JP7187538B2 - Alkali developable photocurable thermosetting resin composition - Google Patents

Description

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

As one of the components of a curable resin composition that can be used for alkali-developable liquid photosolder resist compositions, alkali-developable photosensitive shielding agents, etc., conventionally, a photopolymerization initiator having an oxime bond is used ( For example, Patent Document 1).

Japanese Unexamined Patent Application Publication No. 2011-022328 International Publication No. 2012/043001

A photopolymerization initiator having an oxime bond is a component that can also be used in a curable resin composition used for high-definition materials that require high sensitivity, while a photopolymerization initiator having an oxime bond is included. The curable resin composition gradually deteriorates in optical properties such as sensitivity and resolution during storage. Therefore, it has been difficult to provide a curable resin composition that is excellent in optical properties and the like even after long-term storage.

To address such a problem, for example, Patent Document 2 proposes to store a photopolymerization initiator having an oxime bond and a carboxyl group-containing resin in two liquids to reduce deactivation.

However, since a composition with a high hiding property such as a black color such as an alkali-developable photosensitive shielding agent has poor light transmission, such a composition has a highly sensitive oxime bond for the purpose of improving the sensitivity. When the amount of the photopolymerization initiator is increased, deactivation can be reduced by using two liquids as described above, but it is not complete. There was a case. In particular, in the case of the shielding agent, the generation of coarse particles may cause pinholes in places where the coarse particles are generated in the cured coating film of the shielding agent, resulting in poor appearance.

In view of the above, an object of the present invention is to provide a resin composition which is excellent in resolution, sensitivity, adhesion, etc., and which 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 has excellent solubility in a specific solvent. 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 separate from the alkali-soluble resin, and the solvent to be blended with the photopolymerization initiator having an oxime bond is a ketone solvent of 50% by mass in the solvent. The alkali-developable photocurable thermosetting resin composition is composed of at least a two-liquid system, characterized by comprising the above.
Moreover, it is preferable that the solvent mixed with the photopolymerization initiator having the oxime bond does not contain an ether solvent.
Furthermore, it is preferable to contain a coloring agent.
The coloring agent contains carbon black and a mixed color black coloring agent, and the content of the carbon black is 4 to 10% by mass in terms of solid content per the total amount of the alkali-developable photocurable thermosetting resin composition. and the content of the mixed black colorant is preferably 8 to 20% by mass.
It is preferable that the reactive diluent contains a bifunctional or higher (meth)acrylate modified with either an alkylene oxide or a lactone.
The alkali-developable photocurable thermosetting resin composition is preferably for glass substrates.

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

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

In addition, when isomers exist in the described compounds, all possible isomers can be used in the present invention unless otherwise specified.

In this specification, (meth)acrylate is a generic term for acrylate, methacrylate and mixtures thereof, and the same applies to other similar expressions.

Unless otherwise specified, the solid content means the components constituting the composition other than the solvent (particularly the organic solvent), or the mass or volume thereof.

The curable resin composition of 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 at least the alkali-soluble resin, and the solvent blended with the photopolymerization initiator having an oxime bond is a ketone solvent. It is an alkali-developable photocurable thermosetting resin composition composed of at least a two-liquid system.

In other words, the curable resin composition of the present invention comprises 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 an “oxime-based photopolymerization initiator”. }, and (E) a second composition containing (E-1) a ketone-based solvent of 50% by mass or more in the solvent as a solvent. It is an alkali-developable photocurable thermosetting resin composition (alkali-developable 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 components and components contained in the first composition)
(A) Alkali-soluble resin (an essential component and a component contained in the second composition)
(B-1) Oxime-based photopolymerization initiator (E-1) Ketone-based solvent (essential component, component that may be contained in any or all compositions)
(C) Reactive diluent (D) Thermosetting resin (optional component)
(E) Solvent (B-2) Photopolymerization initiator other than oxime system (F) Other components

Each component of the curable resin composition of the present invention is described below.

Here, (F) other components preferably include a coloring agent. Components (A) to (E) and the colorant will be described below, and (F) and other components other than the colorant will be described.

