WO2019188591A1 - Alkali developable photocurable thermosetting resin composition - Google Patents

Abstract

[Problem] To provide a resin composition which exhibits excellent adhesion, resolution, sensitivity and the like even after long-term storage. [Solution] An alkali developable photocurable thermosetting resin composition which contains at least an alkali soluble resin, a photopolymerization initiator having an oxime bond, a reactive diluent, a thermosetting resin and a solvent, and which is composed of at least two packs of compositions that are configured such that: the alkali soluble resin and the photopolymerization initiator having an oxime bond are blended in different compositions; and a solvent that is blended together with the photopolymerization initiator having an oxime bond contains 50% by mass or more of a ketone solvent.

Description

Alkali development type photocurable thermosetting resin composition

The present invention relates to an alkali development type photocurable thermosetting resin composition that is composed of at least two liquids.

As one of the components of a curable resin composition that can be used for an alkali development type liquid photo solder resist composition, an alkali development type photosensitive shielding agent, etc., a photopolymerization initiator having an oxime bond has been conventionally used ( For example, Patent Document 1).

JP 2011-022328 A International Publication No. 2012/043001

The photopolymerization initiator having an oxime bond includes a photopolymerization initiator having an oxime bond, while being a component that can also be used for a curable resin composition used for a high-definition material that requires high sensitivity. When the curable resin composition is stored, optical properties such as sensitivity and resolution are gradually lowered. For this reason, it has been difficult to provide a curable resin composition excellent in optical characteristics and the like even after long-term storage.

For this problem, for example, Patent Document 2 proposes that the photopolymerization initiator having an oxime bond and the carboxyl group-containing resin are stored separately in two liquids to reduce deactivation.

However, since a composition with high concealability such as black, such as an alkali development type photosensitive shielding agent, has poor light transmission, it has a highly sensitive oxime bond for the purpose of improving sensitivity in such a composition. When the blending amount of the photopolymerization initiator is increased, deactivation can be reduced by using two liquids as described above, but it is not complete, and the photopolymerization initiator having an oxime bond is recrystallized to form coarse particles. There was a case that occurred. In particular, in the case of a shielding agent, the occurrence of coarse particles may cause a pinhole at a place where the coarse particles of the cured coating film of the shielding agent are generated, which may cause poor appearance.

As described above, an object of the present invention is to provide a resin composition that is excellent in adhesion, such as resolution and sensitivity, and can prevent recrystallization even during long-term storage.

As a result of intensive studies, the present inventors have found that a photopolymerization initiator having an oxime bond is excellent in solubility in a specific solvent, reducing the deactivation of the photopolymerization initiator having an oxime bond, and also performing recrystallization. I also found that it can be prevented.

The present invention is a photocurable thermosetting composition containing at least an alkali-soluble resin, a photopolymerization initiator having an oxime bond, a reactive diluent, a thermosetting resin, and a solvent,
The photopolymerization initiator having an oxime bond is blended in a composition different from the alkali-soluble resin, and the solvent blended with the photopolymerization initiator having an oxime bond is a ketone solvent in an amount of 50% by mass. An alkali development type photocurable thermosetting resin composition composed of at least a two-component system, characterized by comprising the above.
Moreover, it is preferable that the solvent mix | blended with the photoinitiator which has the said oxime bond does not contain an ether solvent.
Furthermore, it is preferable to contain a coloring agent.
The colorant contains carbon black and a mixed color black colorant, and the content of the carbon black is 4 to 10% by mass in terms of solid content per total amount of the alkali development type photocurable thermosetting resin composition. In addition, the content of the mixed color black colorant is preferably 8 to 20% by mass.
The reactive diluent preferably contains a bifunctional or higher functional (meth) acrylate modified with either alkylene oxide or lactone.
It is preferable that the alkali development type photocurable thermosetting resin composition is for a glass substrate.

According to the present invention, it is possible to provide a resin composition that is excellent in resolution, sensitivity and adhesion even during long-term storage and can prevent recrystallization.

Hereinafter, the alkali-developable photocurable thermosetting resin composition of the present invention (hereinafter, sometimes simply referred to as “curable resin composition”) will be specifically described. Is not limited at all.

In addition, when an isomer exists in the described compound, all isomers that can exist can be used in the present invention unless otherwise specified.

In the present specification, the term “(meth) acrylate” is a general term for acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions.

The solid content means a component constituting a composition other than a solvent (particularly an organic solvent), or its mass and volume unless otherwise specified.

The curable resin composition of the present invention comprises at least an alkali-soluble resin, a photopolymerization initiator having an oxime bond, a reactive diluent, a thermosetting resin, and a solvent, and a photocurable / thermosetting composition. The photopolymerization initiator having an oxime bond is blended in at least a composition different from the alkali-soluble resin, and the solvent blended with the photopolymerization initiator having an oxime bond is a ketone solvent. It is an alkali development type photocurable thermosetting resin composition that is at least in a two-component system.

In another expression, the curable resin composition of the present invention includes at least (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a reactive diluent, (D) a thermosetting resin, and (E) a photocurable thermosetting composition (photocurable thermosetting material) containing a solvent, (A) a first composition containing at least an alkali-soluble resin, and (B) a photopolymerization initiator. (B-1) a photopolymerization initiator having an oxime bond {hereinafter referred to as “oxime-based photopolymerization initiator”. And (E) a second composition containing (E-1) a ketone solvent in an amount of 50% by mass or more as a solvent, and at least two liquids (or three liquids or more). It is an alkali development type photocurable thermosetting resin composition (alkali development type photocurable thermosetting material) material.

