable.

Solvents other than (E-2) ketones

As the solvent other than ketone, a known solvent can be used. The solvent other than ketone may be used alone or in combination of 1 or more than 2.

Examples of the solvents other than ketones include aromatic hydrocarbon solvents such as toluene, xylene, and tetramethylbenzene; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; alcohol solvents such as ethanol, propanol, 2-methoxypropanol, n-butanol, isobutanol, isoamyl alcohol, ethylene glycol, and propylene glycol; aliphatic hydrocarbon solvents such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha; and N, N-Dimethylformamide (DMF), tetrachloroethylene, terpineol, and the like.

Here, conventionally, an ether solvent or the like has been used as a solvent, but when the ether solvent and the oxime polymerization photoinitiator are simultaneously mixed and stored, it is determined that the oxime polymerization initiator is deactivated. The use of a ketone solvent in place of an ether solvent makes it possible to form a two-component structure without deactivation or recrystallization and without simultaneous compounding with a carboxyl group, and thus, the composition is excellent in storage stability and can be suitably used as a masking material. Therefore, the 2 nd composition containing the oxime-based photopolymerization initiator preferably contains no solvent other than ketone-based one. More specifically, the 1 st composition is not particularly limited, but may be a (E-1) ketone solvent or a solvent other than (E-2) ketone, and the 2 nd composition is a composition in which the solvent is selected from (E-1) ketone solvents, and the ketone solvent must be contained in the solvent in an amount of 50 mass% or more. The content of the ketone solvent in the solvent of the composition 2 may be 55 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, 95 mass% or more, 99 mass% or more, or 100 mass% or more. In the case where the composition 2 contains a solvent other than the ketone solvent, the ester solvent is preferable, and the solvent other than the ketone solvent may be contained to such an extent that the effect of the present invention is not impaired. However, since the ether solvent deactivates the oxime-type photopolymerization initiator, it is preferably not used as a solvent for the composition 2.

The solvent is generally used for the purpose of preparation of the composition, viscosity adjustment at the time of coating on a substrate, and the like. Therefore, the content of the solvent may be appropriately changed according to the purpose.

[ Colorant ]

As the colorant, a known one can be used. The colorant may be used alone or in combination of 2 or more. The colorant may be contained in a composition or all of compositions containing any 1 or more of the 1 st composition and the 2 nd composition.

The colorant may be any of pigments, dyes, and pigments, and may be any of commonly known colorants such as red, blue, green, yellow, white, and black. More specifically, the colorant may be a substance labeled with the following color index (c.i.; release number by the society of dyes and colorists (The Society of Dyers and Colourists)).

As the red colorant, there are: monoazo, disazo, azo lakes, benzimidazolones, perylenes, diketopyrrolopyrroles, condensed azo, anthraquinone, quinacridone and the like. As the blue colorant, there are: the phthalocyanine system, anthraquinone system, etc., and the Pigment system may be used as a compound classified into Pigment (Pigment). In addition to these, metal-substituted or unsubstituted phthalocyanine compounds may be used. As the green colorant, there are likewise: phthalocyanine, anthraquinone and perylene. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds may be used. As yellow colorants, there are: monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like. Examples of the white colorant include rutile-type or anatase-type titanium oxide. As the black colorant, there are: carbon black, graphite, iron oxide, titanium black, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, aniline, molybdenum sulfide, bismuth sulfide, and the like. For the purpose of adjusting the color tone, a colorant such as violet, orange, brown, or the like may be added.

When the curable resin composition of the present invention is used as a solder resist composition, the content of the colorant is 0.03 to 7% by mass, more preferably 0.05 to 5% by mass, in terms of a solid matter conversion, relative to the total amount of the curable resin composition of the present invention (the total amount of all the compositions including the 1 st composition and the 2 nd composition).

Here, the curable resin composition of the present invention can reduce deactivation of the photopolymerization initiator having an oxime bond, and thus can be suitably used for a black mask or the like containing a photopolymerization initiator having high sensitivity.