[(A) alkali-soluble resin]
As the alkali-soluble resin, known ones can be used, and it is preferable to use a carboxyl group-containing resin or a phenolic hydroxyl group-containing resin. In particular, it is preferable to use a carboxyl group-containing resin from the standpoint 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 used as a photosensitive composition for 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 copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, or the like.

(II) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; Carboxyl group-containing urethane resins obtained by polyaddition reaction of diol compounds such as polyols, polyester-based polyols, polyolefin-based polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.

(III) a diisocyanate and a 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 a polyaddition reaction of a meth)acrylate or its partial acid anhydride modified product, a carboxyl group-containing dialcohol compound and a diol compound.

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

(V) One isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, during the synthesis of the resin of (II) or (III). A carboxyl group-containing photosensitive urethane resin that is terminally (meth)acrylated by adding a compound having

(VI) A carboxyl group-containing photosensitive resin obtained by reacting (meth)acrylic acid with a polyfunctional (solid) epoxy resin having a functionality of two or more and adding a dibasic acid anhydride to the hydroxyl groups present in the side chains.

(VII) A carboxyl obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin obtained by further 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) A difunctional oxetane resin is reacted with a dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid, and the resulting primary hydroxyl group is treated with a dibasic such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Carboxyl group-containing polyester resin to which 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; Maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid to the alcoholic hydroxyl group of the reaction product obtained by reacting with a monocarboxylic acid containing an unsaturated group such as acrylic acid. A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as an acid.

(X) A reaction product 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 and reacting an unsaturated group-containing monocarboxylic acid to obtain a reaction product A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride with a substance.

(XI) Obtained by reacting a reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with a monocarboxylic acid containing an unsaturated group 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 further 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 20-200 mgKOH/g, more preferably in the range of 40-150 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 improved, and alkali development is improved. On the other hand, when the acid value is 200 mgKOH/g or less, the dissolution of the exposed area by the developer can be suppressed, so the line may become thinner than necessary, and in some cases, the developer may The resist pattern can be satisfactorily drawn by suppressing the dissolution and peeling of the film.

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 property is good, the moisture resistance of the coating film after exposure is good, film thinning during development can be suppressed, and the decrease in 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.

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

Further, in another aspect, the curable resin composition of the present invention includes, as the carboxyl group-containing resin, the above-described carboxyl group-containing photosensitive resin (A1) and a carboxyl group-containing acrylic copolymer having no alicyclic skeleton. It may contain coalescence. Examples of the carboxyl group-containing acrylic copolymer having no alicyclic skeleton include the styrene copolymer type carboxyl group-containing resin (1) exemplified as the specific example of the carboxyl group-containing resin. When the carboxyl group-containing acrylic copolymer having no alicyclic skeleton is blended, the blending ratio is, for example, 10 to 95 parts by mass, preferably 100 parts by mass of the total 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 its main chain or side chain, that is, a hydroxyl group bonded to a benzene ring. Preferred are compounds 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 phenolic resin, novolak-type alkylphenol resin, bisphenol A novolac resin, dicyclopentadiene-type phenolic resin, Xylok-type phenolic resin, terpene-modified phenolic resin, polyvinylphenols, phenol and aromatic aldehydes having a phenolic hydroxyl group, condensates of 1-naphthol or 2-naphthol and aromatic aldehydes, etc., but are not limited to these. A phenolic hydroxyl-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) Photoinitiator]
<(B-1) Oxime Photopolymerization Initiator>
A known oxime photopolymerization initiator can be used. Also, the oxime-based photopolymerization initiators may be used singly or in combination of two or more.

The oxime photopolymerization initiator is an oxime ester photopolymerization initiator, preferably an oxime ester photopolymerization initiator containing a structural moiety represented by the general formula (I) shown below, and further an oxime having a carbazole structure. Ester-based photopolymerization initiators are more preferred. A dimer oxime ester photopolymerization initiator may be used as the oxime ester photopolymerization initiator having a carbazole structure.

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. Moreover, it may be substituted with one or more hydroxyl groups.

A cycloalkyl group having 5 to 8 carbon atoms is preferable as the cycloalkyl group represented by R1 and R2.

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.

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

In general formula (I-2), R11 has the same definition as R1 in general formula (I), and R12 and R14 each independently have the same meaning as R2 in general formula (I). R13 is 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 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 represents 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 to exposure for direct imaging can be increased and the resolution is excellent. Also, the oxime ester photopolymerization initiator may be a dimer.