Moreover, the curable resin composition of the present invention may contain (F) other components as long as the effects of the present invention are not impaired.

Each component of the curable resin composition of the present invention is classified as follows.
(Essential component, component contained in the first composition)
(A) Alkali-soluble resin (essential component, component contained in the second composition)
(B-1) Oxime-based photopolymerization initiator (E-1) Ketone-based solvent (essential component that may be included in any or all of the compositions)
(C) Reactive diluent (D) Thermosetting resin (optional component)
(E) Solvent (B-2) Photopolymerization initiator other than oxime type (F) Other components

Hereinafter, each component of the curable resin composition of the present invention will be described.

Here, it is preferable that (F) other components include a colorant. Hereinafter, components (A) to (E) and the colorant will be described, and (F) other components other than the colorant will be described.

[(A) Alkali-soluble resin]
As the alkali-soluble resin, known resins can be used, and it is preferable to use a carboxyl group-containing resin or a phenolic hydroxyl group-containing resin. In particular, use of a carboxyl group-containing resin is more preferable from the viewpoint of developability. Moreover, alkali-soluble resin may be used individually by 1 type, and may be used in combination of 2 or more type.

As the carboxyl group-containing resin, in particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is a photosensitive composition for performing alkali development, from the viewpoint of photocurability and development resistance. More preferred. The unsaturated double bond is preferably derived from acrylic acid, methacrylic acid, or derivatives thereof.

(I) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.

(II) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(III) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by polyaddition reaction of (meth) acrylate or a partially acid anhydride modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

(IV) During the synthesis of the resin of (II) or (III), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing photosensitive urethane resin.

(V) During the synthesis of the resin of (II) or (III), one isocyanate group and one or more (meth) acryloyl groups are added in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal (meth) acrylate.

(VI) A carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or higher polyfunctional (solid) epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group present in the side chain.

(VII) A carboxyl obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin and adding a dibasic acid anhydride to the resulting hydroxyl group Group-containing photosensitive resin.

(VIII) Two bases such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are reacted with a dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid on a bifunctional oxetane resin. A carboxyl group-containing polyester resin to which an acid anhydride is added.

(IX) an epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and (meth) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as an acid.

(X) Reaction product obtained by reacting a compound obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.

(XI) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

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

The acid value of the carboxyl group-containing resin is preferably in the range of 20 to 200 mgKOH / g, more preferably in the range of 40 to 150 mgKOH / g. When the acid value of the carboxyl group-containing resin is 20 mgKOH / g or more, the adhesion of the coating film is good and the alkali development is good. On the other hand, when the acid value is 200 mgKOH / g or less, the dissolution of the exposed part by the developer can be suppressed, so that the line is thinner than necessary, or in some cases, the developer without distinguishing between the exposed part and the unexposed part The resist pattern can be satisfactorily drawn by suppressing dissolution and peeling.

The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is 2,000 or more, the tack-free performance is good, the moisture resistance of the coated film after exposure is good, the film loss during development can be suppressed, and the resolution can be suppressed. On the other hand, when the weight average molecular weight is 150,000 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 two or more. When the curable resin composition of this invention contains 2 or more types of carboxyl group-containing resin, it is preferable to contain (A1) carboxyl group-containing photosensitive resin mentioned above, for example.

In another embodiment, the curable resin composition of the present invention includes, as a carboxyl group-containing resin, the above-described (A1) carboxyl group-containing photosensitive resin and a carboxyl group-containing acrylic copolymer having no alicyclic skeleton. It may contain a coalescence. Examples of the carboxyl group-containing acrylic copolymer having no alicyclic skeleton include (1) styrene copolymer type carboxyl group-containing resins mentioned as specific examples of the carboxyl group-containing resin. The blending ratio in the case of blending the carboxyl group-containing acrylic copolymer having no alicyclic skeleton is, for example, 10 to 95 parts by weight, preferably 100 to 95 parts by weight, preferably 100 parts by weight of the entire carboxyl group-containing resin. 10 to 80 parts by mass.

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, it is a compound having two or more phenolic hydroxyl groups in one molecule. Compounds having two or more phenolic hydroxyl groups in one molecule include catechol, resorcinol, hydroquinone, dihydroxytoluene, naphthalenediol, t-butylcatechol, t-butylhydroquinone, pyrogallol, phloroglucinol, bisphenol A, bisphenol F. Bisphenol S, biphenol, bixylenol, novolac-type phenol resin, novolac-type alkylphenol resin, bisphenol A novolak resin, dicyclopentadiene-type phenol resin, Xylok-type phenol resin, terpene-modified phenol resin, polyvinylphenols, phenol Of 1-naphthol or 2-naphthol with aromatic aldehydes However, the present invention is not limited to these. A phenolic hydroxyl group containing compound can be used individually by 1 type or in combination of 2 or more types.

The content of the alkali-soluble resin is not particularly limited, but may be 10 to 95% by mass, preferably 10 to 80% by mass in terms of solid content per curable resin composition.

[(B) Photopolymerization initiator]
<(B-1) Oxime-based photopolymerization initiator>
A well-known thing can be used as an oxime system photoinitiator. Moreover, an oxime system photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

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

In 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 a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group.

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, and a halogen atom.

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

The cycloalkyl group represented by R1 and R2 is preferably a cycloalkyl group 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 and a phenyl group.

