KR102723373B1 - Novel compounds, potential additives and compositions containing the additives - Google Patents

Abstract

A compound represented by the following general formula (1). In the following general formula (1), it is preferable that R ¹ , R ² , R ³ and R ⁴ are -CO-OR ¹¹ , and particularly, it is preferable that R ¹¹ is -CO-OR ¹¹ which is tert-butyl. In the following general formula (1), it is preferable that R ¹ , R ² , R ³ and R ⁴ are a group represented by -CO-OR ¹¹ . The compound represented by the following general formula (1) can be preferably used as a latent additive. The above-mentioned latent additive is preferably used in a photosensitive composition.

Description

Novel compounds, potential additives and compositions containing the additives

The present invention relates to a novel compound, a latent additive comprising the compound which is inactive at room temperature and is activated by heating to a predetermined temperature to exhibit a function, and a composition containing the latent additive. In addition, the present invention relates to a colored photosensitive composition polymerizable by energy rays using the composition, and a color filter using the colored photosensitive composition.

As a method for improving the weather resistance or heat resistance of a resin composition, a method of stabilizing it by adding an ultraviolet absorber or antioxidant is known (Patent Documents 1 to 4).

Phenolic antioxidants have the function of trapping radicals that have a significant effect on the deterioration of polymers. Therefore, when antioxidants are added to a polymerization system, they generally act as so-called polymerization inhibitors, causing curing inhibition, which is a problem. Potential additives have been developed, but satisfactory solubility has not been obtained (Patent Document 5).

Japanese Patent Publication No. 6-179798 Japanese Patent Publication No. 7-109380 Japanese Patent Publication No. 11-071355 Japanese Patent Publication No. 2002-097224 US2015/291772(A1)

Accordingly, the purpose of the present invention is to provide a highly soluble latent additive that is inactive at room temperature and is activated by heating to a predetermined temperature to exhibit a function. In addition, another purpose of the present invention is to provide a heat-resistant composition using the latent additive. In addition, another purpose of the present invention is to provide a colored photosensitive composition containing the composition and a colorant, particularly a colored photosensitive composition suitable for a color filter.

The present inventors, as a result of repeated careful examination, have found that a compound having a specific protecting group functions efficiently as a latent additive, has high solubility and thus good handleability, and that a composition using the same does not cause curing inhibition and has excellent heat resistance because deterioration of an initiator and a colorant is prevented, and further that a colored photosensitive composition containing the composition and a colorant does not lower the brightness of an optical filter (particularly a color filter) and is suitable for a color filter for an image display device such as a liquid crystal display panel, and thus have arrived at the present invention.

The present invention has been made based on the above knowledge and provides a compound represented by the following general formula (1).

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 20 carbon atoms which may or may not have a substituent, an aryl group having 6 to 20 carbon atoms which may or may not have a substituent, an arylalkyl group having 7 to 20 carbon atoms which may or may not have a substituent, a heterocyclic group having 2 to 20 carbon atoms which may or may not have a substituent, a trialkylsilyl group, -CO-OR ¹¹ or -CO-SR ¹² ,

R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may or may not have a substituent, an aryl group having 6 to 20 carbon atoms which may or may not have a substituent, an arylalkyl group having 7 to 20 carbon atoms which may or may not have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may or may not have a substituent.

R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 20 carbon atoms which may or may not have a substituent, an aryl group having 6 to 20 carbon atoms which may or may not have a substituent, an arylalkyl group having 7 to 20 carbon atoms which may or may not have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may or may not have a substituent.

In some cases, multiple R ⁵ s, R ⁶ s, R ⁷ s, and R ⁸ s are combined to form a benzene ring or a naphthalene ring.

Plural R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different,

X ¹ represents a direct bond, an alkylene group having 1 to 4 carbon atoms which may have a substituent, an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, -O-, -S-, -SO ₂ -, -SS-, -SO-, -CO-, -OCO-, or a substituent represented by the following formula (1-1), (1-2) or (1-3),

a, b, c, and d each independently represent an integer from 0 to 4, and e and f each independently represent an integer from 0 to 9.)

(In the above formula, R ⁷¹ represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent,

R ⁷² represents an alkyl group having 1 to 10 carbon atoms, which may or may not have a substituent, an alkoxy group having 1 to 10 carbon atoms, which may or may not have a substituent, an alkenyl group having 2 to 10 carbon atoms, which may or may not have a substituent, or a halogen atom.

i is an integer from 0 to 4.)

(In the above formulas, R ⁷³ and R ⁷⁴ each independently represent an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, an aryl group having 6 to 20 carbon atoms which may or may not have a substituent, an aryloxy group having 6 to 20 carbon atoms which may or may not have a substituent, an arylthio group having 6 to 20 carbon atoms which may or may not have a substituent, an arylalkenyl group having 6 to 20 carbon atoms which may or may not have a substituent, an arylalkyl group having 7 to 20 carbon atoms which may or may not have a substituent, a heterocyclic group having 2 to 20 carbon atoms which may or may not have a substituent, or a halogen atom,

R ⁷³ sometimes forms a ring with adjacent R ^73s .

p represents a number from 0 to 4,

q represents a number from 0 to 8,

g represents a number from 0 to 4,

h represents a number from 0 to 4,

The sum of the numbers of g and h is 2 to 4.)

In addition, the present invention provides a potential additive comprising at least one compound represented by the general formula (1).

In addition, the present invention provides a photosensitive composition containing the potential additive.