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

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, represents a 4,4'-stilbene-diyl group and 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.
As the alkoxy group represented by R23, an alkoxy group having 1 to 8 carbon atoms is preferred.
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) 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 substituents 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.
As the alkoxy group represented by R21 and R22, an alkoxy group having 1 to 8 carbon atoms is preferable.
The phenyl group represented by R21 and R22 may have a substituent, such as an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 17 carbon atoms), 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 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, Ar is a single bond, a phenylene group, a naphthylene group or a thienylene The group n is preferably zero.

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

(B) As the oxime ester photopolymerization initiator, commercially available products such as CGI-325 manufactured by BASF Japan, 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)), Examples include N-1919 and NCI-831 manufactured by ADEKA, TR-PBG-304 manufactured by Changzhou Yuan Electronics New Materials Co., Ltd., and TOE-04-A3 manufactured by Nippon Kagaku Kogyosho.

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

The curable resin composition of the present invention may contain other photopolymerization initiators. Other photopolymerization initiators include, for example, benzophenone-based, acetophenone-based, aminoacetophenone-based, benzoin ether-based, benzyl ketal-based, acylphosphine oxide-based, oxime ether-based, and titanocene-based compounds.

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

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

α-Aminoacetophenone-based photopolymerization initiators containing a structural moiety represented by general formula (II) include 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]
As photopolymerization initiators other than oxime-based ones, known ones can be used. Also, the oxime-based photopolymerization initiators may be used singly or in combination of two or more.

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

[(C) reactive diluent]
A known reactive diluent can be used. Moreover, one type of the reactive diluent may be used alone, or two or more types may be used in combination.

A reactive diluent is a compound having carbon-carbon multiple bonds (double and triple bonds) in the molecule, in other words a photocurable monomer. Examples of 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; ethylene glycol, propylene glycol, diethylene glycol, mono or di (meth) acrylates of alkylene oxide derivatives such as dipropylene glycol; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, di Polyhydric alcohols such as pentaerythritol and trishydroxyethyl isocyanurate, or polyhydric (meth)acrylates of ethylene oxide or propylene oxide adducts thereof; phenols such as phenoxyethyl (meth)acrylate and polyethoxydi(meth)acrylate of bisphenol A (Meth)acrylates of ethylene oxide or propylene oxide adducts of; known (meth)acrylates.

The content of the reactive diluent in the curable resin composition of the present invention is not particularly limited. 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 can be suitably used as a black shielding agent or the like containing a highly sensitive photopolymerization initiator. can.
When the curable resin composition of the present invention is used as a black shielding agent (alkali-developable photosensitive black shielding agent), either an alkylene oxide or a lactone is used as the reactive diluent according to the present invention, that is, the photocurable monomer. Bifunctional or more (preferably trifunctional or more) (meth)acrylate modified with (hereinafter referred to as "(meth)acrylate (c)"). } is preferably contained. This makes it possible to provide a black shielding agent with excellent adhesion to glass substrates. Moreover, when this (meth)acrylate (c) is contained, (A) the alkali-soluble resin is preferably a carboxyl group-containing resin.

Here, the (meth)acrylate (c) may be a bifunctional or higher functional (meth)acrylate, at least a portion of which is modified with an alkylene oxide or a lactone. (Meth)acrylate (c) may be modified with both an alkylene oxide and a lactone.

Although the alkylene oxide is not particularly limited, ethylene oxide and propylene oxide are preferred.

Although the lactone is not particularly limited, it is preferably caprolactone.

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

Specific (meth)acrylates (c) include, for example, bifunctional or higher functional (meth)acrylates among the above-described known (meth)acrylates modified with either alkylene oxide or lactone, such as , alkylene oxide adduct polyols or lactone adduct polyols (meth)acrylates. (Meth)acrylate (c) is, more specifically, EO-modified trimethylolpropane triacrylate, EO-modified pentaerythritol tetraacrylate, EO-modified ditrimethylolpropane tetraacrylate, EO-modified dipentaerythritol hexaacrylate, EO-modified trisacrylate EO-modified fluorenediacrylate, 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 isocyanuric acid triacrylate, and the like. Among these, EO-modified trimethylolpropane triacrylate and caprolactone-modified dipentaerythritol hexaacrylate are preferable.

