阅读说明：本技术 碱显影型光固化性热固化性树脂组合物 (Alkali-developable photocurable and thermosetting resin composition ) 是由 吉田正人 播磨英司 森口史章 于 2019-03-19 设计创作，主要内容包括：[课题]提供：长时间保存时分辨率、灵敏度等、密合性也优异的树脂组合物。[解决方案]一种至少由双组分体系组成的碱显影型光固化性热固化性树脂组合物,其至少含有：碱溶性树脂、具有肟键的光聚合引发剂、反应性稀释剂、热固化性树脂、溶剂,具有肟键的光聚合引发剂与碱溶性树脂配混于不同的组合物,而且与具有肟键的光聚合引发剂配混的溶剂在溶剂中包含50质量％以上的酮系溶剂。([ problem ] to provide: a resin composition having excellent resolution, sensitivity and adhesion even when stored for a long period of time. [ solution ] an alkali-developable photocurable/thermosetting resin composition comprising at least a two-component system, which contains at least: the thermosetting resin composition comprises an alkali-soluble resin, a photopolymerization initiator having an oxime bond, a reactive diluent, a thermosetting resin, and a solvent, wherein the photopolymerization initiator having an oxime bond and the alkali-soluble resin are blended in different compositions, and the solvent blended with the photopolymerization initiator having an oxime bond contains a ketone solvent in an amount of 50 mass% or more in the solvent.)

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

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

2. The alkali-developable photocurable and thermosetting resin composition comprising at least a two-component system according to claim 1, wherein the solvent to be compounded with the photopolymerization initiator having an oxime bond is free from an ether solvent.

3. The alkali-developable photocurable and thermosetting resin composition comprising at least a two-component system according to claim 1 or 2, further comprising a colorant.

4. The alkali-developable photocurable and thermosetting resin composition comprising at least a two-component system according to claim 3, wherein the colorant comprises carbon black and a color-blended black colorant, and the content of the carbon black is 4 to 10% by mass and the content of the color-blended black colorant is 8 to 20% by mass in terms of solid content relative to the total amount of the alkali-developable photocurable and thermosetting resin composition.

5. The alkali-developable photocurable and thermosetting resin composition comprising at least a two-component system according to claim 4, wherein the reactive diluent contains a (meth) acrylate having 2 or more functions modified with any one of an alkylene oxide and a lactone.

6. The alkali-developable photocurable and thermosetting resin composition comprising at least a two-component system according to claim 5, which is used for a glass substrate.

Technical Field

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

Background

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

Disclosure of Invention

Problems to be solved by the invention

A photopolymerization initiator having an oxime bond is a component that can be used also for a curable resin composition used for a high-definition material that requires high sensitivity, and on the other hand, a curable resin composition containing a photopolymerization initiator having an oxime bond gradually decreases optical characteristics such as sensitivity and resolution during storage. Therefore, it is difficult to provide a curable resin composition having excellent optical characteristics and the like even after long-term storage.

To solve such a problem, for example, patent document 2 proposes the following: the photopolymerization initiator having an oxime bond and the carboxyl group-containing resin are stored as two components, and deactivation is reduced.

However, since a composition having high light-shielding properties such as black is poor in light transmission, such as an alkali development type photosensitive masking agent, when the amount of a photopolymerization initiator having an oxime bond with high sensitivity is increased for the purpose of improving sensitivity in such a composition, deactivation can be reduced by forming two components as described above, but this is not complete, and in addition, the photopolymerization initiator having an oxime bond is recrystallized to generate coarse particles. In particular, in the case of a masking agent, pinholes may occur in coarse particles in the cured coating film of the masking agent due to the generation of coarse particles, and this may also cause appearance defects.

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

Means for solving the problems

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

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

the photopolymerization initiator having an oxime bond and the alkali-soluble resin are mixed in different compositions, and the solvent mixed with the photopolymerization initiator having an oxime bond contains not less than 50% by mass of a ketone solvent in the solvent.

