JP6748083B2 - Novel compound, latent additive and composition containing said additive - Google Patents

Description

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

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

Phenolic antioxidants have the effect of trapping radicals that greatly affect the deterioration of polymers, so when antioxidants are added to the polymerization system, they generally act as so-called polymerization inhibitors and cause curing inhibition. Therefore, latent additives have been developed, but satisfactory solubility has not been obtained (Patent Document 5).

JP-A-6-179798 JP-A-7-109380 JP-A-11-071355 JP, 2002-097224, A US2015/291772 (A1)

Therefore, an object of the present invention is to provide a highly soluble latent additive which is inactive at room temperature and which is activated by heating at a predetermined temperature to exhibit its function. Another object of the present invention is to provide a heat resistant composition using the latent additive. Another object of the present invention is to provide a colored photosensitive composition containing the above composition and a colorant, particularly a colored photosensitive composition suitable for a color filter.

As a result of intensive studies, the present inventors have found that a compound having a specific protective group effectively functions as a latent additive, high solubility and good handling property, and a composition using the same. However, it does not cause curing inhibition, and it is found that the heat resistance is excellent because the deterioration of the initiator and the colorant is prevented, and the colored photosensitive composition containing the composition and the colorant is an optical filter. The inventors have reached the present invention by finding that they are suitable for a color filter for an image display device such as a liquid crystal display panel without lowering the brightness of (particularly a color filter).

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

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ独立に、置換基を有している場合もある炭素原子数１〜２０のアルキル基、置換基を有している場合もある炭素原子数６〜２０のアリール基、置換基を有している場合もある炭素原子数７〜２０のアリールアルキル基、置換基を有している場合もある炭素原子数２〜２０の複素環含有基、トリアルキルシリル基、−ＣＯ−Ｏ−Ｒ¹¹又は−ＣＯ−Ｓ−Ｒ¹²を表し、
Ｒ¹¹及びＲ¹²は、それぞれ独立に、水素原子、置換基を有している場合もある炭素原子数１〜２０のアルキル基、置換基を有している場合もある炭素原子数６〜２０のアリール基、置換基を有している場合もある炭素原子数７〜２０のアリールアルキル基又は置換基を有している場合もある炭素原子数２〜２０の複素環含有基を表し、
Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ¹⁰は、それぞれ独立に、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有している場合もある炭素原子数１〜２０のアルキル基、置換基を有している場合もある炭素原子数６〜２０のアリール基、置換基を有している場合もある炭素原子数７〜２０のアリールアルキル基又は置換基を有している場合もある炭素原子数２〜２０の複素環含有基を表し、
複数のＲ^５同士、Ｒ^６同士、Ｒ^７同士及びＲ^８同士は結合してベンゼン環又はナフタレン環を形成していてる場合もあり、
複数のＲ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ¹⁰はそれぞれ同じか異なっている場合もあり、
Ｘ¹は、直接結合、置換基を有している場合もある炭素原子数１〜４のアルキレン基、置換基を有している場合もある炭素原子数３〜２０の脂環式炭化水素基、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＳＳ−、−ＳＯ−、−ＣＯ−、−ＯＣＯ−又は下記式（Ｉ−１）、（Ｉ−２）若しくは（Ｉ−３）で表される置換基を表し、
ａ、ｂ、ｃ及びｄは、それぞれ独立に、０〜４の整数を表し、ｅ及びｆは、それぞれ独立に、０〜９の整数を表す。）

（上記式中、Ｒ^７１は水素原子、置換基を有している場合もあるフェニル基、又は置換基を有している場合もある炭素原子数３〜１０のシクロアルキル基を表し、
Ｒ^７２は置換基を有している場合もある炭素原子数１〜１０のアルキル基、置換基を有している場合もある炭素原子数１〜１０のアルコキシ基、置換基を有している場合もある炭素原子数２〜１０のアルケニル基又はハロゲン原子を表し、
ｉは０〜４の整数である。）