When using (meth)acrylate (c) as a photocurable monomer, one (meth)acrylate (c) may be used alone, or two or more (meth)acrylates (c) may be used in combination. may Furthermore, (meth)acrylate (c) and photocurable monomers other than (meth)acrylate (c) (hereinafter referred to as “other photocurable monomers”) may be used in combination.

Other photocurable monomers are not particularly limited, and the above-described known (meth)acrylates and the like 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. Further, when the content is 45 parts by mass or less, a coating film having good tackiness (no negative sticking) can be obtained.

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

[(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 melamine resins, benzoguanamine resins, melamine derivatives, amino resins such as benzoguanamine derivatives, isocyanate compounds, blocked isocyanate compounds, cyclocarbonate compounds, epoxy compounds, oxetane compounds, episulfide resins, bismaleimide, and carbodiimide resins. etc.

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

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. Compounds having multiple epoxy groups, i.e. polyfunctional epoxy compounds, compounds having multiple oxetanyl groups in the molecule, i.e. polyfunctional oxetane compounds, compounds having multiple thioether groups in the molecule, i.e., episulfide resins, and the like.

As polyfunctional epoxy compounds, epoxidized vegetable oil; bisphenol A type epoxy resin; hydroquinone type epoxy resin; bisphenol type epoxy resin; thioether type epoxy resin; brominated epoxy resin; type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; Bisphenol S type epoxy resin; bisphenol A novolac type epoxy resin; tetraphenylolethane type epoxy resin; heterocyclic epoxy resin; diglycidyl phthalate resin; Glycidyl methacrylate copolymer epoxy resin; cyclohexyl maleimide and glycidyl methacrylate copolymer epoxy resin; epoxy-modified polybutadiene rubber derivative; CTBN-modified epoxy resin, etc., but not limited to these . These epoxy resins can be used singly or in combination of two or more.

Examples of polyfunctional oxetane compounds 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- Oxetanyl)methyl acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate, and polyfunctional oxetanes such as their oligomers or copolymers, as well as oxetane alcohols and novolac resins , poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcinarenes, and etherified products with resins having a hydroxyl group such as silsesquioxane. Other examples include copolymers of unsaturated monomers having an oxetane ring and alkyl (meth)acrylates.

Bisphenol A type episulfide resin etc. are mentioned as a compound which has several cyclic thioether groups in a molecule|numerator. Also, an episulfide resin obtained by replacing the oxygen atom of the epoxy group of the novolac type epoxy resin with a sulfur atom by using a similar synthesis method can also be used.

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; bicyclo alicyclic polyisocyanates such as heptane triisocyanate; and adducts, biurets and isocyanurates of the above-mentioned 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 that can react with the isocyanate blocking agent include the aforementioned polyisocyanate compounds. Examples of isocyanate blocking agents include phenolic blocking agents; lactam blocking agents; active methylene blocking agents; alcohol blocking agents; oxime blocking agents; mercaptan blocking agents; Amine-based blocking agents; imidazole-based blocking agents; imine-based blocking agents, and the like.

The content of the thermosetting resin is not particularly limited, but may be, for example, 0.6 to 2.8 equivalents 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 of these will be described below.

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

Ketone solvents include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl butyl ketone, methyl isobutyl ketone and the like. Among them, cyclohexanone is preferred.

(E-2) Non-Ketone-Based Solvent As the non-ketone-based solvent, known solvents can be used. In addition, the solvents other than ketone-based solvents may be used singly or in combination of two or more.

Non-ketone solvents include aromatic hydrocarbon solvents such as toluene, xylene, tetramethylbenzene; 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, propylene carbonate and other ester solvents; ethanol, propanol, 2-methoxypropanol, n-butanol, isobutyl alcohol , isopentyl 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; N,N-dimethylformamide (DMF), tetrachlorethylene, turpentine oil and the like.