The solvent to be blended with the photopolymerization initiator having an oxime bond preferably does not contain an ether solvent.

The alkali-developable photocurable and thermosetting resin composition preferably further contains a colorant.

Preferably, the colorant comprises carbon black and a melange black colorant, and the content of the carbon black is 4 to 10% by mass and the content of the melange black colorant is 8 to 20% by mass in terms of solid content relative to the total amount of the alkali-developable photocurable/thermosetting resin composition.

The reactive diluent preferably contains a 2-or more-functional (meth) acrylate modified with any of an alkylene oxide and a lactone.

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

ADVANTAGEOUS EFFECTS OF INVENTION

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

Detailed Description

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

When an isomer exists in the compound described above, all isomers that may exist may be used in the present invention unless otherwise specified.

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

The solid component is not particularly limited, and means a component constituting the composition other than the solvent (particularly, an organic solvent), or the mass and volume thereof.

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

The curable resin composition of the present invention is a photocurable and thermosetting composition (photocurable and thermosetting material) containing at least (a) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a reactive diluent, (D) a thermosetting resin, and (E) a solvent, and is an alkali-developable photocurable and thermosetting resin composition (alkali-developable photocurable and thermosetting material) material comprising at least two components (which may be 3 or more) of the composition 1 and the composition 2, the 1 st composition contains at least (A) an alkali-soluble resin, and the 2 nd composition contains (B-1) a photopolymerization initiator having an oxime bond { hereinafter referred to as an "oxime-based photopolymerization initiator" } as the photopolymerization initiator (B), and (E-1) a ketone-based solvent as the solvent (E) in an amount of 50 mass% or more of the solvent.

The curable resin composition of the present invention may contain (F) other components within a range not to impair the effects of the present invention.

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

(an essential component, component contained in the composition No. 1)

(A) Alkali soluble resin

(an essential component, component contained in the composition No. 2)

(B-1) Oxime-based photopolymerization initiator

(E-1) Ketone-based solvent

(as an essential ingredient, optionally included in any or all of the compositions.)

(C) Reactive diluents

(D) Thermosetting resin

(optional Components)

(E) Solvent(s)

(B-2) photopolymerization initiators other than oxime type

(F) Other ingredients

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

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

[ (A) alkali-soluble resin ]

As the alkali-soluble resin, known ones can be used, and a carboxyl group-containing resin or a phenolic hydroxyl group-containing resin is preferably used. In particular, the use of a carboxyl group-containing resin is more preferable from the viewpoint of developability. The alkali-soluble resin may be used alone in 1 kind, or may be used in combination with 2 or more kinds.

As the carboxyl group-containing resin, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is more preferable as a photosensitive composition to be subjected to alkali development, particularly from the viewpoint of photocurability and development resistance. Moreover, the unsaturated double bond thereof is preferably derived from acrylic acid or methacrylic acid, or a derivative thereof.

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

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

(III) a carboxyl group-containing photosensitive polyurethane resin obtained by addition polymerization of a diisocyanate, a (meth) acrylate ester or a partial acid anhydride modified product thereof with a 2-functional epoxy resin such as a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a bixylenol epoxy resin, a biphenol epoxy resin, or the like, a carboxyl group-containing diol compound, and a diol compound.

(IV) in the (II) or (III) resin synthesis, adding (meth) acrylic acid hydroxyl alkyl ester in the molecule having 1 hydroxyl and more than 1 (meth) acryloyl compound, the terminal (meth) acrylic acyl containing carboxyl photosensitive polyurethane resin.

(V) a carboxyl group-containing photosensitive polyurethane resin having a terminal (meth) acrylated by adding a compound having 1 isocyanate group and 1 or more (meth) acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, to the synthesis of the resin of (II) or (III).

(VI) a carboxyl group-containing photosensitive resin obtained by reacting a 2-functional or higher polyfunctional (solid) epoxy resin with (meth) acrylic acid to add a dibasic acid anhydride to a hydroxyl group present in a side chain.