（上記式中、Ｒ^７３及びＲ^７４は、それぞれ独立に、置換基を有している場合もある炭素原子数１〜１０のアルキル基、置換基を有している場合もある炭素原子数６〜２０のアリール基、置換基を有している場合もある炭素原子数６〜２０のアリールオキシ基、置換基を有している場合もある炭素原子数６〜２０のアリールチオ基、置換基を有している場合もある炭素原子数６〜２０のアリールアルケニル基、置換基を有している場合もある炭素原子数７〜２０のアリールアルキル基、置換基を有している場合もある炭素原子数２〜２０の複素環含有基又はハロゲン原子を表し、
Ｒ^７３は、隣接するＲ^７３同士で環を形成している場合もあり、
ｐは０〜４の数を表し、
ｑは０〜８の数を表し、
ｇは０〜４の数を表し、
ｈは０〜４の数を表し、
ｇとｈの数の合計は２〜４である。）

(In the formula, R ¹ , R ² , R ^3, and R ⁴ each independently have a substituent, and may have an alkyl group having 1 to 20 carbon atoms, or a substituent. An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, a hetero group having 2 to 20 carbon atoms which may have a substituent Represents a ring-containing group, a trialkylsilyl group, -CO-O-R ¹¹ or -CO-S-R ¹² ,
R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a carbon atom having 6 to 20 which may have a substituent. Represents an aryl group, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, or a heterocyclic ring-containing group having 2 to 20 carbon atoms which may have a substituent,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently have a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or the number of carbon atoms which may have a substituent. An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may have a substituent, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, or a substituent Represents a heterocyclic ring-containing group having 2 to 20 carbon atoms, which may have
In some cases, a plurality of R ^{5 s} , R ^{6 s} , R ^{7 s,} and R ^{8 s} are bonded to each other 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, and
X ¹ is a direct bond, an alkylene group having 1 to 4 carbon atoms which may have a substituent, or an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent. , -O -, - S -, - SO 2 -, - SS -, - SO -, - CO -, - OCO- or the following formula (I-1), with (I-2) or (I-3) Represents a substituent represented,
a, b, c and d each independently represent an integer of 0 to 4, and e and f each independently represent an integer of 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 has an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, and a substituent. In some cases, it represents an alkenyl group having 2 to 10 carbon atoms or a halogen atom,
i is an integer of 0-4. )

(In the above formulas, R ⁷³ and R ⁷⁴ are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent, and a carbon atom number 6 which may have a substituent. To an aryl group having 6 to 20 carbon atoms, which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and a substituent. An arylalkenyl group having 6 to 20 carbon atoms which may have a substituent, an arylalkyl group having a carbon number of 7 to 20 which may have a substituent and a carbon which may have a substituent Represents a heterocycle-containing group having 2 to 20 atoms or a halogen atom,
R ⁷³ may form a ring with adjacent R ⁷³ ,
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 total number of g and h is 2-4. )

The present invention also provides a latent additive comprising one or more compounds represented by the above general formula (1).

The present invention also provides a photosensitive composition containing the latent additive.

According to the present invention, it is possible to provide a latent additive having high solubility, which is inactive at room temperature and becomes active when heated to a predetermined temperature. Further, the composition containing the latent additive does not cause curing inhibition and is excellent in heat resistance.

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

The number of 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) is 1 As the alkyl group of to 20, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, Examples thereof include 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl, adamantyl and the like.
The aryl group 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 is represented by , Phenyl, naphthyl, anthracenyl and the like.
As an arylalkyl group 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, 9-fluorenylmethyl groups and the like.
Heterocycle-containing 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. Examples of pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl. , Benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinone-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine-3 -Yl and the like, or a group in which a heterocycle is bonded via a divalent bonding group.
Examples of the trialkylsilyl group represented by R ¹ , R ² , R ³ and R ⁴ include trimethylsilane, triethylsilane and ethyldimethylsilane.
Examples of the halogen atom represented by R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include fluorine, chlorine, bromine and iodine.
An alkyl group 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 ; Examples of the substituent for substituting the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, or the heterocyclic ring-containing group having 2 to 20 carbon atoms include ethylene such as vinyl, allyl, acryl and methacryl. Unsaturated group; halogen atom such as fluorine, chlorine, bromine, iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl(benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl , Oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl and other acyl groups; acetyloxy, benzoyloxy and other acyloxy groups; 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-octadecyl. Substituted amino groups such as oxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N,N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino; sulfonamide groups , Sulfonyl group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group, sulfonamide group, phosphonic acid group, phosphoric acid group or carboxyl group, sulfo group, phosphonic acid group, phosphorus Examples thereof include salts of acid groups, and the substitution position thereof is not limited.
In the compound represented by the general formula (1), one in which R ¹ , R ² , R ³ and R ⁴ are —CO—O—R ¹¹ has high solubility and was used as a latent additive. At this time, the cured product of the composition containing it has high heat resistance, which is preferable. Further, it is preferable that R ¹¹ is tert-butyl since it 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 above general formula (1) include methylene, ethylene, propylidene, isopropylidene, butylidene and the like.
Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by X ¹ include cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl and the like.
As the substituent for 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 , R ¹ , R ² , R ³ and R described above are used. ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, What was illustrated as a substituent which substitutes a C7-C20 arylalkyl group or a C2-C20 heterocycle containing group is mentioned.

Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R ⁷¹ in the above formula (1-1) include cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl and the like.
Examples of the alkyl group having 1 to 10 carbon atoms and the halogen atom represented by R ⁷² include the alkyl group and the halogen atom exemplified in the description of the general formula (1).
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-octyl Oxy, iso-octyloxy, tert-octyloxy and the like can be mentioned.
Examples of the alkenyl group having 2 to 10 carbon atoms represented by R ⁷² include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl and the like. ..
A phenyl group or a cycloalkyl group having 3 to 10 carbon atoms represented by R ⁷¹ , and an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a carbon atom represented by R ^72. As the substituent for substituting the alkenyl group of the formulas ^{2 to 10} , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ^{11 described above are used.} And 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 heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R ¹² What was illustrated as a substituent which substitutes is mentioned.

An alkyl group having 1 to 10 carbon atoms represented by R ⁷³ and R ⁷⁴ in the above formula (1-3), an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and carbon. Examples of the heterocyclic ring-containing group having 2 to 20 atoms and the halogen atom include the alkyl group, the aryl group, the arylalkyl group, the heterocyclic ring containing group having 2 to 20 carbon atoms, and the halogen atom exemplified in the above description.
Examples of the aryloxy group having 6 to 20 carbon atoms represented by R ⁷³ and R ⁷⁴ include phenyloxy, naphthyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy and 4-vinylphenyl. Dioxy, 3-iso-propylphenyloxy, 4-iso-propylphenyloxy, 4-butylphenyloxy, 4-tert-butylphenyloxy, 4-hexylphenyloxy, 4-cyclohexylphenyloxy, 4-octylphenyl Oxy, 4-(2-ethylhexyl)phenyloxy, 2,3-dimethylphenyloxy, 2,4-dimethylphenyloxy, 2,5-dimethylphenyloxy, 2.6-dimethylphenyloxy, 3.4-dimethylphenyl Oxy, 3.5-dimethylphenyloxy, 2,4-di-tert-butylphenyloxy, 2,5-di-tert-butylphenyloxy, 2,6-di-tert-butylphenyloxy, 2.4-di-tert- Examples include groups such as 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 groups in which an oxygen atom of the aryloxy group having 6 to 20 carbon atoms is substituted with a sulfur atom.
As the arylalkenyl group having 8 to 20 carbon atoms represented by R ⁷³ and R ⁷⁴ , the oxygen atom of the aryloxy group having 6 to 20 carbon atoms is vinyl, allyl, 1-propenyl, isopropenyl, 2- Examples thereof include groups substituted with an alkenyl group such as butenyl, 1,3-butadienyl, 2-pentenyl and 2-octenyl.
Examples of the ring formed by adjacent R ^73's 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.
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, and an arylthio group having 6 to 20 carbon atoms, which are represented by R ⁷³ and R ^74. As the substituent for substituting the arylalkenyl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, and the heterocyclic ring-containing group having 2 to 20 carbon atoms, R ¹ and R ² described above can be used. , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are alkyl groups having 1 to 20 carbon atoms, and 6 to 6 carbon atoms. What was illustrated as a substituent which substitutes a 20-aryl group, a C7-C20 arylalkyl group, or a C2-C20 heterocyclic ring containing group is mentioned.