According to the present invention, it is possible to provide a highly soluble latent additive that is inactive at room temperature and becomes active by heating to a predetermined temperature. In addition, a composition containing the latent additive does not cause curing inhibition and has excellent heat resistance.

Hereinafter, the present invention will be described in detail based on preferred embodiments.

Examples of the alkyl groups having 1 to 20 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² in the general formula (1) above include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl, adamantyl, etc.

Aryl groups having 6 to 20 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² include phenyl, naphthyl, anthracenyl, etc.

Arylalkyl groups having 7 to 20 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² include benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 2-phenylpropyl, 3-phenylpropyl, fluorenyl, indenyl and 9-fluorenylmethyl groups.

The heterocyclic group containing 2 to 20 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² is pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzoimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinon-1-yl, 2-piperidon-1-yl, Examples thereof include 2,4-deoxyimidazolidin-3-yl, 2,4-deoxyoxazolidin-3-yl, or a group in which a heterocycle is bonded through a divalent bonding group.

Examples of trialkylsilyl groups represented by R ¹ , R ² , R ³ , and R ⁴ include trimethylsilane, triethylsilane, and ethyldimethylsilane.

Halogen atoms represented by R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include fluorine, chlorine, bromine and iodine.

^Substituents substituting the ^{alkyl group having 1 to 20 carbon atoms, the aryl group having 6} to 20 carbon atoms ^, the arylalkyl group having 7 to 20 carbon atoms or the heterocyclic group having 2 to 20 carbon atoms, represented ^by R ¹ , R 2 , R ^{3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 ,} R ¹⁰ , R 11 and R 12, include ethylenically unsaturated groups such as vinyl, allyl, acrylic and methacryl; halogen atoms such as fluorine, chlorine, bromine and iodine; Acyl groups such as acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaroyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, and carbamoyl; acyloxy groups such as acetyloxy and benzoyloxy; Amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, Substituted amino groups such as N,N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, and phenylsulfonylamino; sulfonamide groups, sulfonyl groups, carboxyl groups, cyano groups, sulfo groups, hydroxyl groups, nitro groups, mercapto groups, imide groups, carbamoyl groups, sulfonamide groups, phosphonic acid groups, phosphoric acid groups, or salts of carboxyl groups, sulfo groups, phosphonic acid groups, and phosphoric acid groups, and the substitution positions are not limited.

In the compound represented by the general formula (1), it is preferable that R ¹ , R ² , R ³ and R ⁴ are -CO-OR ¹¹ because this has high solubility and, when used as a latent additive, the cured product of a composition containing it has high heat resistance. In addition, it is preferable that R ¹¹ is tert-butyl because this has high solubility and, when used as a latent additive, the cured product of a composition containing it has high heat resistance.

Examples of the alkylene group having 1 to 4 carbon atoms represented by X ¹ in the general formula (1) above include methylene, ethylene, propylidene, isopropylidene, butylidene, etc.

Alicyclic hydrocarbon groups having 3 to 20 carbon atoms represented by X ¹ include cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl.

As a substituent substituting the ^alkylene group having 1 to 4 carbon atoms or the alicyclic hydrocarbon group ^{having 3} to 20 carbon atoms represented by ^{X 1} , ^examples thereof include those exemplified as substituents substituting the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, the arylalkyl ^group having 7 to 20 carbon ^atoms or the heterocycle-containing group having 2 to 20 carbon atoms, represented by the above-mentioned R ¹ , R ² , R ³ , R ⁴ , ^R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 .

Cycloalkyl groups having 3 to 10 carbon atoms represented by R ⁷¹ in the above formula (1-1) include cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, and cyclooctyl.

The alkyl group and halogen atom having 1 to 10 carbon atoms represented by R ⁷² may include the alkyl group and halogen atom exemplified in the explanation of the general formula (1) above.

Examples of the alkoxy group having 1 to 10 carbon atoms represented by R ⁷² include methyloxy, ethyloxy, iso-propyloxy, butyloxy, sec-butyloxy, tert-butyloxy, iso-butyloxy, amyloxy, iso-amyloxy, tert-amyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy, tert-heptyloxy, 1-octyloxy, iso-octyloxy, tert-octyloxy, etc.

Alkenyl groups having 2 to 10 carbon atoms represented by R ⁷² include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, and 2-octenyl.

As a substituent substituting the phenyl group or the cycloalkyl group having 3 to 10 carbon atoms represented by R ⁷¹ , and the alkyl group having 1 to ¹⁰ carbon atoms, the ^{alkoxy group} having 1 to 10 carbon atoms or the alkenyl group having 2 to 10 carbon atoms represented by R ⁷² , examples thereof include those exemplified as substituents substituting the alkyl group having 1 to 20 carbon ^atoms , ^the aryl group having 6 to 20 carbon atoms ^, the arylalkyl group having 7 to 20 carbon atoms or the ^heterocycle -containing group having 2 to 20 carbon atoms represented by the above-mentioned R ¹ , R ² , R ³ , R ⁴ , ^R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 .

As the alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, the heterocyclic group having 2 to 20 carbon atoms, and the halogen ^{atom represented by R 73 and} R 74 in the above formula (1-3), examples thereof include the alkyl group, aryl group, arylalkyl group, heterocyclic group having 2 to 20 carbon atoms, and halogen atom exemplified in the above description.