When the curable resin composition of the present invention is used as a black masking agent (alkali-developable photosensitive black masking agent) or the like, the content of the colorant is preferably 5 to 50% by mass, in terms of solid content conversion, relative to the total amount of the alkali-developable photosensitive black masking agent, from the viewpoint of improving the concealing properties of the cured product, and thus both the masking properties and the resolution can be achieved. More preferably 10 to 30 mass%.

Here, when the curable resin composition of the present invention is used as a black shielding agent (alkali development type photosensitive black shielding agent) or the like, the colorant preferably contains carbon black, and it is preferable to use carbon black in combination with a mixed-color black-based colorant. In particular, when the carbon black and the mixed-color black-based colorant are used in combination, it is preferable that the carbon black is 4 to 10% by mass, preferably 4 to 8% by mass, and the mixed-color black-based colorant is 8 to 20% by mass, preferably 12 to 16% by mass, based on the total amount of the alkali-developable photosensitive black-based masking agent, in terms of solid matter conversion.

The mixed-color black-based colorant means a colorant obtained by mixing colorants such as a red colorant, a blue colorant, a green colorant, a yellow colorant, a violet colorant, and an orange colorant so as to be black or a color close to black. The mixed-color black colorant is preferably added to the resin composition in advance with each colorant, but each colorant constituting the mixed-color black colorant may be added to the resin composition separately.

[ (F) other Components ]

The other components include: known additives commonly used in curable resin compositions, such as fillers, heat curing catalysts, photoinitiation aids, cyanate ester compounds, elastomers, mercapto compounds, urethanization catalysts, thixotropic agents, adhesion promoters, block copolymers, chain transfer agents, polymerization inhibitors, copper inhibitors, antioxidants, rust inhibitors, micro-silica, thickeners such as organobentonites and montmorillonite, defoamers such as silicones, fluorine-based and polymer-based and/or leveling agents, silane coupling agents such as imidazoles, thiazoles and triazoles, and flame retardants such as phosphinates, phosphate derivatives and phosphorus compounds such as phosphazene compounds.

< Effect >

The alkali-developable photocurable and thermosetting resin composition of the present invention comprises at least a1 st composition and a2 nd composition, wherein the 1 st composition comprises at least (A) an alkali-soluble resin, and the 2 nd composition comprises at least (B-1) an oxime photopolymerization initiator and (E-1) a ketone solvent. The compositions can be stored in a state where they are not in contact or are not easily in contact, for example, by being stored in different containers. With this configuration, the solvent preferably used in the curable resin composition acts on the oxime photopolymerization initiator, and thus the oxime photopolymerization initiator is prevented from being deactivated and recrystallized, and long-term storage stability can be achieved.

< Usage >

The curable resin composition of the present invention is suitable for forming a permanent coating film such as a solder resist layer, a coverlay layer, an interlayer insulating layer, a masking agent used for an FPD (flat panel display) and the like of a printed circuit board, a flexible printed circuit board, and for forming a resist film, particularly, a printed circuit board excellent in optical characteristics, and therefore suitable for increasing the density and the thickness thereof. The curable resin composition of the present invention can be used for producing a shielding image such as a printing ink, an inkjet ink, a photomask producing material, a sample sheet producing material for printing, a dielectric pattern, an electrode (conductor circuit) pattern, a wiring pattern of an electronic component, a conductive paste, a conductive film, a black matrix, and the like.

< Method of use >)

Next, as an example of a method for using the alkali-developable photocurable and thermosetting resin composition of the present invention, a method for forming a cured product of the alkali-developable photocurable and thermosetting resin composition on a substrate will be described.

In the following, the case where the alkali-developable photocurable and thermosetting resin composition of the present invention is formed into a two-component system composed of the 1 st composition and the 2 nd composition will be described. Compositions 1 and 2 were obtained as follows: the alkali-soluble resin and the oxime-based photopolymerization initiator are mixed in different compositions, and the solvent of the composition containing the oxime-based photopolymerization initiator is a ketone-based solvent, and the raw materials are mixed in advance. The alkali-developable photocurable and thermosetting resin composition of the present invention is assumed to be used in a state where a predetermined storage time has elapsed in general, but may be used immediately without providing a predetermined storage time.