Specific examples of the compound represented by the general formula (1) include the compounds represented by the following [Chemical formula 5] to [Chemical formula 7], but the present invention is not limited to these compounds.

The method for producing the compound represented by the general formula (1) is not particularly limited, but examples thereof include JP-A-57-111375, JP-A-3-173843, JP-A-6-128195, JP-A-7-206771, and JP-A-7-206771. -252191, the phenolic compound produced by the method described in each of Japanese Patent Publication No. 2004-501128, and acid anhydrides, acid chlorides, Boc-forming reagents, alkyl halide compounds, silyl chloride compounds, allyl ether compounds, etc. It can be obtained by reacting.

The compound represented by the above general formula (1) is used for semiconductors, photosensitive photographs, lithographic printing plates, intermediates of pharmaceutical compounds, thermal papers, latent antioxidants, latent ultraviolet absorbers, etc. It can be used as a latent additive.
The latent additive of the present invention contains at least one compound represented by the general formula (1).
The above-mentioned latent additive is inactive in a pre-baking step at room temperature or 150° C. or lower, and is protected by heating at 100 to 250° C. or at 80 to 200° C. in the presence of an acid/base catalyst. Is desorbed and becomes active.

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% by mass, more preferably 0.005 to 5% by mass.

The photosensitive composition of the present invention is a composition whose properties are changed by light irradiation. A positive resist is one that is soluble in a chemical reaction, and a negative resist is one that is insoluble in a chemical reaction. .. The photosensitive composition of the present invention contains the latent additive of the present invention as a latent antioxidant, as well as a polymerizable compound having an ethylenic unsaturated bond having an acid value and a photoradical polymerization initiator.
As the polymerizable compound having an ethylenically unsaturated bond having an acid value, (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid , Vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl], ω-carboxy poly Polymeric mono(meth)acrylates having carboxy groups and hydroxyl groups at both ends such as caprolactone mono(meth)acrylate, hydroxyethyl (meth)acrylate malate, hydroxypropyl (meth)acrylate malate, dicyclopentadiene malate, or Unsaturated polybasic acids such as polyfunctional (meth)acrylates having one carboxyl group and two or more (meth)acryloyl groups; phenol and/or cresol novolac epoxy resin, biphenyl skeleton, and novolac epoxy having naphthalene skeleton Resins, bisphenol A novolac type epoxy compounds, dicyclopentadiene novolac type epoxy compounds and other novolac type epoxy compounds, polyphenylmethane type epoxy resins having polyfunctional epoxy groups, epoxy compounds represented by the following general formula (I), etc. A resin obtained by reacting an unsaturated monobasic acid on an epoxy group of an epoxy resin, or an unsaturated monobasic acid acting on an epoxy group of an epoxy resin such as an epoxy compound represented by the following general formula (1), and a polybasic acid Reaction of resins obtained by reacting with anhydride, polyfunctional acrylates containing hydroxyl groups such as pentaerythritol triacrylate, dipentaerythritol pentaacrylate and dibasic acid anhydrides such as succinic anhydride, phthalic anhydride and tetrahydrophthalic anhydride Examples thereof include polyfunctional acrylates having an acid value that is a substance.

（式中、Ｘ⁴¹は直接結合、置換基を有している場合もある炭素原子数１〜４のアルキレン基、置換基を有している場合もある炭素原子数３〜２０の脂環式炭化水素基、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＳＳ−、−ＳＯ−、−ＣＯ−、−ＯＣＯ−又は上記（１−１）〜（１−３）で表される置換基を表し、
Ｒ⁴¹、Ｒ⁴²、Ｒ⁴³及びＲ⁴⁴は、それぞれ独立に、水素原子、置換基を有している場合もある炭素原子数１〜５のアルキル基、置換基を有している場合もある炭素原子数１〜８のアルコキシ基、置換基を有している場合もある炭素原子数２〜５のアルケニル基又はハロゲン原子を表し、
ｍは０〜１０の整数である。）