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

In general formula (I-2), R11 has the same meaning as R1 in general formula (I), and R12 and R14 each independently has the same meaning as R2 in 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, or an alkoxycarbonyl group having 2 to 12 carbon atoms. Group (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain) Good) or a phenoxycarboxylic group.

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

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

In 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 benzofuryl group, or a benzothienyl group.
Ar is a single bond or an alkylene group having 1 to 10 carbon atoms, vinylene group, phenylene group, biphenylene group, pyridylene group, naphthylene group, anthrylene group, thienylene group, furylene group, 2,5-pyrrole-diyl group, It represents a 4,4′-stilbene-diyl group or a 4,2′-styrene-diyl group.
n represents an integer of 0 to 1.

The alkyl group represented by R23 is preferably an alkyl group having 1 to 17 carbon atoms.
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. Examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms) and an alkoxy group (preferably having 1 to 8 carbon atoms). An amino group, an alkylamino group (preferably an alkyl group having 1 to 8 carbon atoms) or a dialkylamino group (preferably an alkyl group having 1 to 8 carbon atoms).
The naphthyl group represented by R23 may have a substituent, and examples of the substituent include the same groups as the above-described substituent that the phenyl group represented by R23 may have.

The alkyl group represented by R21 and R22 is preferably an alkyl group having 1 to 17 carbon atoms.
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. Examples of the substituent include an alkyl group (preferably having a carbon number of 1 to 17), an alkoxy group (preferably having a carbon number of 1 to 1). 8), an amino group, an alkylamino group (preferably an alkyl group having 1 to 8 carbon atoms) or a dialkylamino group (preferably an alkyl group having 1 to 8 carbon atoms).
The naphthyl group represented by R21 and R22 may have a substituent, and examples of the substituent include the same groups as the substituents that the phenyl group represented by R21 and R22 may have. .

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

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

(B) As oxime ester photopolymerization initiators, commercially available products such as CGI-325, Irgacure OXE01 (1.2-octanedione, 1- [4- (phenylthio)-, 2- ( O-benzoyloxime)]), Irgacure OXE02 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)), ADEKA N-1919, NCI-831, Changzhou Power Electronics New Materials Co., Ltd. TR-PBG-304, Nippon Chemical Industry Co., Ltd. TOE-04-A3, and the like.

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

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

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

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

As the α-aminoacetophenone photopolymerization initiator containing a structural moiety represented by the general formula (II), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like.

[(B-2) Photopolymerization initiator other than oxime type]
As the photopolymerization initiator other than the oxime type, known ones can be used. Moreover, an oxime system photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of photopolymerization initiators other than oximes include known and commonly used compounds such as benzophenone, acetophenone, aminoacetophenone, benzoin ether, benzyl ketal, acylphosphine oxide, oxime ether, and titanocene. It is done.

[(C) Reactive diluent]
Known reactive diluents can be used. Moreover, a reactive diluent may be used individually by 1 type, and may be used in combination of 2 or more type.

The reactive diluent is a compound having a carbon-carbon multiple bond (double bond and triple bond) in the molecule, in other words, a photocurable monomer. Such reactive diluents include alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like Hydroxyalkyl (meth) acrylates; mono- or di (meth) acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, di Polyhydric alcohols such as pentaerythritol and trishydroxyethyl isocyanurate, or polyvalents of these ethylene oxide or propylene oxide adducts ) Acrylates; (meth) acrylates of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A; glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, tri Known (meth) acrylates such as (meth) acrylates of glycidyl ether such as glycidyl isocyanurate; and melamine (meth) acrylate;

The content of the reactive diluent in the curable resin composition of the present invention is not particularly limited. For example, it is 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. do it.

Here, since the curable resin composition of the present invention can reduce the deactivation of the photopolymerization initiator having an oxime bond, it is preferably used for a black shielding agent containing a highly sensitive photopolymerization initiator. it can.
When the curable resin composition of the present invention is used as a black shielding agent (alkali development type photosensitive black shielding agent), the reactive diluent according to the present invention, that is, any one of alkylene oxide and lactone as a photocurable monomer. A bifunctional or higher (preferably a trifunctional or higher) (meth) acrylate modified with (hereinafter referred to as “(meth) acrylate (c)”). } Is preferably contained. Thereby, the black shielding agent excellent in the adhesiveness to a glass base material can be provided. Moreover, when this (meth) acrylate (c) is contained, it is preferable that (A) alkali-soluble resin is carboxyl group-containing resin.

Here, the (meth) acrylate (c) is only required that at least a part of the bifunctional or higher (meth) acrylate is modified with 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 is preferably caprolactone.

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

As specific (meth) acrylate (c), for example, among the known (meth) acrylates described above, a bifunctional or higher functional (meth) acrylate modified with either alkylene oxide or lactone, for example, And (meth) acrylates of alkylene oxide adduct polyols or lactone adduct polyols. More specifically, (meth) acrylate (c) is EO-modified trimethylolpropane triacrylate, EO-modified pentaerythritol tetraacrylate, EO-modified ditrimethylolpropane tetraacrylate, EO-modified dipentaerythritol hexaacrylate, EO-modified trisacrylate. Roxyethyl triisocyanurate, EO-modified full orange acrylate, EO-modified bisphenol A epoxy diacrylate, EO-modified bisphenol F epoxy diacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol F diacrylate, EO-modified glycerin diglycidyl ether ( (Meth) acrylate, EO-modified trimethylolpropane triglycidyl ether (meth) acrylate, EO-modified triglycidyl (Meth) acrylate isocyanurate, caprolactone-modified dipentaerythritol hexaacrylate, etc. caprolactone-modified isocyanuric acid triacrylate. Among these, EO-modified trimethylolpropane triacrylate and caprolactone-modified dipentaerythritol hexaacrylate are preferable.