[ Method of Forming cured product ]

The cured product is generally obtained by performing a resin layer forming process, an exposing process, a developing process, and a heat curing process. The following describes each step.

(Resin layer Forming step)

The composition 1 and the composition 2 are mixed and, if necessary, viscosity is adjusted with an organic solvent to form a coating composition. Next, the coating composition is coated on the substrate at a desired thickness. Then, the organic solvent contained in the coating composition is volatilized and dried to form a resin layer on the substrate.

Examples of the substrate include a printed circuit board and a flexible printed circuit board on which a circuit is formed in advance, and the following: copper-clad laminates of all grades (FR-4 etc.) which are made of materials such as copper-clad laminates for high-frequency circuits, including paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven fabric epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluorine/polyethylene/polyphenylene oxide/cyanate ester; and polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, and the like.

In particular, in the case where the present invention is an alkali-developable photosensitive black mask, the substrate is preferably a glass substrate.

The shape and type of the glass substrate may be appropriately changed according to the application. Since the alkali-developable photosensitive black mask has high resolution and high adhesion to a glass substrate, not only a flat glass substrate but also a curved glass substrate can be used.

Examples of the coating method include screen printing, curtain coating, spray coating, and roll coating.

The coating film thickness can be suitably set so that the film thickness after drying is in the range of 0.5 to 100. Mu.m, 0.5 to 50. Mu.m, 2 to 40. Mu.m, or 2 to 20. Mu.m.

Examples of the drying means include a hot air circulation type drying furnace, an IR furnace, a hot plate, and a convection oven.

The drying conditions are, for example, as follows: the drying temperature may be set to 50 to 130℃and the drying time may be set to 1 to 30 minutes.

(Exposure Process)

The resin layer is selectively irradiated with an active light (exposed).

The exposure method is not particularly limited, and may be a method of patterning through a photomask having a predetermined exposure pattern formed thereon, or may be a method of patterning through laser direct imaging such as h-ray direct imaging (HDI).

Examples of the irradiation light source of the active light include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, and a metal halide lamp.

The exposure method may be classified into a contact exposure method in which exposure is performed in a state where the photomask is in contact with the resin layer, and a non-contact exposure method in which exposure is performed in a state where the photomask is not in contact with the resin layer.

Since the photomask of the contact exposure method is in contact with the resin layer, the resolution is high, and when the photomask is removed after exposure, the resin layer may adhere to the photomask, and continuous productivity may be deteriorated such as contamination of the photomask or abnormal stop of the automatic exposure machine. Since the non-contact exposure method is a distance from the photomask to the resin layer, the productivity is high continuously, and the resolution is liable to be low.

The resin layer obtained by using the alkali-developable photosensitive black mask of the present invention can be used in either of the above-mentioned non-contact exposure method and contact exposure method.

(Developing step)

After the exposure step, the resin layer is developed with an aqueous alkali solution to remove the unexposed portions of the resin layer, thereby forming a pattern.

Examples of the developing method include dipping, spraying, brushing, and the like.

Examples of the aqueous alkali include aqueous alkali such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines.

(Heat curing Process)

The exposed portion of the resin layer is thermally cured, and a cured product (for example, a black mask portion) having a predetermined pattern is formed on a glass substrate or the like.

The heat curing conditions may be, for example, 140 to 180 ℃.

Here, the glass substrate provided with the cured product (black shielding portion) of the alkali-developable photosensitive black shielding agent of the present invention can be used for various applications, and is preferably used for various display devices, and particularly preferably used for forming in-vehicle displays.

Examples

Embodiment 1

[ (A) Synthesis of carboxyl group-containing resin ]

220 Parts of cresol novolak type epoxy resin (registered trademark "epilon" N-695, epoxy equivalent: 220, manufactured by Dain ink chemical industry Co., ltd.) was placed in a four-necked flask equipped with a stirrer and a reflux condenser, 214 parts of carbitol acetate was added thereto, and the mixture was heated and dissolved. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of dimethylbenzylamine as a reaction catalyst were added. The mixture was heated to 95 to 105℃and 72 parts of acrylic acid was slowly added dropwise thereto and reacted for 16 hours. The reaction product is cooled to 80-90 ℃, 106 parts of tetrahydrophthalic anhydride is added to react for 8 hours, and the reaction product is taken out after cooling.