(In the formula, X ⁴¹ is a direct bond, an alkylene group having 1 to 4 carbon atoms which may have a substituent, and an alicyclic group having 3 to 20 carbon atoms which may have a substituent. hydrocarbon group, -O -, - S -, - SO 2 -, - SS -, - SO -, - CO -, - OCO- or substituted represented by the above (1-1) to (1-3) Represents a group,
R ⁴¹ , R ⁴² , R ^43, and R ⁴⁴ each independently have a hydrogen atom, a substituent group, or an alkyl group having 1 to 5 carbon atoms, or a substituent group. Represents an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, or a halogen atom,
m is an integer of 0-10. )

These polymerizable compounds having an ethylenically unsaturated bond having an acid value can be used alone or in admixture of two or more. The content of the polymerizable compound having an ethylenically unsaturated bond having an acid value in the photosensitive composition of the present invention is preferably 20 to 80% by mass in the solid content, more preferably 30 to 70% by mass in the solid content. preferable. Further, it can be used in combination with a polymerizable compound having an ethylenically unsaturated bond having no acid value. When two or more kinds are mixed and used, they may be previously copolymerized and used as a copolymer.

Examples of the polymerizable compound having an ethylenic unsaturated bond having no acid value include (meth)acrylic acid-2-hydroxyethyl, (meth)acrylic acid-2-hydroxypropyl, (meth)acrylic acid glycidyl, The following compound No. A1-No. A4, 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, dimethyl (meth)acrylate Aminoethyl, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, (meth ) Ethylhexyl acrylate, phenoxyethyl (meth)acrylate, tetrahydrofuryl (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, 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, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, Unsaturated monobasic acids such as pentaerythritol tri(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate, polyester (meth)acrylate oligomer and polyhydric alcohols or polyhydric alcohols Esters of phenols; Metal salts of unsaturated polybasic acids such as zinc (meth)acrylate and magnesium (meth)acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydro Phthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride Acid anhydrides of unsaturated polybasic acids such as oleic acid adducts, dodecenyl succinic anhydride, and methylhymic acid anhydride; (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriaminetris(meth)acrylamide, xylylenebis(meth) Amides of unsaturated monobasic acids and polyamines such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth)acrylamide; unsaturated aldehydes such as acrolein; (meth)acrylonitrile, α-chloroacrylonitrile, cyanation Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol. , Vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether and other unsaturated aromatic compounds; methyl vinyl ketone and other unsaturated ketones; vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl piperidine, etc. Unsaturated amine compounds; 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, N-cyclohexylmaleimide; indene, 1 -Indenes such as methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polymer molecules such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, polysiloxane Macromonomers having a mono(meth)acryloyl group at the chain end; (meth)acrylonitrile, other vinyl compounds such as ethylene, propylene, butylene, vinyl chloride, vinyl acetate, and polymethylmethacrylate macromonomers, polystyrene macromonomers, etc. Copolymers of macromonomers, monomethacrylates of tricyclodecane skeleton, N-phenylmaleimide, methacryloyloxymethyl-3-ethyloxetane, and (meth)acrylic acid, and Karens made by Showa Denko KK A copolymer of (meth)acrylic acid obtained by reacting an isocyanate compound having an unsaturated bond such as MOI and AOI, vinyl chloride, vinylidene chloride, divinyl succinate, Diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compound of hydroxyl group-containing vinyl monomer and polyisocyanate compound, hydroxyl group-containing vinyl monomer And a reaction product of a hydroxyl group-containing polyfunctional acrylate such as a vinyl epoxy compound of a polyepoxy compound, pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and a polyfunctional isocyanate such as tolylene diisocyanate and hexamethylene diisocyanate.

The content of the polymerizable compound having an ethylenic unsaturated bond having no acid value in the photosensitive composition of the invention is preferably 20 to 80% by mass in the solid content, more preferably 30 to 60% by mass in the solid content. preferable.

In order to improve the developability of the photosensitive composition by adjusting the acid value, in the photosensitive composition of the present invention, a monofunctional or polyfunctional compound having an ethylenically unsaturated bond having the acid value is further added. Functional epoxy compounds can be used. The polymerizable compound having an ethylenically unsaturated bond having the above acid value preferably has an acid value of the solid content in the range of 5 to 120 mgKOH/g, and the amount of the monofunctional or polyfunctional epoxy compound used is the above acid. It is preferable to select it so as to satisfy the value.