When (meth) acrylate (c) is used as the photocurable monomer, one type of (meth) acrylate (c) may be used alone, or two or more types of (meth) acrylate (c) may be used in combination. May be. Furthermore, you may use combining (meth) acrylate (c) and photocurable monomers other than (meth) acrylate (c) (henceforth "other photocurable monomers").

Other photocurable monomers are not particularly limited, and the known (meth) acrylates described above may be used.

The content of (meth) acrylate (c) is preferably 10 to 45 parts by mass with respect to 100 parts by mass of (A) alkali-soluble resin (preferably carboxyl group-containing resin). When the content of (meth) acrylate (c) is 10 parts by mass or more, good resolution can be obtained. Moreover, in the case of 45 mass parts or less, a favorable tackiness (no negative sticking) coating film can be obtained.

When other photocurable monomers are blended, the total content of (meth) acrylate (c) and other photocurable monomers is (A) 100 parts by mass of an alkali-soluble resin (preferably a carboxyl group-containing resin). It is preferably 10 to 45 parts by mass, and the other photocurable monomer is preferably 0 to 50% by weight.

[(D) Thermosetting resin]
A well-known thing can be used as a thermosetting resin. Moreover, a thermosetting resin can be used individually by 1 type or in combination of 2 or more types.

Examples of thermosetting resins include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, benzoguanamine derivatives, isocyanate compounds, blocked isocyanate compounds, cyclocarbonate compounds, epoxy compounds, oxetane compounds, episulfide resins, bismaleimides, carbodiimide resins. Etc.

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

The thermosetting resin having a plurality of cyclic (thio) ether groups in the molecule is a compound having a plurality of 3, 4 or 5-membered cyclic (thio) ether groups in the molecule. A compound having a plurality of epoxy groups, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, that is, an episulfide resin, and the like can be mentioned.

Polyfunctional epoxy compounds include epoxidized vegetable oils; bisphenol A type epoxy resins; hydroquinone type epoxy resins; bisphenol type epoxy resins; thioether type epoxy resins; brominated epoxy resins; novolac type epoxy resins; biphenol novolac type epoxy resins; Type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; trihydroxyphenylmethane type epoxy resin; bixylenol type or biphenol type epoxy resin or a mixture thereof; Bisphenol S type epoxy resin; Bisphenol A novolak type epoxy resin; Tetraphenylol ethane type epoxy resin; Heterocyclic epoxy resin; Phthalate resin; Tetraglycidylxylenoylethane resin; Naphthalene group-containing epoxy resin; Epoxy resin having dicyclopentadiene skeleton; Glycidyl methacrylate copolymer epoxy resin; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Polybutadiene rubber derivatives; CTBN-modified epoxy resins and the like can be mentioned, but are not limited thereto. These epoxy resins can be used alone or in combination of two or more.

Examples of the polyfunctional oxetane compound include 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-oxetanyl) methyl acrylate, (3-ethyl-3- In addition to polyfunctional oxetanes such as oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin , Poly (p-hydroxystyrene), cardo type bi Phenols, calixarenes, calix resorcin arenes or etherified products such as the resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin. Moreover, episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin by the sulfur atom using the same synthesis method can also be used.

Examples of amino resins such as melamine derivatives and benzoguanamine derivatives include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.

As the isocyanate compound, a polyisocyanate compound can be blended. Polyisocyanate compounds include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, and Aromatic polyisocyanates such as 2,4-tolylene dimer; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; Cycloaliphatic polyisocyanates such as heptane triisocyanate; and adducts of the isocyanate compounds listed above Burette body and isocyanurate products thereof.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. As an isocyanate compound which can react with an isocyanate blocking agent, the above-mentioned polyisocyanate compound etc. are mentioned, for example. As an isocyanate block agent, for example, phenol block agent; lactam block agent; active methylene block agent; alcohol block agent; oxime block agent; mercaptan block agent; acid amide block agent; imide block agent; Examples include amine-based blocking agents; imidazole-based blocking agents; imine-based blocking agents.

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

[(E) Solvent]
(E) Solvents include (E-1) ketone solvents and (E-2) solvents other than ketone solvents. Each will be described below.

(E-1) Ketone solvent As the ketone solvent, known solvents can be used. Moreover, a ketone solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl butyl ketone, and methyl isobutyl ketone. Of these, cyclohexanone is preferred.

(E-2) Solvents other than ketones As the solvents other than ketones, known solvents can be used. In addition, solvents other than ketones may be used alone or in combination of two or more.

Non-ketone solvents include aromatic hydrocarbon solvents such as toluene, xylene and tetramethylbenzene; ethyl acetate, butyl acetate, isobutyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate , Ester solvents such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate; ethanol, propanol, 2-methoxypropanol, n-butanol, isobutyl alcohol Alcohol solvents such as isopentyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon solvents such as tan and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, N, N-dimethylformamide (DMF), tetrachloroethylene, turpentine oil, etc. It is done.