Here, conventionally, an ether-based solvent or the like has been used as a solvent, but when an ether-based solvent is blended together with an oxime-based polymerization photoinitiator and stored, the oxime-based photopolymerization initiator is deactivated. found out. By blending with a ketone-based solvent instead of an ether-based solvent, it does not deactivate and recrystallize, and by not blending with carboxyl groups at the same time, it has excellent storage stability and can be used as a shielding material. becomes. Therefore, it is preferable that the second composition containing the oxime-based photopolymerization initiator does not contain any solvent other than ketone-based solvents. More specifically, the solvent in the first composition is not particularly limited, and may be (E-1) a ketone solvent or (E-2) a non-ketone solvent, and the second composition In (E-1), it is preferable to select a solvent from ketone solvents, and the ketone solvent must be contained in the solvent in an amount of 50% by mass or more. In addition, 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. When the second composition contains a solvent other than a ketone solvent, it is preferably an ester solvent, and may contain a solvent other than the ketone solvent to the extent that the effects of the present invention are not impaired. However, the ether-based solvent deactivates the oxime-based photopolymerization initiator, so it is preferable not to use it as the solvent for the second composition.

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

[Coloring agent]
A known coloring agent can be used. 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 may be contained in any one or more compositions including the first composition and the second composition, or in all compositions.

As the coloring agent, conventionally known coloring agents such as red, blue, green, yellow, white and black can be used, and any of pigments, dyes and pigments can be used. More specifically, the coloring agent includes those assigned the following Color Index (C.I.; published by The Society of Dyers and Colorists) numbers.

Examples of red colorants include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone colorants. Blue colorants include phthalocyanine-based, anthraquinone-based, and the like, and pigment-based compounds classified as pigments can be used. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used. Green coloring agents include phthalocyanines, anthraquinones, and perylenes. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used. Yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone colorants. Examples of white colorants include rutile-type and 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. Molybdenum sulfide, bismuth sulfide, etc. In addition, coloring agents such as purple, orange, and 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 (all compositions including the first composition and the second composition) 0.03 to 7% by mass, more preferably 0.05% to 5% by mass, in terms of solid content per total amount).

Here, since the curable resin composition of the present invention can reduce the deactivation of the photopolymerization initiator having an oxime bond, it can be suitably used as a black shielding agent or the like containing a highly sensitive photopolymerization initiator. can.

When the curable resin composition of the present invention is used as a black shielding agent (alkali-developable photosensitive black shielding agent) or the like, the content of the coloring agent is adjusted from the viewpoint of improving the hiding property of the cured product, and the alkali-developable photosensitive By containing 5 to 50% by mass in terms of solid content based on the total amount of the black shielding agent, both shielding properties and resolution can be achieved, which is preferable. More preferably, it 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-developable photosensitive black shielding agent) or the like, the coloring agent preferably contains carbon black. It is preferable to use together with the agent. In particular, when carbon black and a mixed black colorant are used in combination, carbon black is 4 to 10% by mass, preferably 4 to 8% by mass, based on the total amount of the alkali-developable photosensitive black shielding agent, and preferably 4 to 8% by mass, and , the mixed black colorant is preferably 8 to 20% by mass, preferably 12 to 16% by mass.

Note that the mixed black colorant is a colorant mixed with a red colorant, a blue colorant, a green colorant, a yellow colorant, a purple colorant, an orange colorant, etc. so as to obtain a black color or a color close to black. The resulting colorant is shown. The mixed black colorant is preferably added to the resin composition after mixing each colorant in advance, but each colorant constituting the mixed black colorant may be added individually to the resin composition. .

[(F) Other components]
Other components include known additives commonly used in curable resin compositions, such as fillers, thermosetting catalysts, photoinitiator aids, cyanate compounds, elastomers, mercapto compounds, urethanization catalysts, and thixotropic agents. , adhesion promoters, block copolymers, chain transfer agents, polymerization inhibitors, copper damage inhibitors, antioxidants, rust inhibitors, fine powdered silica, organic bentonite, thickeners such as montmorillonite, silicone-based, fluorine-based, Antifoaming agents and/or leveling agents such as high molecular weight agents; silane coupling agents such as imidazole, thiazole and triazole; be done.