Examples of the monofunctional epoxy compound 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, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl 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 monoxide, 1,2-epoxy- 4-vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide and the like can be mentioned.

As the polyfunctional epoxy compound, it is preferable to use one or more selected from the group consisting of bisphenol type epoxy compounds and glycidyl ethers, because a colored alkali developable photosensitive composition having better characteristics can be obtained. As the bisphenol type epoxy compound, an epoxy compound represented by the above general formula (I) can be used, and, for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used. Examples of the 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 1,1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri(glycidyloxymethyl)propane, 1,1,1-tri(glycidyloxymethyl)ethane, 1,1,1-tri(glycidyloxy) Methyl)methane and 1,1,1,1-tetra(glycidyloxymethyl)methane.
Other novolac type epoxy compounds such as phenol novolac type epoxy compound, biphenyl novolac type epoxy compound, cresol novolac type epoxy compound, bisphenol A novolac type epoxy compound, dicyclopentadiene novolac type epoxy compound; 3,4-epoxy-6-methyl Alicyclic epoxies such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compounds; glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester; glycidyl amines such as tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol, N,N-diglycidylaniline Heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as dicyclopentadiene dioxide; Naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclo A pentadiene type epoxy compound or the like can also be used.

The photoradical polymerization initiator may be any compound that can initiate radical polymerization by receiving light irradiation, and examples thereof include ketones such as acetophenone compounds, benzyl compounds, benzophenone compounds, and thioxanthone compounds. Examples of preferable compounds include oxime compounds and oxime compounds.

Examples of the acetophenone compound include diethoxyacetophenone, 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-dimethylaminoacetophenone, p-tertiarybutyldichloroacetophenone, p-tertiarybutyltrichloroacetophenone, p-azidobenzal Acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) -Butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2- Methyl-1-propan-1-one and the like can be mentioned.

Examples of the benzyl compound include benzyl and anisyl.

Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenylsulfide. ..

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

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

（式中、Ｒ^５１及びＲ^５２は、それぞれ独立に、水素原子、シアノ基、置換基を有している場合もある炭素原子数１〜２０のアルキル基、置換基を有している場合もある炭素原子数６〜３０のアリール基、置換基を有している場合もある炭素原子数７〜３０のアリールアルキル基又は置換基を有している場合もある炭素原子数２〜２０の複素環含有基を表し、
Ｒ^５３及びＲ^５４は、それぞれ独立に、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ^５５、ＯＲ^５６、ＳＲ^５７、ＮＲ^５８Ｒ^５９、ＣＯＲ^６０、ＳＯＲ^６１、ＳＯ_２Ｒ^６２又はＣＯＮＲ^６３Ｒ^６４を表し、Ｒ^５３及びＲ^５４は、互いに結合して環を形成していてもよく、
Ｒ^５５、Ｒ^５６、Ｒ^５７、Ｒ^５８、Ｒ^５９、Ｒ^６０、Ｒ^６１、Ｒ^６２、Ｒ^６３及びＲ^６４は、それぞれ独立に、置換基を有している場合もある炭素原子数１〜２０のアルキル基、置換基を有している場合もある炭素原子数６〜３０のアリール基、置換基を有している場合もある炭素原子数７〜３０のアリールアルキル基又は置換基を有している場合もある炭素原子数２〜２０の複素環含有基を表し、
Ｘ^２は、酸素原子、硫黄原子、セレン原子、ＣＲ^７５Ｒ^７６、ＣＯ、ＮＲ^７７又はＰＲ^７８を表し、
Ｘ^３は、単結合又はＣＯを表し、
Ｒ^５１、Ｒ^５２、Ｒ^５５、Ｒ^５６、Ｒ^５７、Ｒ^５８、Ｒ^５９、Ｒ^６０、Ｒ^６５、Ｒ^６６、Ｒ^６７及びＲ^６８中の炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基又は炭素原子数７〜３０のアリールアルキル基を表し、該アルキル基又はアリールアルキル基中のメチレン基は、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基又は複素環含有基で置換されていてもよく、−Ｏ−で置き換えられていてもよく、
Ｒ^５３及びＲ^５４は、それぞれ独立に、隣接するどちらかのベンゼン環と一緒になって環を形成していてもよく、
ａは、０〜４の整数を表し、
ｂは、０〜５の整数を表す。）