Aryloxy groups having 6 to 20 carbon atoms represented by R ⁷³ and R ⁷⁴ include phenyloxy, naphthyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy, 4-vinylphenyloxy, 3-iso-propylphenyloxy, 4-iso-propylphenyloxy, 4-butylphenyloxy, 4-tert-butylphenyloxy, 4-hexylphenyloxy, 4-cyclohexylphenyloxy, 4-octylphenyloxy, 4-(2-ethylhexyl)phenyloxy, 2,3-dimethylphenyloxy, 2,4-dimethylphenyloxy, 2,5-dimethylphenyloxy, 2,6-dimethylphenyloxy, 3,4-dimethylphenyloxy, 3,5-dimethylphenyloxy, 2,4-di-tert-butylphenyloxy, 2,5-di-tert-butylphenyloxy, Examples of such groups include 2,6-di-tert-butylphenyloxy, 2,4-di-tert-pentylphenyloxy, 2,5-tert-amylphenyloxy, 4-cyclohexylphenyloxy, 2,4,5-trimethylphenyloxy, and ferrocenyloxy.

Examples of the arylthio group having 6 to 20 carbon atoms represented by R ⁷³ and R ⁷⁴ include a group in which the oxygen atom of the aryloxy group having 6 to 20 carbon atoms is replaced with a sulfur atom.

Examples of the arylalkenyl group having 8 to 20 carbon atoms represented by R ⁷³ and R ⁷⁴ include groups in which the oxygen atom of the aryloxy group having 6 to 20 carbon atoms is substituted with an alkenyl group such as vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, or 2-octenyl.

Rings formed by adjacent R ^73s include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, and a lactam ring.

As a substituent substituting an ^alkyl group having 1 to ¹⁰ carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an aryl alkenyl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 ^carbon atoms, represented by R ^{73 and} R 74, a substituent substituting an alkyl group having 1 to 20 carbon atoms, ^{an aryl} group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms, represented ^by the above-mentioned R ¹ , ^{R 2} , R ³ , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R ¹¹ and R ¹² Examples of substituents can be given.

Specific examples of compounds represented by the above general formula (1) include compounds represented by the following chemical formulas, but the present invention is not limited to these compounds.

The method for producing the compound represented by the general formula (1) above is not particularly limited, but for example, the compound can be obtained by reacting a phenol compound produced by the method described in each of Japanese Patent Application Laid-Open No. 57-111375, Japanese Patent Application Laid-Open No. 3-173843, Japanese Patent Application Laid-Open No. 6-128195, Japanese Patent Application Laid-Open No. 7-206771, Japanese Patent Application Laid-Open No. 7-252191, and Japanese Patent Application Laid-Open No. 2004-501128 with an acid anhydride, an acid chloride, a Boc-forming reagent, an alkyl halide compound, a silyl chloride compound, an allyl ether compound, or the like.

The compound represented by the above general formula (1) can be used as a latent additive for semiconductors, photosensitive photography, lithographic printing plates, intermediates of pharmaceutical compounds, thermal paper, latent antioxidants, latent ultraviolet absorbers, etc.

The potential additive of the present invention contains at least one compound of the general formula (1).

The above potential additive is inactive in a prebaking process at room temperature or below 150°C, and becomes active by removing the protective group when heated at 100 to 250°C or by heating at 80 to 200°C in the presence of an acid/base catalyst.

The photosensitive composition of the present invention contains the latent additive of the present invention. In the photosensitive composition of the present invention, the content of the latent additive of the present invention is preferably 0.001 to 20 mass%, more preferably 0.005 to 5 mass%.

The photosensitive composition of the present invention is a composition whose properties change by light irradiation, and there is a positive type resist that is soluble in a chemical reaction, and a negative type resist that is insoluble in a chemical reaction. The photosensitive composition of the present invention contains, in addition to the latent additive of the present invention as a latent antioxidant, a polymerizable compound having an ethylenically unsaturated bond having an acid value and a photoradical polymerization initiator.

Polymerizable compounds having an ethylenically unsaturated bond having the above acid value include (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl], ω-carboxypolycaprolactone mono(meth)acrylate, mono(meth)acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals, such as hydroxyethyl(meth)acrylate·maleate, hydroxypropyl(meth)acrylate·maleate, dicyclopentadiene·maleate, or one carboxyl group and two or more Unsaturated polybasic acids such as polyfunctional (meth)acrylates having a (meth)acryloyl group; Examples thereof include novolac-type epoxy compounds such as phenol and/or cresol novolac epoxy resins, novolac epoxy resins having a biphenyl skeleton or a naphthalene skeleton, bisphenol A novolac-type epoxy compounds, dicyclopentadiene novolac-type epoxy compounds, polyphenylmethane-type epoxy resins having a polyfunctional epoxy group, resins in which an unsaturated monobasic acid is reacted on an epoxy group of an epoxy resin such as an epoxy compound represented by the following general formula (I), resins obtained by reacting an unsaturated monobasic acid on an epoxy group of an epoxy resin such as an epoxy compound represented by the following general formula (I) and further reacting a polybasic acid anhydride, polyfunctional acrylates having a hydroxyl group such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and polyfunctional acrylates having an acid value which are reaction products of dibasic acid anhydrides such as succinic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride.

(In the formula, X ⁴¹ represents a direct bond, an alkylene group having 1 to 4 carbon atoms which may have a substituent, an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, -O-, -S-, -SO ₂ -, -SS-, -SO-, -CO-, -OCO-, or a substituent represented by the above (1-1) to (1-3),

R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms which may or may not have a substituent, an alkoxy group having 1 to 8 carbon atoms which may or may not have a substituent, an alkenyl group having 2 to 5 carbon atoms which may or may not have a substituent, or a halogen atom.

m is an integer from 0 to 10.)