Here, conventionally, solvents such as ethers have been used as the solvent. However, when an ether solvent is blended and stored simultaneously with the oxime polymerization photoinitiator, the oxime photopolymerization initiator is deactivated. I understood. By blending with a ketone solvent instead of an ether solvent, it does not deactivate and recrystallize, and is not blended with a carboxyl group at the same time, making it a two-part solution with excellent storage stability and suitable for use as a shielding material. It becomes. Accordingly, it is preferable that the second composition containing the oxime photopolymerization initiator does not contain any solvent other than the ketone. More specifically, in the first composition, there is no particular need to limit the solvent, and it may be (E-1) a ketone solvent or (E-2) a solvent other than a ketone solvent, and the second composition. In (E-1), a solvent is preferably selected from the ketone solvents, and the ketone solvent should be contained in an amount of 50% by mass or more in the solvent. The content of the ketone solvent in the solvent in the second composition is 55% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass. % Or more and 100% by mass. In the second composition, when a solvent other than the ketone solvent is included, an ester solvent is preferable, and a solvent other than the ketone solvent may be included to the extent that the effects of the present invention are not impaired. However, it is preferable not to use the ether solvent as the solvent of the second composition because the oxime photopolymerization initiator is deactivated.

Solvents are generally used for the purpose of preparing the composition and adjusting the viscosity when applied onto the substrate. Therefore, the content of the solvent can be appropriately changed according to the purpose.

[Colorant]
A well-known thing can be used as a coloring agent. Moreover, a coloring agent may be used individually by 1 type, and may be used in combination of 2 or more type. This coloring agent should just be contained in any 1 or more types of compositions including a 1st composition and a 2nd composition, or all the compositions.

As the colorant, conventionally known colorants such as red, blue, green, yellow, white, and black can be used, and any of pigments, dyes, and pigments may be used. More specifically, examples of the colorant include those with the following color index numbers (CI; issued by The Society of Dyers and Colorists).

Examples of the red colorant include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. As the blue colorant, there are phthalocyanine series, anthraquinone series, and the like, and as the pigment series, compounds classified as pigments can be used. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used. Similarly, the green colorant includes phthalocyanine, anthraquinone and perylene. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used. Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone. Examples of the white colorant include rutile type or anatase type titanium oxide. Black colorants include carbon black, graphite, iron oxide, titanium black, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, and aniline. System, molybdenum sulfide, bismuth sulfide and the like. In addition, a colorant such as purple, orange or brown may be added for the purpose of adjusting the color tone.

When the curable resin composition of the present invention is used as a solder resist composition, the content of the colorant is the total amount of the curable resin composition of the present invention (of all compositions including the first composition and the second composition). The total amount) is 0.03 to 7% by mass, more preferably 0.05% to 5% by mass in terms of solid content.

Here, since the curable resin composition of the present invention can reduce the deactivation of the photopolymerization initiator having an oxime bond, it is preferably used for a black shielding agent containing a highly sensitive photopolymerization initiator. it can.

When the curable resin composition of the present invention is used as a black screening agent (alkali development type photosensitive black screening agent) or the like, the content of the colorant is alkali development type photosensitivity from the viewpoint of improving the concealability of the cured product. It is preferable that the black shielding agent is contained in an amount of 5 to 50% by mass in terms of solid content, since both shielding properties and resolution can be achieved. More preferably, the content is 10% by mass to 30% by 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 carbon black and mixed black coloring It is preferable to use an agent in combination. In particular, when carbon black and a mixed color black colorant are used in combination, the carbon black is 4 to 10% by mass, preferably 4 to 8% by mass, in terms of solid content, based on the total amount of the alkali developing type photosensitive black shielding agent, and The mixed color black colorant is 8 to 20% by mass, preferably 12 to 16% by mass.

Note that the mixed color black colorant is a mixture of a colorant such as a red colorant, a blue colorant, a green colorant, a yellow colorant, a purple colorant, and an orange colorant so that the color is close to black or black. The colorant obtained in this way is shown. The mixed color black colorant is preferably added to the resin composition after mixing each colorant in advance, but each colorant constituting the mixed color black colorant may be added to the resin composition individually. .

[(F) Other ingredients]
As other components, known additives generally used in curable resin compositions, such as fillers, thermosetting catalysts, photoinitiator aids, cyanate compounds, elastomers, mercapto compounds, urethanization catalysts, thixotropic agents , Adhesion promoter, block copolymer, chain transfer agent, polymerization inhibitor, copper damage inhibitor, antioxidant, rust inhibitor, fine powder silica, organic bentonite, montmorillonite and other thickeners, silicone-based, fluorine-based, Anti-foaming agents and / or leveling agents such as polymers, silane coupling agents such as imidazole, thiazole, and triazole, flame retardants such as phosphinates, phosphate derivatives, phosphorous compounds such as phosphazene compounds, etc. It is done.

<Effect>
The alkali-developable photocurable thermosetting resin composition of the present invention includes (A) a first composition containing at least an alkali-soluble resin, (B-1) an oxime-based photopolymerization initiator, and (E- 1) A second composition containing at least a ketone solvent. Each composition can be stored in a state where it is not in contact with or difficult to contact, for example, by being contained in a separate container. By constituting in this way, it is possible to prevent the solvent preferably used in the curable resin composition from acting on the oxime photopolymerization initiator to deactivate and recrystallize the oxime photopolymerization initiator, and to store for a long time. Sex can be achieved.

<Application>
The curable resin composition of the present invention is used to form a permanent coating film such as a solder resist for printed wiring boards and flexible printed wiring boards, coverlays, interlayer insulating layers, shielding agents used for FPD (flat panel display), and etching resist. It is suitable for the formation of a film, and in particular, because of its excellent optical characteristics, it is suitable for the formation of a printed wiring board with a high density and a high fineness. In addition, the curable resin composition of the present invention includes printing ink, inkjet ink, photomask preparation material, printing proof preparation material, dielectric pattern, electrode (conductor circuit) pattern, wiring pattern of electronic parts, conductive paste, conductive It can be used for production of shielding images such as films and black matrices.