The photosensitive resin having both an ethylenically unsaturated bond and a carboxyl group thus obtained was as follows: the nonvolatile matter was 65%, the acid value of the solid matter was 85mgKOH/g, and the weight-average molecular weight Mw was about 3500. Hereinafter, this resin solution is referred to as "A-1 varnish".

The weight average molecular weight of the obtained resin was measured by high performance liquid chromatography to which three pumps LC-804, KF-803 and KF-802 manufactured by Shimadzu corporation were connected.

Raw material of alkali development type photo-curing thermosetting resin composition

[ (A) carboxyl group-containing resin ]

A-1 varnish

[ (B) photopolymerization initiator ]

(B-1) an oxime-based photopolymerization initiator

TOE-04-A3 (manufactured by Japanese chemical industry Co., ltd.)

(B-2) photopolymerization initiator other than oxime system

Omnirad TPO (IGM RESINS Co., ltd.)

[ (C) reactive diluent ]

DPHA (dipentaerythritol hexaacrylate, manufactured by Japanese chemical Co., ltd.)

[ (D) Heat-curable resin ]

JER828 (Mitsubishi chemical corporation)

[ (E) solvent ]

(E-1) Ketone solvent

Cyclohexanone

Solvents other than (E-2) ketones

Dipropylene glycol monomethyl ether

1-Methoxy-2-propanol

Diethylene glycol monoethyl ether acetate

[ (F) other Components (colorants) ]

Perylene Red colorant (C.I.pigment Red 149)

Phthalocyanine Blue colorant (C.I.pigment Blue 15:3)

Anthraquinone Yellow colorant (C.I. pigment Yellow 147)

Carbon Black (C.I.pigment Black 7)

Preparation of alkali-developable photocurable and thermosetting resin compositions of examples and comparative examples >

Based on the component compositions shown in table 1, the respective components were mixed and pre-mixed by a mixer, and then kneaded and dispersed to prepare alkali-developable photocurable and thermosetting resin compositions of examples and comparative examples, which were composed of the 1 st and 2 nd compositions. The contents in the table represent parts by mass. In the table, the contents calculated by solid content conversion are shown for the components other than the solvent (E).

TABLE 1

Further, as comparative examples 3 to 6, compositions in which the 1 st composition and the 2 nd composition were mixed in advance were prepared for the alkali-developable photocurable and thermosetting resin compositions of each example and each comparative example.

< Evaluation >

For each of the compositions thus obtained, the presence or absence and size of recrystallized grains were confirmed after leaving for 7 days or 120 days at room temperature. Then, the 1 st composition and the 2 nd composition were mixed, and photosensitivity, resolution and adhesion were evaluated by the following evaluation methods. The evaluation results are shown in table 2.

[ Coating film production conditions ]

The resultant film was applied to a glass substrate with an applicator so that the thickness of the film became 10 μm after drying, and dried in a hot air circulation type drying oven at 80℃for 30 minutes to prepare a coating film.

[ Sensitivity ]

A step exposure meter (Kodak No. 2) was adhered to the dried coating film, and exposure was performed at 1000mJ/cm ² using an exposure machine for a metal halide lamp, and after development, the sensitivity was evaluated based on the number of steps obtained from the step exposure meter. The evaluation criteria are as follows.

The number of steps obtained in (a) is 7 or more.

The number of steps obtained was less than 7.

Resolution

On the dried coating film, exposure was performed at 1000mJ/cm ² with an exposure machine for a metal halide lamp, and after development, the line of the minimum width formed was read and evaluated for resolution.

(L/s=100/100 residues).

X. L/s=100 and/100 is not remained.

[ Adhesion ]

According to the test method of JIS (Japanese Industrial Standard) D-0202, 100 cross-cuts were made in a grid form on a cured coating film of a test piece, and then the peeled portion after the peeling test by a cellophane tape was visually determined. The evaluation criteria are as follows.