These polymerizable compounds having ethylenically unsaturated bonds with acid values can be used alone or in combination of two or more. The content of the polymerizable compound having ethylenically unsaturated bonds with acid values in the photosensitive composition of the present invention is preferably 20 to 80 mass% of the solid content, more preferably 30 to 70 mass% of the solid content. In addition, it can be used in combination with a polymerizable compound having ethylenically unsaturated bonds that do not have an acid value. When using two or more types in combination, they may be copolymerized in advance and used as a copolymer.

As polymerizable compounds having an ethylenically unsaturated bond that does not have the above acid value, for example, (meth)acrylate-2-hydroxyethyl, (meth)acrylate-2-hydroxypropyl, (meth)acrylate glycidyl, the following compounds No. A1 to No. A4, (meth)acrylate methyl, (meth)acrylate butyl, (meth)acrylate isobutyl, (meth)acrylate-t-butyl, (meth)acrylate cyclohexyl, (meth)acrylate n-octyl, (meth)acrylate isooctyl, (meth)acrylate isononyl, (meth)acrylate stearyl, (meth)acrylate lauryl, (meth)acrylate methoxyethyl, (meth)acrylate dimethylaminomethyl, (meth)acrylate dimethylaminoethyl, (Meth)acrylic acid aminopropyl, (meth)acrylic acid dimethylaminopropyl, (meth)acrylic acid ethoxyethyl, (meth)acrylic acid poly(ethoxy)ethyl, (meth)acrylic acid butoxyethoxyethyl, (meth)acrylic acid ethylhexyl, (meth)acrylic acid phenoxyethyl, (meth)acrylic acid tetrahydrofuryl, (meth)acrylic acid vinyl, (meth)acrylic acid allyl, (meth)acrylic acid benzyl, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, Esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols, such as trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate, and polyester (meth)acrylate oligomers; metal salts of unsaturated polybasic acids, such as zinc (meth)acrylate and magnesium (meth)acrylate; Acid anhydrides of unsaturated polybasic acids such as maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, and methylhimic anhydride; Amides of unsaturated monobasic acids and polyhydric amines such as (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriaminetris(meth)acrylamide, xylylenebis(meth)acrylamide, α-chloroacrylamide, and N-2-hydroxyethyl(meth)acrylamide; Unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; unsaturated aromatic compounds such as styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, and vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, and vinylpiperidine; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and allyl glycidyl ether; Unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; macromonomers having a mono(meth)acryloyl group at the terminal of the polymer molecular chain such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane; (Meth)acrylonitrile, ethylene, propylene, butylene, vinyl chloride, vinyl acetate, and other vinyl compounds, and macromonomers such as polymethyl methacrylate macromonomer, polystyrene macromonomer, monomethacrylates having a tricyclodecane skeleton, N-phenylmaleimide, methacryloyloxymethyl-3-ethyloxetane, and the like, copolymers of (meth)acrylic acid, and copolymers of (meth)acrylic acid reacted with isocyanate compounds having unsaturated bonds such as Karenz MOI and AOI manufactured by Showa Denko Co., Ltd., vinyl chloride, vinylidene chloride, divinylsuccinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinylthioether, vinylimidazole, vinyloxazoline, vinylcarbazole, Examples thereof include vinyl urethane compounds of vinyl pyrrolidone, vinyl pyridine, hydroxyl-containing vinyl monomers and polyisocyanate compounds, vinyl epoxy compounds of hydroxyl-containing vinyl monomers and polyepoxy compounds, reaction products of hydroxyl-containing polyfunctional acrylates such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and polyfunctional isocyanates such as tolylene diisocyanate and hexamethylene diisocyanate.

The content of the polymerizable compound having an ethylenically unsaturated bond without an acid value in the photosensitive composition of the invention is preferably 20 to 80 mass% of the solid content, more preferably 30 to 60 mass% of the solid content.

Since the developability of the photosensitive composition is improved by adjusting the acid value, in the photosensitive composition of the present invention, a monofunctional or polyfunctional epoxy compound can be further used together with the polymerizable compound having an ethylenically unsaturated bond having the acid value described above. The polymerizable compound having an ethylenically unsaturated bond having the acid value described above preferably has an acid value of 5 to 120 mgKOH/g in the solid content, and the amount of the monofunctional or polyfunctional epoxy compound used is preferably selected so as to satisfy the acid value described above.

The above monofunctional epoxy compounds include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, Examples thereof include p-methoxyglycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methylcresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, and propylene oxide.

As the above-mentioned multifunctional epoxy compound, it is preferable to use at least one selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers, because a colored alkaline-developable photosensitive composition having even better properties can be obtained. As the above-mentioned bisphenol-type epoxy compound, in addition to the epoxy compound represented by the above-mentioned general formula (I), a bisphenol-type epoxy compound such as a hydrogenated bisphenol-type epoxy compound can also be used. The above glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri(glycidyloxymethyl)propane, 1,1,1-tri(glycidyloxymethyl)ethane, 1,1,1-tri(glycidyloxymethyl)methane, Examples include 1,1,1,1-tetra(glycidyloxymethyl)methane.

In addition, novolac-type epoxy compounds such as phenol novolac-type epoxy compounds, biphenyl novolac-type epoxy compounds, cresol novolac-type epoxy compounds, bisphenol A novolac-type epoxy compounds, and dicyclopentadiene novolac-type epoxy compounds; alicyclic epoxy compounds such as 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 1-epoxyethyl-3,4-epoxycyclohexane; glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, and dimer acid glycidyl ester; Glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, N,N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate; dioxide compounds such as dicyclopentadiene dioxide; naphthalene-type epoxy compounds, triphenylmethane-type epoxy compounds, dicyclopentadiene-type epoxy compounds, etc. can also be used.