<How to use>
Next, as an example of a method for using the alkali development type photocurable thermosetting resin composition of the present invention, a method for forming a cured product of the alkali development type photocurable thermosetting resin composition on a substrate will be described. To do.

In addition, below, the case where the alkali development type photocurable thermosetting resin composition of the present invention is a two-component system composed of a first composition and a second composition will be described. In the first composition and the second composition, the alkali-soluble resin and the oxime photopolymerization initiator are blended in different compositions, and the solvent of the composition containing the oxime photopolymerization initiator is a ketone solvent. Thus, it is obtained by mixing each raw material in advance. In addition, although it is assumed that the alkali development type photocurable thermosetting resin composition of the present invention is usually used after a predetermined storage period, it is used immediately without providing a predetermined storage period. May be.

[Method of forming cured product]
The cured product is generally obtained by executing a resin layer forming step, an exposure step, a developing step, and a thermosetting step. Each process will be described below.

(Resin layer forming process)
The first composition and the second composition are mixed, and if necessary, the viscosity is adjusted with an organic solvent to obtain a coating composition. Next, the coating composition is applied to the substrate with a desired thickness. Next, the organic solvent contained in the coating composition is evaporated and dried to form a resin layer on the substrate.

In addition to printed circuit boards and flexible printed circuit boards with pre-circuit formation, paper substrates such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy , Copper-clad laminates of all grades (FR-4 etc.), etc., using polyimide, polyphenylene ether, polyphenylene oxide, cyanate ester, etc. A film, a PET film, a glass substrate, a ceramic substrate, a wafer plate, etc. can be mentioned.

In particular, when the present invention is an alkali development type photosensitive black shielding agent, the substrate is preferably a glass substrate.

The shape and type of the glass substrate can be appropriately changed according to the application. Since the alkali development type photosensitive black shielding agent described above has high resolution and high adhesion to a glass substrate, not only a flat glass substrate but also a curved glass substrate should be used. Is also possible.

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

The coating film thickness may be appropriately set, for example, so that the film thickness after drying is in the range of 0.5 to 100 μm, 0.5 to 50 μm, 2 to 40 μm, or 2 to 20 μm.

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 may be, for example, a drying temperature of 50 to 130 ° C. and a drying time of 1 to 30 minutes.

(Exposure process)
The resin layer is selectively irradiated (exposed) with actinic rays.

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

Examples of active light irradiation light sources include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, xenon lamps, and metal halide lamps.

Here, the exposure method includes a contact exposure method in which exposure is performed in a state in which the photomask and the resin layer are in contact, and a non-contact exposure method in which exposure is performed in a state in which the photomask and the resin layer are not in contact with each other. And can be classified.

In the contact exposure method, since the photomask and the resin layer are in contact with each other, the resolution is high. On the other hand, when removing the photomask after exposure, the resin layer adheres to the photomask, and the photomask In some cases, continuous productivity may deteriorate due to contamination of the automatic exposure machine or abnormal stoppage of the automatic exposure machine. In the non-contact exposure method, since the distance between the photomask and the resin layer is large, the continuous productivity is high, but the resolution tends to be low.

The resin layer obtained by using the preferred alkali development type photosensitive black shielding agent of the present invention can be used in any of the non-contact exposure method and the contact exposure method described above.

(Development process)
After the exposure step, development is performed with an alkaline aqueous solution to remove an unexposed portion of the resin layer and form a pattern.

Developing methods include dipping method, shower method, spray method, brush method and the like.

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

(Thermosetting process)
The exposed portion of the resin layer is thermally cured to form a cured product (for example, a black shielding portion) having a predetermined pattern on a glass substrate or the like.

The thermosetting conditions may be 140 to 180 ° C., for example.

Here, the glass substrate provided with the cured product (black shielding part) of the alkali development type photosensitive black shielding agent of the present invention can be used for various applications, but preferably for various display devices, It is particularly preferable for an in-vehicle display.

<< First Example >>
[(A) Synthesis of carboxyl group-containing resin]
A cresol novolac type epoxy resin (manufactured by Dainippon Ink & Chemicals, Inc., registered trademark “Epiclon” N-695, epoxy equivalent: 220) was placed in a four-necked flask equipped with a stirrer and a reflux condenser, 214 parts of tall acetate was added and dissolved by heating. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of dimethylbenzylamine as a reaction catalyst were added. This mixture was heated to 95 to 105 ° C., and 72 parts of acrylic acid was gradually added dropwise to react for 16 hours. The reaction product was cooled to 80 to 90 ° C., 106 parts of tetrahydrophthalic anhydride was added, allowed to react for 8 hours, cooled and taken out.
The photosensitive resin having both an ethylenically unsaturated bond and a carboxyl group thus obtained had a nonvolatile content of 65%, a solid acid value of 85 mgKOH / g, and a weight average molecular weight Mw of about 3,500. 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 in which three pumps LC-804, KF-803, and KF-802 manufactured by Shimadzu Corporation were connected.