(In the formula, R ⁵¹ and R ⁵² are each independently a hydrogen atom, a cyano group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; An aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent or a hetero group having 2 to 20 carbon atoms which may have a substituent Represents a ring-containing group,
R ⁵³ and R ⁵⁴ are each independently 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 Represents CONR ⁶³ R ⁶⁴ , R ⁵³ and R ⁵⁴ may be bonded to 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 have a carbon atom number of 1 to 1 which may have a substituent. It has an alkyl group having 20 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, or a substituent. In some cases, it represents a heterocyclic ring-containing group having 2 to 20 carbon atoms,
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 have} an alkyl group having 1 to 20 carbon atoms and the number of carbon atoms. It represents an aryl group having 6 to 30 or an arylalkyl group having 7 to 30 carbon atoms, and the methylene group in the alkyl group or arylalkyl group contains a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group or a heterocycle. It may be substituted with a group or -O-,
R ⁵³ and R ⁵⁴ may independently form a ring together with either of the adjacent benzene rings,
a represents an integer of 0 to 4,
b represents an integer of 0 to 5. )

Other photoradical polymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(cyclopentadienyl)-bis[2,6-difluoro-3-(pyr-1-yl)]titanium. And so on.

These photo-radical polymerization initiators may be used alone or in combination of two or more depending on the desired performance.

The photoradical polymerization initiator as described above is preferably 0.1 to 30% by mass, and particularly preferably 0.5 to 10% by mass in the solid content of the photosensitive composition of the present invention. If the content of the photoradical polymerization initiator is less than 0.1% by mass, curing by exposure may be insufficient, and if it is more than 30% by mass, the photoradical initiator is precipitated in the photosensitive composition. There is a case.

The present invention also provides a colored photosensitive composition. This colored photosensitive composition contains the above-mentioned photosensitive composition and a colorant. The cured product of the colored photosensitive composition is preferably used as a color filter.
In the above colored photosensitive composition, the content of the colorant is preferably 0.01 to 50% by mass, more preferably 0.1 to 30% by mass.

Examples of the colorant include dyes and pigments.
The dye is not particularly limited as long as it is a compound having absorption at 380 to 1200 nm, and examples thereof include azo compounds, anthraquinone compounds, indigoid compounds, triarylmethane compounds, xanthene compounds, alizarin compounds, acridine compounds, stilbene compounds, thiazole compounds. , Naphthol compounds, quinoline compounds, nitro compounds, indamine compounds, oxazine 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, spirooxazine compounds, merocyanine compounds, oxonol compounds, styryl compounds, pyrylium compounds, rhodanin compounds, oxazolone compounds, phthalimide compounds, cinnoline compounds, naphthoquinone compounds, azaanthraquinone compounds, porphyrin compounds, azaporphyrin compounds, pyromethene compounds, Examples include dyes such as quinacridone compounds, diketopyrrolopyrrole compounds, indigo compounds, acridine compounds, azine compounds, azomethine compounds, aniline compounds, quinacridone compounds, quinophthalone compounds, quinoneimine compounds, iridium complex compounds, europium complex compounds, and these. You may mix and use two or more.

As the pigment, it is possible to use an inorganic pigment or an organic pigment, for example, nitroso compound, nitro compound, azo compound, diazo compound, xanthene compound, quinoline compound, anthraquinone compound, coumarin compound, phthalocyanine compound, isoindolinone compound, iso Indoline compounds, quinacridone compounds, anthanthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids; metal complex compounds of azo dyes and cyanine dyes; Lake pigment; carbon black obtained by furnace method, channel method, thermal method, or carbon black such as acetylene black, ketjen black or lamp black; the carbon black prepared and coated with an epoxy resin, the carbon black previously prepared Those obtained by dispersing the resin in a solvent and adsorbing 20 to 200 mg/g of the resin, treating the above carbon black with an acidic or alkaline surface, and having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml/100 g or less. The total amount of oxygen calculated from CO and CO ₂ in volatile matter at 950° C. is 9 mg or more per 100 m ² of surface area of 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; hydrophobic resin, chromium oxide green, milori blue, cobalt green, cobalt blue, manganese-based, ferrocyanide, phosphate ultramarine, navy blue , Ultramarine, Cerulean blue, Pyridian, Emerald green, Lead sulfate, Yellow lead, Zinc yellow, Red iron oxide (Red iron (III) oxide), Cadmium red, Synthetic iron black, Amber, etc. it can. These pigments may be used alone or in combination of two or more.