The above-mentioned photo-radical polymerization initiator may be a compound capable of initiating radical polymerization by being irradiated with light, and examples thereof include ketone compounds such as acetophenone compounds, benzyl compounds, benzophenone compounds, and thioxanthone compounds, and oxime compounds.

Examples of acetophenone compounds include diethoxyacetphenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, p-dimethylaminoacetphenone, p-tert-butyldichloroacetphenone, p-tert-butyltrichloroacetphenone, p-azidebenzalacetphenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, benzoin, benzoin methyl ether, Examples thereof include benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one.

Benzyl compounds include benzyl and anisyl.

Examples of benzophenone compounds include benzophenone, o-benzoyl methyl benzoate, Mihira's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide.

Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

Among oxime compounds, a compound represented by the following general formula (II) is particularly preferable from the viewpoints of sensitivity and heat resistance.

(In the formula, R ⁵¹ and R ⁵² each independently represent a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may or may not have a substituent, an aryl group having 6 to 30 carbon atoms which may or may not have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may or may not have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may or may not have a substituent,

R ⁵³ and R ⁵⁴ each independently represent a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, R ⁵⁵ , OR ⁵⁶ , SR ⁵⁷ , NR ⁵⁸ R ⁵⁹ , COR ⁶⁰ , SOR ⁶¹ , SO ₂ R ⁶² or CONR ⁶³ R ⁶⁴ , and R ⁵³ and R ⁵⁴ may be combined with each other to form a ring,

R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent an alkyl group having 1 to 20 carbon atoms which may or may not have a substituent, an aryl group having 6 to 30 carbon atoms which may or may not have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may or may not have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may or may not have a substituent.

X ² represents an oxygen atom, a sulfur atom, a selenium atom, CR ⁷⁵ R ⁷⁶ , CO, NR ⁷⁷ or PR ⁷⁸ ,

X ³ represents a single bond or CO,

R ⁵¹ , R ⁵² , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ and R ⁶⁸ represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, and the methylene group in the alkyl group or arylalkyl group may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group or a heterocyclic group, and may be substituted with -O-,

R ⁵³ and R ⁵⁴ may each independently form a ring with either adjacent benzene ring,

a represents an integer from 0 to 4,

b represents an integer from 0 to 5.)

Other photoradical polymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(phenyl-1-yl)]titanium, etc.

These photo-radical polymerization initiators can be used in combination of one or more types depending on the desired performance.

The amount of the photo radical polymerization initiator as described above is preferably 0.1 to 30 mass%, particularly 0.5 to 10 mass%, of the solid content of the photosensitive composition of the present invention. If the amount of the photo radical polymerization initiator is less than 0.1 mass%, curing by exposure may become insufficient, and if it is greater than 30 mass%, the photo radical polymerization initiator may precipitate in the photosensitive composition.

According to the present invention, a colored photosensitive composition is also provided. The colored photosensitive composition contains the photosensitive composition and a colorant. A cured product of the colored photosensitive composition is preferably used as a color filter.

In the above-mentioned colored photosensitive composition, the content of the colorant is preferably 0.01 to 50 mass%, more preferably 0.1 to 30 mass%.

The above coloring agent may include a dye or pigment. As a dye, there is no particular limitation as long as it is a compound having an absorption in the range of 380 to 1200 nm, and examples thereof include azo compounds, anthoraquinone compounds, indigoid compounds, triarylmethane compounds, xanthene compounds, alizalin compounds, acridine compounds, stilbene compounds, thiazole compounds, naphthol compounds, quinoline compounds, nitro compounds, indamine compounds, oxadine compounds, phthalocyanine compounds, cyanine compounds, diimmonium compounds, cyanoethenyl compounds, dicyanostyrene compounds, rhodamine compounds, perylene compounds, polyenenaphtholactam compounds, coumarin compounds, squarylium compounds, croconium compounds, spiropyran compounds, spiroxadine compounds, merocyanine compounds, oxonol compounds, styryl compounds, pyrylium compounds, rhodanine compounds, oxazolone compounds, phthalimide compounds, cinnoline compounds, naphthoquinone compounds, azaanthraquinone compounds, Examples of dyes include porphyrin compounds, azaporphyrin compounds, pyrromethene compounds, quinacridone compounds, diketopyrrolopyrrole compounds, indigo compounds, acridine compounds, azine compounds, azomethine compounds, aniline compounds, quinacridone compounds, quinophthalone compounds, quinone imine compounds, iridium complex compounds, and europium complex compounds, and these may be used in combination.

As the pigment, an inorganic pigment or organic pigment can be used, and examples thereof include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthanthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxadine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acid; metal complex compounds of azo dyes and cyanine dyes; lake pigments; carbon black obtained by a furnace method, a channel method or a thermal method, or carbon black such as acetylene black, Ketjen black or lamp black; The carbon black above is adjusted and coated with an epoxy resin, the carbon black above is dispersed in advance with a resin in a solvent and 20 to 200 mg/g of the resin is adsorbed, the carbon black above is surface-treated with acid or alkali, the average particle size is 8 nm or more and the DBP absorption is 90 ml/100 g or less, the total oxygen amount calculated from CO and _CO2 in the volatile matter at 950°C is 9 mg or more per 100 m2 of the surface area of the carbon black; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; Organic or inorganic pigments such as hydrophobic resin, chromium oxide green, milori blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate ultramarine, prussian blue, ultramarine, cerulean blue, viridian, emerald green, lead sulfate, yellow lead, zinc sulfur, bengala (red iron (III) oxide), cadmium red, synthetic iron black, and amber can be used. These pigments can be used alone or in combination.