(VII) a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a 2-functional (solid) epoxy resin with epichlorohydrin with (meth) acrylic acid to add a dibasic acid anhydride to the resulting hydroxyl group.

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

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

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

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

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

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

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

The carboxyl group-containing resin may be used alone in 1 kind, or in combination of 2 or more kinds. When the curable resin composition of the present invention contains 2 or more kinds of carboxyl group-containing resins, for example, the above-mentioned (a1) carboxyl group-containing photosensitive resin is preferably contained.

In another embodiment of the curable resin composition of the present invention, the carboxyl group-containing resin may contain the carboxyl group-containing photosensitive resin (a1) and a carboxyl group-containing acrylic copolymer having no alicyclic skeleton. Examples of the carboxyl group-containing acrylic copolymer having no alicyclic skeleton include (1) styrene copolymer type carboxyl group-containing resins listed as specific examples of the above carboxyl group-containing resins. The compounding ratio in the case of compounding the carboxyl group-containing acrylic copolymer having no alicyclic skeleton is, for example, 10 to 95 parts by mass, preferably 10 to 80 parts by mass, based on 100 parts by mass of the entire carboxyl group-containing resin.

The phenolic hydroxyl group-containing resin is not particularly limited as long as it has a phenolic hydroxyl group in the main chain or side chain, that is, a hydroxyl group bonded to a benzene ring. Preferred are compounds having 2 or more phenolic hydroxyl groups in 1 molecule. Examples of the compound having 2 or more phenolic hydroxyl groups in 1 molecule include: catechol, resorcinol, hydroquinone, dihydroxytoluene, naphthalene diol, tert-butylcatechol, tert-butylhydroquinone, pyrogallol, phloroglucinol, bisphenol a, bisphenol F, bisphenol S, biphenol, binaphthol, novolak-type phenol resin, novolak-type alkylphenol resin, bisphenol a novolak resin, dicyclopentadiene-type phenol resin, Xylok-type phenol resin, terpene-modified phenol resin, polyvinyl phenol, a condensate of a phenol and an aromatic aldehyde having a phenolic hydroxyl group, a condensate of 1-naphthol or 2-naphthol and an aromatic aldehyde, and the like, but is not limited thereto. The phenolic hydroxyl group-containing compound may be used alone in 1 kind, or in combination of 2 or more kinds.

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

[ (B) photopolymerization initiator ]

[ B-1 ] Oxime-based photopolymerization initiator

As the oxime-based photopolymerization initiator, known ones can be used. The oxime photopolymerization initiator may be used alone in 1 kind, or may be used in combination with 2 or more kinds.

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

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

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

The alkyl group represented by R1 and R2 is preferably an alkyl group having 1 to 20 carbon atoms, and may contain 1 or more oxygen atoms in the alkyl chain. Further, the hydroxyl group may be substituted by 1 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 a structural moiety represented by the general formula (I) include: oxime ester compounds having a carbazole skeleton, such as 1, 2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime) ], compounds represented by the following formula (I-1), 2- (acetoxyiminomethyl) thioxanthen-9-one, and 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyloxime), and compounds represented by the following general formula (I-2), and the like.

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

Such an oxime ester photopolymerization initiator is preferable because it can improve the sensitivity of the curable resin composition of the present invention to exposure for direct imaging and is excellent in resolution. The oxime ester photopolymerization initiator may be a dimer.

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

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

Ar represents a single bond, or an alkylene group having 1 to 10 carbon atoms, a vinylene group, a phenylene group, a biphenylene group, a pyridylene group, a naphthylene group, an anthracenylene group, a thienylene group, a furylidene group, a 2, 5-pyrrole-diyl group, 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 optionally have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), an amino group, an alkylamino group (preferably having 1 to 8 carbon atoms in the alkyl group), a dialkylamino group (preferably having 1 to 8 carbon atoms in the alkyl group), and the like.