<effect>
The alkali-developable photocurable thermosetting resin composition of the present invention comprises (A) a first composition containing at least an alkali-soluble resin, (B-1) an oxime photopolymerization initiator, and (E- 1) a second composition containing at least a ketone solvent. Each composition can be stored in a state in which they do not or hardly come into contact with each other, for example, by being housed in separate containers. By configuring in this way, the solvent preferably used in the curable resin composition can be prevented from acting on the oxime-based photopolymerization initiator to deactivate and recrystallize the oxime-based photopolymerization initiator, and can be stored for a long time. can achieve sexuality.

<Application>
The curable resin composition of the present invention is used for forming permanent coating films such as solder resists, coverlays, interlayer insulating layers, and shielding agents used in FPDs (flat panel displays) and etching resists for printed wiring boards and flexible printed wiring boards. It is suitable for forming films, and in particular, it is suitable for forming printed wiring boards with high density and fine lines due to its excellent optical properties. The curable resin composition of the present invention can also be used for printing inks, inkjet inks, photomask production materials, printing proof production materials, dielectric patterns, electrode (conductor circuit) patterns, wiring patterns for electronic parts, conductive pastes, conductive It can be used for producing shielding images such as films and black matrices.

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

In addition, below, the case where the alkali-developable photocurable thermosetting resin composition of the present invention is a two-liquid system comprising a first composition and a second composition will be described. The first composition and the second composition are blended in compositions containing different alkali-soluble resins and oxime-based photopolymerization initiators, and the solvent of the composition containing the oxime-based photopolymerization initiator is a ketone-based solvent. Thus, it is obtained by mixing each raw material in advance. The alkali-developable photocurable thermosetting resin composition of the present invention is usually assumed to be used after a predetermined storage period, but it can be used immediately without a predetermined storage period. may be

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

(Resin layer forming step)
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. The coating composition is then applied to the desired thickness on the substrate. Next, the organic solvent contained in the coating composition is evaporated and dried to form a resin layer on the substrate.

As a base material, in addition to pre-formed printed wiring boards and flexible printed wiring boards, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy, synthetic fiber epoxy , all grades (FR-4, etc.) copper-clad laminates using materials such as copper-clad laminates for high-frequency circuits using fluorine, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate ester, etc., and other polyimides Films, PET films, glass substrates, ceramic substrates, wafer plates and the like can be mentioned.

Especially when the present invention is an alkali-developable photosensitive black shielding agent, the substrate is preferably a glass substrate.

The shape and type of the glass substrate can be appropriately changed depending on the application. Since the alkali-developable photosensitive black shielding agent described above has high resolution and high adhesion to glass substrates, not only flat glass substrates but also curved glass substrates can be used. is also possible.

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

The coating film thickness may be appropriately set 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.

Drying means include, for example, a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, and the like.

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 with actinic rays (exposure).

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

Irradiation light sources for actinic rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps and metal halide lamps.

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

In the contact exposure method, since the photomask and the resin layer are in contact with each other, the resolution is high. Contamination, abnormal stoppage of the automatic exposure machine, etc. may cause continuous productivity to deteriorate. In the non-contact exposure method, the distance between the photomask and the resin layer is long, so the continuous productivity is high, but the resolution tends to be low.

The resin layer obtained using the preferable alkali-developable photosensitive black shielding agent of the present invention can be used in both the non-contact exposure method and the contact exposure method described above.

(Development process)
After the exposure step, the resin layer is patterned by removing the unexposed portion by developing with an alkaline aqueous solution.

Dipping method, shower method, spray method, brush method and the like can be used as the developing method.

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

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

Thermal curing conditions may be, for example, 140 to 180°C.

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 purposes, and is preferably used for various display devices. It is particularly preferable to use it for an in-vehicle display.

<<First Embodiment>>
[(A) Synthesis of carboxyl group-containing resin]
220 parts of a cresol novolac type epoxy resin (manufactured by Dainippon Ink and Chemicals Co., Ltd., 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., 72 parts of acrylic acid was gradually added dropwise, and the mixture was reacted for 16 hours. This reaction product was cooled to 80 to 90° C., 106 parts of tetrahydrophthalic anhydride was added, reacted for 8 hours, cooled, and taken out.
The thus obtained photosensitive resin having both ethylenically unsaturated bonds and carboxyl groups 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. This resin solution is hereinafter referred to as A-1 varnish.
The weight average molecular weight of the obtained resin was measured by high performance liquid chromatography using three pumps LC-804, KF-803 and KF-802 manufactured by Shimadzu Corporation.