As the above inorganic pigment or organic pigment, a commercially available pigment may be used, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

In the colored photosensitive composition of the present invention, it is preferable to use a dye as the colorant, and it is particularly preferable to use a triarylmethane compound and a cyanoethenyl compound. By using a dye, particularly a triarylmethane compound and a cyanoethenyl compound, as the colorant, the heat resistance of the colorant is further increased, and as a result, the effect of making the color change before and after firing of the colored photosensitive composition smaller is exerted.

A solvent may be further added to the above photosensitive composition and colored photosensitive composition. As the solvent, typically, a solvent capable of dissolving or dispersing each of the above components as necessary, for example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and taxanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol, diacetone alcohol, etc.; ether ester solvents such as ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, 1-t-butoxy-2-propanol, 3-methoxybutyl acetate, cyclohexanol acetate, etc.; BTX solvents such as benzene, toluene, xylene, etc.; Aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene, and pinene; Examples thereof include paraffin solvents such as mineral spirits, Swasol #310 (Cosmo Matsuyama Sekiyu Co., Ltd.), and Solvesso #100 (Exxon Chemical Co., Ltd.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide; N-methylpyrrolidone; dimethyl sulfoxide; and water. These solvents can be used alone or as a mixed solvent of two or more. Among these, ketones, ether ester solvents, etc., especially propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc. are preferable because they have good compatibility between the resist and the photoradical polymerization initiator in the photosensitive composition.

The above photosensitive composition and the above colored photosensitive composition may further contain an inorganic compound. Examples of the above inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; layered clay minerals, Milori blue, calcium carbonate, magnesium carbonate, cobalt-based, manganese-based, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, and copper.

In the above photosensitive composition and the above colored photosensitive composition, when a pigment and/or an inorganic compound is used, a dispersant can be added. As the dispersant, any material capable of dispersing and stabilizing a coloring material and an inorganic compound may be used, and commercially available dispersants, for example, products from Big Chemistry, BYK series, etc., can be used, and a polymer dispersant composed of polyester, polyether, and polyurethane having a basic functional group, a polymer dispersant having a nitrogen atom as the basic functional group, wherein the functional group having the nitrogen atom is an amine and/or a quaternary salt thereof, and an amine value of 1 to 100 mgKOH/g is preferably used.

In addition, the photosensitive composition and the colored photosensitive composition may contain, as necessary, conventional additives such as thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, and phenothiazine; plasticizers; adhesion promoters; fillers; antifoaming agents; leveling agents; surface conditioners; antioxidants such as phenol antioxidants, phosphate antioxidants, and thioether antioxidants; ultraviolet absorbers; dispersing agents; anticoagulants; catalysts; effect accelerators; crosslinking agents, and thickeners.

In addition, by using another organic polymer together with the polymerizable compound having an ethylenically unsaturated bond having the above acid value, the properties of the cured product of the colored photosensitive composition of the present invention can also be improved. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin, and the like. Among these, polystyrene, (meth)acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferable.

The above photosensitive composition and the above colored photosensitive composition may also contain a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, melamine, etc.

As the above chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl(4-methylthio)phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, Mercapto compounds such as 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), disulfide compounds obtained by oxidizing the above mercapto compounds, iodinated alkyl compounds such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid, trimethylolpropane tris(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), Examples thereof include aliphatic polyfunctional thiol compounds such as hexaneditiol, decaneditiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, the following Compound No. C1, trimercaptopropionate tris(2-hydroxyethyl)isocyanurate, Showa Denko products Karenz MT BD1, PE1, NR1, etc.

As the above surfactant, fluorine surfactants such as perfluoroalkyl phosphate ester and perfluoroalkyl carboxylate, anionic surfactants such as higher fatty acid alkali salt, alkyl sulfonate and alkyl sulfate, cationic surfactants such as higher amine halogenate and quaternary ammonium salt, nonionic surfactants such as polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester and fatty acid monoglyceride, amphoteric surfactants, silicone surfactants and the like can be used, and these can also be used in combination.

As the above silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among these, a silane coupling agent having an isocyanate group, a methacryloyl group, or an epoxy group, such as KBE-9007, KBM-502, or KBE-403, is preferably used.

As the above melamine compound, examples thereof include compounds in which all or part (at least two) of the active methylol groups (CH ² OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea are alkyl etherified. Here, the alkyl groups constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, and they may be the same as or different from each other. In addition, a methylol group that is not alkyl etherified may self-condense within one molecule, or may condense between two molecules to form an oligomer component as a result. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, and the like can be used. Among these, alkyl etherified melamine such as hexamethoxymethylmelamine and hexabutoxymethylmelamine is preferable.

The above photosensitive composition and colored photosensitive composition can be applied onto a support substrate such as soda glass, quartz glass, a semiconductor substrate, metal, paper, plastic, etc. by known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing, immersion, etc. In addition, after once applied onto a support substrate such as a film, it can also be transferred onto another support substrate, and there is no limitation on the application method.

In addition, as a light source of the active light used when curing the photosensitive composition and the colored photosensitive composition, a light emitting light having a wavelength of 300 to 450 nm can be used, and examples thereof include ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, etc.