<Raw material of alkali development type photocurable thermosetting resin composition>
[(A) Carboxyl group-containing resin]
A-1 Varnish [(B) Photopolymerization initiator]
(B-1) Oxime-based photopolymerization initiator TOE-04-A3 (Nippon Chemical Industry Co., Ltd.)
(B-2) Photopolymerization initiator other than oxime type Omnirad TPO (manufactured by IGM Resins)
[(C) Reactive diluent]
DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)
[(D) Thermosetting resin]
JER828 (Mitsubishi Kasei)
[(E) Solvent]
(E-1) Ketone solvent Solvent other than cyclohexanone (E-2) ketone Dipropylene glycol monomethyl ether 1-methoxy-2-propanol Diethylene glycol monoethyl ether acetate [(F) Other components (colorant)]
Perylene red colorant (CI Pigment Red 149)
Phthalocyanine blue colorant (CI Pigment Blue 15: 3)
Anthraquinone yellow colorant (CI Pigment Yellow 147)
Carbon black (CI Pigment Black 7)

<Preparation of alkali development type photocurable thermosetting resin composition according to Examples and Comparative Examples>
Based on the component composition shown in Table 1, each component is blended, premixed with a stirrer, then kneaded and dispersed, and the alkali development comprising the first composition and the second composition according to Examples and Comparative Examples A mold photocurable thermosetting resin composition was prepared. Content in a table | surface shows a mass part. Moreover, about components other than (E) solvent in a table | surface, content in conversion of solid content is shown.

Further, as Comparative Examples 3 to 6, preparations were prepared in which the first composition and the second composition of the alkali development type photocurable thermosetting resin composition according to each Example and each Comparative Example were mixed in advance. did.

<Evaluation>
Each composition thus obtained was allowed to stand at room temperature for 7 days or 120 days, and then the presence and size of recrystallized particles were confirmed. Next, the 1st composition and the 2nd composition were mixed and photosensitivity, resolution, and adhesiveness were evaluated based on the following evaluation methods. These evaluation results are shown in Table 2.

[Coating film preparation conditions]
The film was coated on a glass substrate with an applicator so that the film thickness after drying was 10 μm, and dried at 80 ° C. for 30 minutes in a hot-air circulating drying furnace to prepare a coating film.

[sensitivity]
A step tablet (Kodak No. 2) was brought into close contact with the dried coating film, exposed to 1000 mJ / cm ² using a metal halide lamp exposure machine, developed, and then the sensitivity was evaluated from the number of steps obtained from the step tablet. The evaluation criteria are as follows.
O ... The number of obtained stages is 7 or more.
X: The obtained number of stages is less than 7.

[Resolution]
The dried coating film was exposed to 1000 mJ / cm ² using a metal halide lamp exposure machine and developed, and then the formed minimum width line was read to evaluate the resolution.
O ... L / S = 100/100 remains.
X ... L / S = 100/100 does not remain.

[Adhesion]
According to the test method of JIS (Japanese Industrial Standards) D-0202, 100 crosscuts were put in a checkerboard pattern on the cured coating film of the test piece, and then the peeled part after the peeling test with a cellophane adhesive tape was visually judged. . The evaluation criteria are as follows.
O ... 100 squares remain.
X ... 100 squares do not remain.

[Recrystallization]
The size of the recrystallized particles was confirmed with a grindometer (0-25 μm). When the size of the recrystallized particles is 5 μm or more, pinholes are generated when the film thickness of the cured coating film of each composition is 10 μm, resulting in poor appearance. In addition, when there was no recrystallized particle and when the size of the recrystallized particle was less than 5 μm, no pinhole was generated even when the film thickness of the cured coating film of each composition was 10 μm.
〇 ・ ・ ・ No recrystallized particles.
Δ: Size of recrystallized particles is less than 5 μm.
X: Recrystallized particle size of 5 μm or more.
[OD value]
The glass substrate was attached to a transmission densitometer (manufactured by Sakata Inx Engineering, model number: X-Rite 361T, light source wavelength: 400 to 800 nm) with the film side facing the measuring device, and the OD value was evaluated.
○ OD value is over 4 △ OD value is 3 or more and 4 or less × OD value is less than 3

<< Second Example >>
<Raw material for alkali developing photosensitive black shielding agent>
(A) Carboxyl group-containing resin, A-1 varnish (B) Photopolymerization initiator, B-1: TOE-04-A3 (manufactured by Nippon Chemical Industry Co., Ltd.)
B-2: Omnirad TPO (IGM Resins)
(C) Photocurable monomer (reactive diluent)
C-1: M-360 (manufactured by Toagosei Co., Ltd., EO-modified trimethylolpropane triacrylate)
C-2: DPCA-120 (manufactured by Nippon Kayaku Co., Ltd., caprolactone-modified dipentaerythritol hexaacrylate)
C-3: TMPTA (trimethylolpropane triacrylate)
C-4: DPHA (dipentaerythritol hexaacrylate)
(D) Thermosetting resin / jER834 (Mitsubishi Chemical Co., epoxy resin)
(E) Solvent, cyclohexanone, DPM (dipropylene glycol monomethyl ether)
(F-1) Colorant / Carbon Black (CI Pigment Black 7)
Perylene-based red colorant (CI Pigment Red 149)
-Phthalocyanine blue colorant (CI Pigment Blue 15: 3)
Anthraquinone yellow colorant (CI Pigment Yellow 147)
(F-2) Other components / leveling agent: BYK-361N (manufactured by Big Chemie Japan)

<Preparation of alkali developing photosensitive black shielding agent according to Examples and Comparative Examples>
Based on the component compositions shown in Tables 3 to 4, the respective components were blended, premixed with a stirrer, kneaded and dispersed, and from the first composition and the second composition according to Examples and Comparative Examples An alkali development photosensitive black shielding agent was prepared. In addition, content in a table | surface shows a mass part. Moreover, about components other than (E) organic solvent in a table | surface, content in conversion of solid content is shown.