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

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 optionally has a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), an amino group, an alkylamino group (preferably having 1 to 8 carbon atoms in the alkyl group), a dialkylamino group (preferably having 1 to 8 carbon atoms in the alkyl group), and the like.

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

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

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

As the oxime ester photopolymerization initiator (B), commercially available products include: CGI-325 manufactured by BASF Japan K.K., Irgacure OXE01(1- [4- (phenylthio) ] -1, 2-octanedione 2- (O-benzoyloxime)), Irgacure OXE02(1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime)), N-1919 manufactured by ADEKA K.K., NCI-831, TR-PBG-304 manufactured by Changzhou powerful new electron material Co., Ltd., TOE-04-A3 manufactured by Nippon chemical industry Co., Ltd., etc.

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

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

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

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

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

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

As the photopolymerization initiator other than the oxime type, known ones can be used. The oxime photopolymerization initiator may be used alone in 1 kind, or may be used in combination with 2 or more kinds.

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

[ (C) reactive diluent ]

As the reactive diluent, a known one can be used. The reactive diluent may be used alone in 1 kind, or may be used in combination with 2 or more kinds.

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

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

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

When the curable resin composition of the present invention is used as a black masking agent (alkali development type photosensitive black masking agent), the (meth) acrylate { hereinafter, referred to as "(meth) acrylate (c)") having 2 or more functions (preferably 3 or more functions) modified with any one of an alkylene oxide and a lactone is preferably contained as the reactive diluent, i.e., the photocurable monomer of the present invention. Thus, a black blocking agent having excellent adhesion to a glass substrate can be provided. When the (meth) acrylate (c) is contained, the alkali-soluble resin (a) is preferably a carboxyl group-containing resin.

Here, the (meth) acrylate (c) may be one in which at least a part of the 2 or more functional (meth) acrylate is modified with an alkylene oxide or a lactone. The (meth) acrylic ester (c) may be modified with both an alkylene oxide and a lactone.

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

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

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

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

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

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

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

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

[ (D) thermosetting resin ]

As the thermosetting resin, a known thermosetting resin can be used. The thermosetting resin may be used alone in 1 kind or in combination with 2 or more kinds.

Examples of the thermosetting resin include an amino resin such as a melamine resin, a benzoguanamine resin, a melamine derivative, or a benzoguanamine derivative, an isocyanate compound, a blocked isocyanate compound, a cyclic carbonate compound, an epoxy compound, an oxetane compound, an episulfide resin, a bismaleimide, and a carbodiimide resin.

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

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

Examples of the polyfunctional epoxy compound include: epoxidizing a vegetable oil; bisphenol a type epoxy resin; hydroquinone type epoxy resins; bisphenol type epoxy resins; thioether type epoxy resins; brominated epoxy resins; a novolac type epoxy resin; a diphenol novolak-type epoxy resin; bisphenol F type epoxy resins; hydrogenated bisphenol a type epoxy resin; glycidyl amine type epoxy resins; hydantoin type epoxy resins; an alicyclic epoxy resin; trihydroxyphenyl methane type epoxy resin; a bixylenol-type or biphenol-type epoxy resin or a mixture thereof; bisphenol S type epoxy resin; bisphenol a novolac type epoxy resin; tetrahydroxyphenylethane-type epoxy resins; a heterocyclic epoxy resin; diglycidyl phthalate resin; tetraglycidyl toloyl ethane resin; a naphthalene group-containing epoxy resin; an epoxy resin having a dicyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resin; a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivatives; CTBN-modified epoxy resins, etc., but are not limited thereto. These epoxy resins may be used alone in 1 kind or in combination of 2 or more kinds.

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-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, methyl (3-methyl-3-oxetanyl) methacrylate, methyl (3-ethyl-3-oxetanyl) methacrylate, methyl (3-oxetanyl) acrylate, and the like, In addition to polyfunctional oxetanes such as oligomers and copolymers thereof, there may be mentioned etherates of oxetanol and hydroxyl group-containing resins such as novolak resins, poly (p-hydroxystyrene), Cardo-type bisphenols, calixarenes, and silsesquioxanes. Further, there can be mentioned: and copolymers of unsaturated monomers having an oxetane ring and alkyl (meth) acrylates.