In addition, by using laser light as an exposure light source, a laser direct drawing method that forms an image directly from digital information such as a computer without using a mask is useful because it can improve not only productivity but also resolution and positional accuracy, and as the laser light, light having a wavelength of 340 to 430 nm is preferably used, but lasers that emit light in the visible to infrared range, such as an argon ion laser, a helium-neon laser, a YAG laser, and a semiconductor laser, are also used. When these lasers are used, an intensifying dye that absorbs in the corresponding range from visible to infrared is added to the photosensitive composition and the colored photosensitive composition.

The photosensitive composition and colored photosensitive composition of the present invention can also be patterned through a double patterning process in which patterning is performed twice using two photosensitive compositions or colored photosensitive compositions.

The above photosensitive composition and the colored photosensitive composition (or the cured product thereof) are used in a photocurable paint or varnish, a photocurable adhesive, a printed circuit board, or a color filter in a liquid crystal display panel for color displays such as a color TV, a PC monitor, a portable information terminal, and a digital camera, a color filter of a CCD image sensor, a photo spacer, a black column spacer, an electrode material for a plasma display panel, a touch panel, a touch sensor, a powder coating, a printing ink, a printing plate, an adhesive, a dental composition, a resin for stereolithography, a gel coat, a photoresist for electronics, an electroplating resist, an etching resist, both liquid and dry films, a solder resist, a resist for manufacturing a color filter for various display purposes or for forming a structure in a manufacturing process of a plasma display panel, an electroluminescent display device, and an LCD, a composition for sealing electric and electronic components, a solder resist, a magnetic recording material, a microscopic mechanical component, It can be used for various purposes such as waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, materials for manufacturing three-dimensional objects by stereolithography, materials for holographic recording, image recording materials, microelectronic circuits, decolorizing materials, decolorizing materials for image recording materials, decolorizing materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, photoresist materials used for forming dielectric layers in sequential lamination of printed circuit boards, photoresist materials for 3D mounting or as protective films, and there are no particular limitations on the uses.

The photosensitive composition of the present invention can be used for a transparent conductive film, a reflective film, a polarizing plate, a protective film, etc. by curing, and can be used as a transparent laminate by sequentially applying the above-mentioned respective layers to a transparent substrate, irradiating active light through a mask having a predetermined pattern shape, developing the exposed film with a developer, and heating the developed film. As the transparent laminate, for example, there can be mentioned one in which transparent thin film layers and metal thin film layers made of a composite oxide of indium oxide and cerium oxide are alternately formed on a transparent substrate. A photosensitive composition containing the compound of the present invention as a latent additive may be used for each of the above-mentioned layers, and the photosensitive composition may be used for one or more layers. The transparent laminate of the present invention is preferably used for a display device.

The photosensitive composition of the present invention can be used as a transparent structure by curing. As the transparent structure, examples thereof include: a columnar article called a photo spacer (PS) or a column spacer (CS); a fine pattern of (nano)imprinting; an inkjet receiving layer used in the manufacture of electronic devices such as the manufacture of large-scale advertising signboards, or the printing of color filters or alignment films for liquid crystal displays. The transparent structure of the present invention is preferably used in a display device.

The above-mentioned colored photosensitive composition is used for the purpose of forming pixels of a color filter, and is particularly useful as a photosensitive composition for forming a color filter for a display device for an image display device such as a liquid crystal display panel.

The color filter for the above display device is preferably formed by (1) a step of forming a film of the above-described colored photosensitive composition on a substrate, (2) a step of irradiating the film with active light through a mask having a predetermined pattern shape, (3) a step of developing the film after exposure with a developer, and (4) a step of heating the film after development. In addition, the colored photosensitive composition of the present invention is also useful as a colored photosensitive composition for an inkjet method without a developing step.

As the above mask, a multi-level mask such as a halftone mask or a gray scale mask may be used.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, etc., but the present invention is not limited to these examples, etc.

[Examples 1-1 to 1-3] Synthesis of compounds No. 1 to No. 3

To an ethyl acetate solution of 1 equivalent of a phenol compound (3 times the theoretical amount), 0.2 equivalents of 4-dimethylaminopyridine were added at room temperature, and 5 equivalents of di-tert-butyl dicarbonate were added dropwise at 10°C or lower, and the mixture was stirred at room temperature for 2 hours under a nitrogen atmosphere. Oil and water were separated, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, the viscosity-lowering component was removed with silica gel, and then crystallization was performed. The obtained solid was dried under reduced pressure at 60°C for 3 hours, and the target products were respectively obtained. That the obtained solid was the target product was confirmed by ^1H -nmR and IR. The results are shown in [Table 1] to [Table 2].

[Table 1]

[Table 2]

[Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-2] Preparation of Photosensitive Compositions No. 1 to No. 3 and Comparative Photosensitive Compositions No. 1 to No. 2

50.9 g of SPC-1000 (PGMEA solution having a solid content of 29%, manufactured by Showa Denko), 11.9 g of Aronix M-450 (manufactured by Toagosei), 1.04 g of OXE-01 (manufactured by BASF), 34.0 g of PGMEA, 2.9 g of FZ2122 (PGMEA solution having a solid content of 1%, manufactured by Dow Corning Toray), and 0.81 g of the compound described in [Table 3] were mixed and stirred until the insoluble matter disappeared, thereby obtaining photosensitive compositions No. 1 to No. 3 and comparative photosensitive compositions No. 1 to No. 2. Comparative compound No. 1 used in comparative photosensitive composition No. 1 refers to the following comparative compound No. 1.