<Evaluation>
For each of Examples 3 to 14, each evaluation of sensitivity, resolution, adhesion, recrystallization, and OD value was performed under the same coating film forming conditions and evaluation method as in Example 1.
The evaluation results of Examples 3 to 14 were equivalent to those of Example 1.
The evaluation results of Comparative Examples 7 to 9 were equivalent to those of Comparative Example 1.

Furthermore, the resolution, adhesion, tackiness, and OD value of the photosensitive black shielding agent thus obtained were evaluated based on the following evaluation methods. These evaluation results are also shown in Tables 3 to 4.

[Resolution 2]
On a chemically strengthened glass plate (Dragonrail, manufactured by AGC), a shielding material is applied by air spray so that the film thickness after drying becomes 10 μm. After drying (80 ° C., 30 min), a predetermined photomask is applied to the coating film. It was made to adhere and exposed (exposure amount on the shielding material: 700 mJ / cm ² ), and then developed (1 wt% Na ₂ CO ₃ , 30 ° C., 0.2 MPa, 60 sec) to prepare a test piece. The thinnest remaining line in the test piece was visually confirmed. The evaluation criteria are as follows.
A: The minimum remaining line width after development is 50 μm or less.
○: The minimum remaining line width is more than 50 μm and 100 μm or less.
Δ: The minimum remaining line width is more than 100 μm and 150 μm or less.
X: The minimum remaining line width is more than 150 μm.

[Adhesion 2 (cross cut)]
On a chemically strengthened glass plate (Dragonrail, manufactured by AGC), a shielding material is applied by air spray so that the film thickness after drying becomes 10 μm. After drying (80 ° C., 30 min), a predetermined photomask is applied to the coating film. It was made to adhere and exposed (exposure amount on the shielding material 700 mJ / cm ² ). Next, development (1 wt% Na ₂ CO ₃ , 30 ° C., 0.2 MPa, 60 sec), post UV (metal halide lamp, 1000 mJ / cm ² ), and thermal curing (150 ° C., 60 min) were sequentially performed to prepare test pieces.
In accordance with JISK5400, 100 mm grids (10 × 10) of 1 mm are made on the test piece film, and transparent adhesive tape (Nichiban Co., Ltd., width: 18 mm) is completely adhered on the grid, and the tape is immediately applied. While maintaining one end of the substrate at a right angle to the glass substrate, it was momentarily pulled apart, and the number of grids remaining without being completely removed was examined. The evaluation criteria are as follows.
○: 100% of the grid pattern remained.
(Triangle | delta): 95% or more and less than 100% remain | survived.
X: A grid of less than 95% remained.

[Tackiness]
On a chemically strengthened glass plate (Dragonrail, manufactured by AGC), a shielding material is applied by air spray so that the film thickness after drying becomes 10 μm. After drying (80 ° C., 30 min), a predetermined photomask is applied to the coating film. It was made to adhere and exposed (exposure amount on the shielding material 700 mJ / cm ² ). Subsequently, the photomask was peeled off from the coating film by hand, and the ease of peeling of the mask at that time and the presence or absence of adhesion marks on the photomask were visually confirmed. The evaluation criteria are as follows.
◎: No resistance when peeling and no adhesion marks ○: No resistance when peeling and adhesion marks are inconspicuous △: Feeling resistance when peeling and adhesion marks are not outstanding ×: Feeling resistance when peeling The shielding material is transferred to the photomask.

[OD value 2 (light shielding property)]
The glass substrate was attached to a transmission densitometer (manufactured by Sakata Inx Engineering, model number: X-Rite 361T, light source wavelength: 400 to 800 nm) with the film side facing the measuring device, and the OD value was evaluated. The evaluation criteria are as follows.
◎: OD value is 6 or more ○: OD value is 5 or more and less than 6 △: OD value is 4 or more and less than 5 ×: OD value is less than 4

Claims (6)

1. A photocurable thermosetting composition containing at least an alkali-soluble resin, a photopolymerization initiator having an oxime bond, a reactive diluent, a thermosetting resin, and a solvent,
   The photopolymerization initiator having an oxime bond is blended in a composition different from the alkali-soluble resin, and the solvent blended with the photopolymerization initiator having an oxime bond is a ketone solvent in an amount of 50% by mass. An alkali-developable photocurable thermosetting resin composition comprising at least a two-component system, comprising the above.
2. The alkali-developable photocurable heat composition according to claim 1, wherein the solvent blended with the photopolymerization initiator having an oxime bond does not contain an ether solvent. Curable resin composition.
3. The alkali developing type photo-curable thermosetting resin composition according to claim 1 or 2, further comprising a colorant.
4. The colorant contains carbon black and a mixed color black colorant, and the content of the carbon black is 4 to 10% by mass in terms of solid content per total amount of the alkali development type photocurable thermosetting resin composition. The alkali-developable photocurable thermosetting composition comprising at least a two-component system according to claim 3, wherein the mixed color black colorant is present in an amount of 8 to 20% by mass. Resin composition.
5. 5. The alkali according to claim 4, wherein the reactive diluent contains a bifunctional or higher functional (meth) acrylate modified with either alkylene oxide or lactone. Development type photocurable thermosetting resin composition.
6. An alkali development type photocurable thermosetting resin composition comprising at least a two-component system according to claim 5, wherein the composition is used for a glass substrate.