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

Examples of the amino resin such as a melamine derivative and a benzoguanamine derivative include methylolmelamine compounds, methylolbenzoguanamine compounds, methylolglycoluril compounds, methylolurea compounds, and the like.

As the isocyanate compound, a polyisocyanate compound may be compounded. Examples of the polyisocyanate compound include: aromatic polyisocyanates such as 4, 4' -diphenylmethane diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, naphthylene-1, 5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and 2, 4-tolylene diisocyanate dimer; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; alicyclic polyisocyanates such as bicycloheptane triisocyanate; and adducts, biuret and isocyanurate of the above-exemplified isocyanate compounds, and the like.

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

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

[ (E) solvent ]

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

(E-1) Ketone-based solvent

As the ketone solvent, a known one can be used. The ketone solvent may be used alone in 1 kind, or may be used in combination with 2 or more kinds.

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

(E-2) solvents other than ketone solvents

As the solvent other than ketone solvents, known solvents can be used. Further, the solvent other than ketone solvents may be used alone in 1 kind, or may be used in combination with 2 or more kinds.

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

Here, conventionally, an ether-based solvent or the like is used as the solvent, but when the ether-based solvent and the oxime-based polymerization photoinitiator are blended and stored at the same time, it is judged that the oxime-based photopolymerization initiator is deactivated. By blending with a ketone solvent instead of an ether solvent, a two-component composition can be formed without simultaneously blending with a carboxyl group without deactivation or recrystallization, and thus, the two-component composition has excellent storage stability and can be suitably used as a masking material. Therefore, the oxime-based photopolymerization initiator-containing composition 2 is preferably free of solvents other than ketone-based ones. More specifically, the solvent in composition 1 is not particularly limited, but may preferably be a (E-1) ketone solvent or a solvent other than the (E-2) ketone solvent, and in composition 2, the solvent is selected from the (E-1) ketone solvents, and the ketone solvent must be contained in an amount of 50 mass% or more. The content of the ketone solvent in the solvent of the composition 2 may be 55 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, 95 mass% or more, 99 mass% or more, or 100 mass%. When the composition 2 contains a solvent other than the ketone solvent, the ester solvent is preferable, and the solvent other than the ketone solvent may be contained to the extent that the effect of the present invention is not impaired. However, the ether solvent is preferably not used as the solvent for the composition 2 because the oxime photopolymerization initiator is deactivated by the ether solvent.

The solvent is generally used for the purpose of preparation of a composition, adjustment of viscosity when applied to a substrate, and the like. Therefore, the content of the solvent may be appropriately changed depending on the purpose.

[ coloring agent ]

As the colorant, a known colorant can be used. Further, 1 kind of the colorant may be used alone, or 2 or more kinds may be used in combination. The colorant may be contained in any 1 or more of the compositions including the 1 st composition and the 2 nd composition or in the entire composition.

As the colorant, a commonly known colorant such as red, blue, green, yellow, white, black, or the like can be used, and any of pigments, dyes, and pigments can be used. More specifically, The colorant includes a color index (C.I.; issued by The Society of Dyers and Colourists) as described below.

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

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

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

When the curable resin composition of the present invention is used as a black masking agent (alkali development type photosensitive black masking agent) or the like, the content of the colorant is preferably 5 to 50% by mass in terms of solid content relative to the total amount of the alkali development type photosensitive black masking agent from the viewpoint of improving the hiding property of a cured product, so that both the masking property and the resolution can be satisfied. More preferably 10 to 30% by mass.