[Table 3]

[Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-2] Preparation of colored photosensitive compositions No. 1 to No. 3 and comparative colored photosensitive compositions No. 1 to No. 3

1.26 g of SPC-1000 (PGMEA solution having a solid content of 29%, manufactured by Showa Denko), 0.30 g of Aronix M-450 (manufactured by Toagosei), 0.03 g of OXE-01 (manufactured by BASF), 0.85 g of PGMEA, 0.08 g of FZ2122 (PGMEA solution having a solid content of 1%, manufactured by Dow Corning Toray), and 0.02 g of the latent additive described in [Table 3(a)] were mixed and stirred until no insoluble matter disappeared. Further, 0.95 g of PGMEA was added to 0.05 g of the colorant described in [Table 3A], stirred, and dissolved. The resulting colorant solution was added and stirred until uniform, to obtain colored photosensitive compositions No. 1 to No. 3 and comparative colored photosensitive compositions No. 1 to No. 3.

[Table 3A]

Compounds A to C in [Table 3A] represent compounds A to C below, respectively.

[Evaluation examples 1-1 to 1-3 and comparative evaluation examples 1-1 to 1-2] Evaluation of heat resistance by sintering

The photosensitive compositions No. 1 to No. 3 prepared in Examples 2-1 to 2-3 and the comparative photosensitive compositions No. 1 to No. 2 prepared in Comparative Examples 2-1 to 2-2 were each coated on a glass substrate under the conditions of 410 rpm × 7 sec, and dried on a hot plate (90°C, 90 sec). The obtained coating film was exposed (150 mJ/cm2) with an ultra-high pressure mercury lamp. The coating film after exposure was fired under the conditions of 230°C × 30 min. The transmittance at 400 nm of the coating film after firing was measured and evaluated. The results are shown in [Table 4].

[Table 4]

From the above results, it can be said that the photosensitive composition containing the compound of the present invention as a latent additive maintains a high level of transparency after firing, and that the heat resistance is equivalent to that of the comparative photosensitive composition No. 1 and superior to that of the comparative photosensitive composition No. 2, compared to the comparative photosensitive composition containing the comparative compound as a latent additive.

[Evaluation Examples 2-1 to 2-3 and Comparative Evaluation Example 2-1] Measurement of solubility

For compounds No. 1 to No. 3 and comparative compound No. 1, the solubility in propylene glycol-1-monomethyl ether-2-acetate (PGMEA) was measured. The results are shown in [Table 5].

[Table 5]

From the above results, it is clear that the compound of the present invention has high solubility and good handling properties when used in a photosensitive composition.

[Evaluation examples 3-1 to 3-3 and comparative evaluation examples 3-1 to 3-3] Evaluation of heat resistance by firing of colored photosensitive composition

The colored photosensitive compositions No. 1 to No. 3 prepared in Examples 3-1 to 3-3 and the comparative colored photosensitive compositions No. 1 to No. 3 prepared in Comparative Examples 3-1 to 3-3 were each coated on a glass substrate under the conditions of 410 rpm × 7 sec, and dried on a hot plate (90°C, 90 sec). The obtained coating film was exposed (150 mJ/cm2) with an ultra-high pressure mercury lamp. The coated film after exposure was fired under the conditions of 230°C × 30 min, and the color difference (ΔE _ab* ) before and after firing was investigated. The results are shown in [Table 6].

[Table 6]

From the above results, it can be seen that the colored photosensitive composition containing the compound of the present invention as a potential additive has less change in color after firing and the heat resistance of the colorant remains high, compared to the comparative photosensitive composition containing the same colorant.

From the above results, it is clear that the compound of the present invention has high solubility, and a photosensitive composition using the compound as a latent additive has excellent heat resistance and is useful as a latent additive.

Claims (9)

A curable photosensitive composition containing a latent additive comprising at least one compound represented by the following general formula (1), a polymerizable compound having an ethylenically unsaturated bond having an acid value, a photoradical polymerization initiator, and a solvent,
A curable photosensitive composition wherein the content of the potential additive in the composition is 0.005 to 5 mass%.

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent -CO-OR ¹¹ ,
R ¹¹ represents an alkyl group having 1 to 20 carbon atoms, which may have a substituent.
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 20 carbon atoms, which may have a substituent,
Multiple R ⁹ and R ¹⁰ may be the same or different,
X ¹ represents an alkylene group having 1 to 4 carbon atoms, which may have a substituent.
a, b, c and d each independently represent an integer from 1 to 4, e and f each independently represent an integer from 0 to 9,
The substituents substituting the alkyl group having 1 to 20 carbon atoms represented by R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are an ethylenically unsaturated group, a halogen atom, an acyl group, an acyloxy group, a substituted amino group, a sulfonamide group, a sulfonyl group, a carboxyl group, a cyano group, a sulfo group, a nitro group, a mercapto group, an imide group, a carbamoyl group, a sulfonamide group, a phosphonic acid group or a phosphoric acid group, or a salt of a carboxyl group, a sulfo group, a phosphonic acid group or a phosphoric acid group.) A transparent laminate formed using a cured product of the curable photosensitive composition described in claim 1. A transparent structure formed using a cured product of the curable photosensitive composition described in claim 1. A display device comprising at least a portion of the transparent laminate described in claim 2 or the transparent structure described in claim 3. A colored photosensitive composition containing the curable photosensitive composition described in claim 1 and a colorant. A color filter formed using a cured product of the colored photosensitive composition described in claim 5. delete delete delete