<Raw materials for alkali-developable photocurable thermosetting resin composition>
[(A) Carboxyl Group-Containing Resin]
A-1 varnish [(B) photoinitiator]
(B-1) Oxime-based photopolymerization initiator TOE-04-A3 (manufactured by Nippon Kagaku Kogyosho 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 (manufactured by Mitsubishi Kasei Corporation)
[(E) solvent]
(E-1) Ketone-based solvent Cyclohexanone (E-2) Non-ketone-based solvent Dipropylene glycol monomethyl ether 1-methoxy-2-propanol Diethylene glycol monoethyl ether acetate [(F) Other components (coloring agent)]
Perylene-based red colorant (CI Pigment Red 149)
Phthalocyanine blue coloring agent (C.I. Pigment Blue 15:3)
Anthraquinone-based yellow colorant (CI Pigment Yellow 147)
Carbon black (CI Pigment Black 7)

<Preparation of alkali-developable photocurable thermosetting resin compositions according to Examples and Comparative Examples>
Based on the component composition shown in Table 1, each component was blended, premixed with a stirrer, kneaded and dispersed, and alkali development consisting of the first composition and the second composition according to the examples and comparative examples. A type photocurable thermosetting resin composition was prepared. Contents in the table indicate parts by mass. In addition, in the table, the content of components other than (E) solvent is shown in terms of solid content.

Further, as Comparative Examples 3 to 6, compositions obtained by pre-mixing the first composition and the second composition of the alkali-developable photocurable thermosetting resin composition according to each example and each comparative example were prepared. 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 was checked. Next, the first composition and the second composition were mixed and evaluated for photosensitivity, resolution and adhesion based on the following evaluation methods. These evaluation results are shown in Table 2.

[Conditions for preparing coating film]
It was applied to a glass substrate with an applicator so that the film thickness after drying was 10 μm, and dried in a hot air circulating drying oven at 80° C. for 30 minutes to prepare a coating film.

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

[Resolution]
After drying, the coating film was exposed to light at 1000 mJ/cm ² using a metal halide lamp exposing machine, developed, and the formed minimum width line was read to evaluate the resolution.
Good: 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 cross-cuts were made in a grid pattern on the cured coating film of the test piece, and then the peeled portions after the peeling test with cellophane adhesive tape were visually determined. . In addition, the evaluation criteria are as follows.
O: 100 squares remain.
x: 100 squares are not left.

[Recrystallization]
The size of the recrystallized grains was confirmed with a grindometer (0-25 μm). If the size of the recrystallized particles is 5 µm or more, pinholes will occur and the appearance will be poor when the film thickness of the cured coating film of each composition is 10 µm. When there were no recrystallized particles and when the size of the recrystallized particles was less than 5 µm, pinholes did not occur even when the film thickness of the cured coating film of each composition was 10 µm.
O: No recrystallized particles.
Δ: The size of the recrystallized particles is less than 5 μm.
x: The size of recrystallized grains is 5 μm or more.
[OD value]
The film side of the glass substrate was directed toward the measuring instrument, and a transmission densitometer (manufactured by Sakata Inx Engineering Co., model number: X-Rite 361T, light source wavelength: 400 to 800 nm) was installed to evaluate the OD value.
○ ... OD value is over 4 △ ... OD value is 3 or more and 4 or less × ... OD value is less than 3

<<Second embodiment>>
<Raw material for alkali-developable photosensitive black shielding agent>
(A) carboxyl group-containing resin A-1 varnish (B) photopolymerization initiator B-1: TOE-04-A3 (manufactured by Nippon Kagaku Kogyosho Co., Ltd.)
・ B-2: Omnirad TPO (manufactured by 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 (manufactured by Mitsubishi Chemical Corporation, epoxy resin)
(E) Solvent, cyclohexanone, DPM (dipropylene glycol monomethyl ether)
(F-1) Colorant/carbon black (CI Pigment Black 7)
・Perylene-based red colorant (C.I.Pigment Red 149)
・Phthalocyanine blue colorant (C.I.Pigment Blue 15:3)
・ Anthraquinone-based yellow colorant (C.I.Pigment Yellow 147)
(F-2) Other components/leveling agent: BYK-361N (manufactured by BYK-Chemie Japan)

<Preparation of alkali-developable photosensitive black shielding agents according to Examples and Comparative Examples>
Based on the component compositions shown in Tables 3 and 4, each component was blended, premixed with a stirrer, and then kneaded to disperse, according to Examples and Comparative Examples, from the first composition and the second composition. An alkali-developable photosensitive black screening agent was prepared. In addition, content in a table|surface shows a mass part. In addition, in the table, the content of components other than (E) organic solvent is shown in terms of solid content.