100 Of (1) the grid remains.

No grid of 100 remained.

[ Recrystallization ]

The size of the recrystallized grains was confirmed by a milling tester (0-25 μm). When the size of the recrystallized grains was 5 μm or more, pinholes and poor appearance were generated when the film thickness of the cured coating film of each composition was 10 μm, and therefore 5 μm or more was marked as x. In the case where the recrystallized grains were not present and the size of the recrystallized grains was smaller than 5. Mu.m, pinholes were not generated even when the film thickness of the cured coating film of each composition was 10. Mu.m.

And (c) no recrystallized grains.

The size of the DeltaDeltaDeltaDeltaDeltaSigma recrystallized grains is less than 5 μm.

The size of the recrystallized grains is 5 μm or more.

[ OD value ]

The OD value was evaluated by mounting the film-coated side of the glass substrate on a transmission densitometer (SAKATA INX ENG.CO., LTD., model X-Rite 361T, light source wavelength 400 to 800 nm) toward the measuring instrument.

OD value exceeds 4

The DeltaDeltaDeltaDeltaOD value is 3 or more and 4 or less

OD value of less than 3

TABLE 2

Embodiment 2

< Raw Material of alkali developing photosensitive Black masking agent >)

(A) Carboxyl group-containing resin

A-1 varnish

(B) Photopolymerization initiator

B-1: TOE-04-A3 (manufactured by Japanese chemical industry Co., ltd.)

B-2: omnirad TPO (IGM RESINS Co., ltd.)

(C) Photocurable monomer (reactive diluent)

C-1: m-360 (EO-modified trimethylolpropane triacrylate, manufactured by Toyama Synthesis Co., ltd.)

C-2: DPCA-120 (hexaacrylate dipentaerythritol modified by caprolactone, manufactured by Japanese chemical Co., ltd.)

C-3: TMPTA (Trimethylol propane triacrylate)

C-4: DPHA (dipentaerythritol hexaacrylate)

(D) Thermosetting resin

JER834 (epoxy resin manufactured by Mitsubishi chemical Co., ltd.)

(E) Solvent(s)

Cyclohexanone

DPM (dipropylene glycol monomethyl ether)

(F-1) colorant

Carbon Black (C.I.pigment Black 7)

Perylene Red colorant (C.I.pigment Red 149)

Phthalocyanine Blue colorant (C.I.pigment Blue 15:3)

Anthraquinone Yellow colorant (C.I. pigment Yellow 147)

(F-2) other Components

Leveling agent: BYK-361N (BYK Japan KK.)

Preparation of alkali-developable photosensitive Black masking Agents of examples and comparative examples

Based on the component compositions shown in tables 3to 4, the respective components were blended, premixed by a mixer, and then kneaded and dispersed to prepare alkali-developable photosensitive black screening agents of examples and comparative examples, which were composed of the 1 st and 2 nd compositions. The content in the table represents parts by mass. In the table, the content calculated by solid content conversion is shown for the components other than the organic solvent (E).

< Evaluation >

For examples 3 to 14, the same coating film formation conditions and evaluation methods as in example 1 were used to evaluate each of sensitivity, resolution, adhesion, recrystallization, and OD value.

The evaluation results of examples 3 to 14 were the same as those of example 1.

The evaluation results of comparative examples 7 to 9 are the same as those of comparative example 1.

Further, the photosensitive black mask thus obtained was evaluated for resolution, adhesion, tackiness, and OD value based on the following evaluation method. The evaluation results are shown in tables 3 to 4.

[ Resolution 2]

The masking material was applied onto a chemically strengthened glass plate (Dragontrail, manufactured by AGC corporation) by air spraying so that the film thickness after drying became 10um, and after drying (80 ℃ for 30 minutes), a predetermined photomask was adhered to the coating film, and exposure was performed (the exposure amount on the masking material was 700mJ/cm ²), and then development (1 wt% na ₂CO₃, 30 ℃ for 0.2mpa,60 seconds) was performed to produce a test piece. To visually confirm the thinnest residual line in the test piece. The evaluation criteria are as follows.

And (3) the following materials: the minimum residual line width after development is 50 μm or less.