When the curable resin composition of the present invention is used as a black blocking agent (alkali development type photosensitive black blocking agent) or the like, carbon black is preferably contained as a colorant, and carbon black and a color-mixed black colorant are preferably used in combination. Particularly, when carbon black is used in combination with the mixed color black colorant, it is desirable that the carbon black is contained in an amount of 4 to 10% by mass, preferably 4 to 8% by mass, and the mixed color black colorant is contained in an amount of 8 to 20% by mass, preferably 12 to 16% by mass, in terms of solid content, based on the total amount of the alkali development type photosensitive black screening agent.

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

[ (F) other ingredients ]

Other components include: known additives generally used in curable resin compositions include fillers, heat curing catalysts, photo initiation aids, cyanate ester compounds, elastomers, mercapto compounds, urethane catalysts, thixotropic agents, adhesion promoters, block copolymers, chain transfer agents, polymerization inhibitors, copper inhibitors, antioxidants, rust inhibitors, thickeners such as fine powder silica, organobentonite and montmorillonite, antifoaming and/or leveling agents such as silicone, fluorine and polymer systems, silane coupling agents such as imidazole, thiazole and triazole systems, and flame retardants such as phosphinic acid salts, phosphoric acid ester derivatives and phosphorus compounds such as phosphazene compounds.

< Effect >

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

< use >)

The curable resin composition of the present invention is suitable for forming a permanent coating film such as a solder resist, a cover lay layer, an interlayer insulating layer, and a shielding agent used in an FPD (flat panel display) of a printed circuit board or a flexible printed circuit board, and for forming a resist film, and is particularly excellent in optical characteristics, and therefore, suitable for forming a printed circuit board with high density and high definition. The curable resin composition of the present invention can be used for the production of mask images such as printing inks, inkjet inks, photomask production materials, printing sheet production materials, dielectric patterns, electrode (conductor circuit) patterns, wiring patterns of electronic components, conductive pastes, conductive films, and black matrices.

< method of use >

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

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

[ method of Forming cured product ]

The cured product is generally obtained by performing a resin layer forming step, an exposure step, a developing step, and a thermosetting step. The respective steps will be explained below.

(resin layer Forming step)

The composition 1 and the composition 2 are mixed, and the viscosity is adjusted by an organic solvent as necessary to form a coating composition. Next, the coating composition is applied to the substrate in a desired thickness. Next, the organic solvent contained in the coating composition is evaporated and dried to form a resin layer on the substrate.

Examples of the base material include, in addition to a printed wiring board and a flexible printed wiring board on which a circuit is formed in advance: copper-clad laminates of all grades (e.g., FR-4) such as copper-clad laminates for high-frequency circuits using paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven fabric epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluorine/polyethylene/polyphenylene ether (polyphenylene oxide)/cyanate ester, and the like; and polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, and the like.

In particular, in the case of the alkali development type photosensitive black mask of the present invention, the substrate is preferably a glass substrate.

The shape and type of the glass substrate may be appropriately changed depending on the application. The alkali development type photosensitive black masking agent has high resolution and high adhesion to a glass substrate, and therefore, not only a flat glass substrate but also a curved glass substrate can be used.

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

The coating film thickness can be set to a range of 0.5 to 100 μm, 0.5 to 50 μm, 2 to 40 μm, or 2 to 20 μm, for example, in terms of the film thickness after drying.

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

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

(Exposure Process)

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

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

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

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

The contact exposure method has a high resolution because the photomask is in contact with the resin layer, but may cause continuous deterioration in productivity such as contamination of the photomask or abnormal stoppage of the automatic exposure machine due to adhesion of the resin layer to the photomask when the photomask is removed after exposure. In the non-contact exposure method, since the distance between the photomask and the resin layer is long, continuous productivity is high, and resolution tends to be low.

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

(developing step)

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

Examples of the developing method include a dipping method, a shower method, a spray method, a brush method, and the like.

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

(Heat curing step)

The exposed portion of the resin layer is thermally cured to form a cured product (e.g., a black mask portion) having a predetermined pattern on a glass substrate or the like.

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

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