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

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

[Resolution 2]
A shielding material is applied to a chemically strengthened glass plate (Dragontrail, manufactured by AGC) with an air spray so that the film thickness after drying is 10 μm, and after drying (80 ° C., 30 min), a predetermined photomask is applied to the coating film. They were brought into close contact with each other, exposed to light (exposure amount on 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. In addition, 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 over 150 μm.

[Adhesion 2 (cross cut)]
A shielding material is applied to a chemically strengthened glass plate (Dragontrail, manufactured by AGC) with an air spray so that the film thickness after drying is 10 μm, and after drying (80 ° C., 30 min), a predetermined photomask is applied to the coating film. It was brought into close contact and exposed to light (exposure amount on 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 a test piece.
In accordance with JISK5400, 100 grids (10 × 10) of 1 mm are made on the film of the test piece, and a transparent adhesive tape (manufactured by Nichiban Co., Ltd., width: 18 mm) is completely attached on the grid, and the tape is immediately applied. While keeping one end of the glass substrate at a right angle, it was pulled apart instantaneously, and the number of grids remaining without being completely peeled off was examined. Evaluation criteria are as follows.
◯: 100% of the grid pattern remained.
Δ: 95% or more and less than 100% of the grid pattern remained.
x: Less than 95% of the grid pattern remained.

[Tackiness]
A shielding material is applied to a chemically strengthened glass plate (Dragontrail, manufactured by AGC) with an air spray so that the film thickness after drying is 10 μm, and after drying (80 ° C., 30 min), a predetermined photomask is applied to the coating film. It was brought into close contact and exposed to light (exposure amount on shielding material: 700 mJ/cm ² ). Next, the photomask was peeled off from the coating film by hand, and the easiness of peeling of the mask at that time and the presence or absence of adhesion traces of the photomask were visually confirmed. In addition, the evaluation criteria are as follows.
◎: No resistance when peeling and no adhesion marks ○: No resistance when peeling and adhesion marks are not noticeable △: Resistance is felt when peeling and adhesion marks are not noticeable ×: Resistance is felt when peeling and Shielding material transferred to photomask

[OD value 2 (light shielding property)]
The film side of the glass substrate was directed toward the measuring instrument, and a transmission densitometer (manufactured by Sakata Inx Engineering Co., model number: X-Rite 361T, light source wavelength: 400 to 800 nm) was installed to evaluate the OD value. 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)

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 separate from the alkali-soluble resin, and the solvent to be blended with the photopolymerization initiator having an oxime bond is a ketone solvent of 50% by mass in the solvent. An alkali-developable photocurable thermosetting resin composition comprising at least two liquids comprising the above. 2. The alkali-developable photocurable heat composition according to claim 1, wherein the solvent mixed with the photopolymerization initiator having an oxime bond does not contain an ether solvent. A curable resin composition. 3. The alkali-developable photocurable thermosetting resin composition according to claim 1 or 2, which is composed of at least a two-liquid system, further comprising a colorant. The coloring agent contains carbon black and a mixed color black coloring agent, and the content of the carbon black is 4 to 10% by mass in terms of solid content per the total amount of the alkali-developable photocurable thermosetting resin composition. and the content of the mixed black colorant is 8 to 20% by mass. elastic resin composition. 5. An alkali composed of at least a two-liquid system according to claim 4, characterized in that said reactive diluent contains a di- or higher-functional (meth)acrylate modified with either an alkylene oxide or a lactone. Developable photocurable thermosetting resin composition. 6. The alkali-developable photocurable thermosetting resin composition according to claim 5, which is composed of at least a two-liquid system, for use as a glass substrate.