O: the minimum residual line width exceeds 50 μm and is 100 μm or less.

Delta: the minimum residual line width exceeds 100 μm and is 150 μm or less.

X: the minimum residual linewidth exceeds 150 μm.

[ Adhesion 2 (cross-hatching) ]

The masking material was applied to a chemically strengthened glass plate (Dragontrail, manufactured by AGC corporation) by air spraying so that the film thickness after drying became 10um, and after drying (80 ℃ for 30 minutes), a predetermined photomask was adhered to the coating film, and exposure was performed (the exposure amount on the masking material was 700mJ/cm ²). Next, a test piece was produced by developing (1 wt% Na ₂CO₃, 30 ℃,0.2MPa,60 seconds), post-UV (metal halide lamp, 1000mJ/cm ²), and heat curing (150 ℃,60 minutes) in this order.

According to JISK5400, 100 (10X 10) grids of 1mm were formed on a film of a test piece, a transparent adhesive tape (width: 18mm, manufactured by Nichiban Co., ltd.) was completely adhered to the grids, and the number of grids remaining after incomplete peeling was examined while immediately maintaining one end of the tape at right angles to the glass substrate. The evaluation criteria are as follows.

O: the grid remained at 100%.

Delta: the grid remains more than 95% and less than 100%.

X: the grid residue was less than 95%.

[ Tackiness ]

The masking material was applied to a chemically strengthened glass plate (Dragontrail, manufactured by AGC corporation) by air spraying so that the film thickness after drying became 10um, and after drying (80 ℃ for 30 minutes), a predetermined photomask was adhered to the coating film, and exposure was performed (the exposure amount on the masking material was 700mJ/cm ²). Then, the photomask was peeled from the coating film by hand to visually confirm the easiness of peeling of the mask and the presence or absence of adhesion marks of the photomask at this time. The evaluation criteria are as follows.

And (3) the following materials: no resistance during peeling and no adhesion mark

O: no resistance during peeling and no obvious adhesion mark

Delta: the peeling resistance was felt and the seal mark was inconspicuous

X: resistance at peeling is felt and the masking material is transferred to the photomask

[ OD value 2 (light shielding Property) ]

The OD value was evaluated by mounting the film-coated side of the glass substrate on a transmission densitometer (SAKATA INX ENG.CO., LTD., model X-Rite 361T, light source wavelength 400 to 800 nm) toward the measuring instrument. The evaluation criteria are as follows.

And (3) the following materials: OD value is above 6

O: OD value is 5 or more and less than 6

Delta: OD value is 4 or more and less than 5

X: OD value is lower than 4

TABLE 3

TABLE 4

Claims (4)

1. An alkali-developable photocurable and thermosetting resin composition comprising at least a two-component system, characterized by comprising at least: an alkali-soluble resin, a photopolymerization initiator having an oxime bond, a reactive diluent, a thermosetting resin, a solvent, a colorant,

The photopolymerization initiator having an oxime bond and the alkali-soluble resin are compounded in different compositions, and a solvent compounded with the photopolymerization initiator having an oxime bond contains 50% by mass or more of a ketone-based solvent in the solvent,

The colorant comprises carbon black, or a mixture of a mixed-color black-based colorant and carbon black,

The reactive diluent contains a (meth) acrylate having a 2-or more function modified with either one of an alkylene oxide and a lactone.

2. The alkali-developable photocurable and thermosetting resin composition consisting at least of a two-component system according to claim 1, wherein the solvent compounded with the photopolymerization initiator having an oxime bond does not contain an ether-based solvent.

3. The alkali-developable photocurable and thermosetting resin composition composed at least of a two-component system according to claim 1 or 2, wherein the colorant comprises carbon black and a mixed-color black-based colorant, the content of the carbon black is 4 to 10 mass% and the content of the mixed-color black-based colorant is 8 to 20 mass% in terms of solid content conversion with respect to the total amount of the alkali-developable photocurable and thermosetting resin composition.

4. The alkali-developable photocurable and thermosetting resin composition consisting at least of a two-component system according to claim 1, wherein it is used for a glass substrate.