As the above-mentioned inorganic pigment or organic pigment, a commercially available pigment may be used, and 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 and the like.

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 enhanced, and as a result, the change in chromaticity before and after baking of the colored photosensitive composition is smaller. The effect is played.

A solvent may be further added to the photosensitive composition and the colored photosensitive composition. The solvent is usually a solvent capable of dissolving or dispersing each of the above components, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc. Ketones; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, acetic acid-n-propyl acetate, isopropyl acetate , Ester solvents such as n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol, iso- or n-propanol, Alcohol solvents such as iso- or n-butanol, amyl alcohol and diacetone alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether. Ether ester solvents such as acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, 1-t-butoxy-2-propanol, 3-methoxybutyl acetate, cyclohexanol acetate; BTX solvents such as benzene, toluene and xylene. Hexane, heptane, octane, cyclohexane and other aliphatic hydrocarbon solvents; terpine oil, D-limonene, pinene and other terpene hydrocarbon oils; mineral spirits, Swazol #310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # Paraffinic solvents such as 100 (Exxon Chemical Co., Ltd.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane; halogenated aromatic hydrocarbons such as chlorobenzene. System solvent; carbitol system solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water and the like, These solvents can be used as one kind or as a mixed solvent of two or more kinds. Among these, ketones, ether ester solvents and the like, particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone and the like are preferable because the resist and the photoradical polymerization initiator have good compatibility in the photosensitive composition.

The photosensitive composition and the colored photosensitive composition may further contain an inorganic compound. Examples of the 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 silicates, calcium silicates, aluminum hydroxide, platinum, gold, silver, copper Etc.

When using a pigment and/or an inorganic compound in the said photosensitive composition and the said colored photosensitive composition, a dispersing agent can be added. The dispersant may be any colorant, as long as it can disperse and stabilize an inorganic compound, and a commercially available dispersant such as BYK series manufactured by BYK-Chemie can be used. A polyester having a basic functional group, Polyether, a polymer dispersant composed of polyurethane, having a nitrogen atom as a basic functional group, the functional group having a nitrogen atom is an amine, and/or a quaternary salt thereof, and having an amine value of 1 to 100 mgKOH/g. Those are preferably used.

In the photosensitive composition and the colored photosensitive composition, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, or phenothiazine; a plasticizer; an adhesion promoter. Fillers; Defoamers; Leveling agents; Surface modifiers; Antioxidants such as phenol-based antioxidants, phosphite-based antioxidants, thioether-based antioxidants; UV absorbers; Dispersion aids; Agglomeration inhibitors Conventional additives such as a catalyst, an effect accelerator, a cross-linking agent and a thickener can be added.

Further, the properties of the cured product of the colored photosensitive composition of the present invention can be improved by using another organic polymer together with the polymerizable compound having an ethylenically unsaturated bond having the above acid value. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, and (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 Examples thereof include polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, and epoxy resin. Among these, polystyrene, (meth)acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferable.

A chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, melamine and the like can be further used in combination with the photosensitive composition and the colored photosensitive composition.

A sulfur atom-containing compound is generally used as the chain transfer agent and the sensitizer. 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, 3-mercapto-2-butanol, mercaptophenol , 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis Mercapto compounds such as (3-mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid Iodinated alkyl compounds such as trimethylolpropane tris(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediolbisthio Propionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate , Pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, the following compound no. C1, aliphatic polyfunctional thiol compounds such as tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, Karenz MT BD1, PE1, NR1 manufactured by Showa Denko KK, etc. may be mentioned.

Examples of the above-mentioned surfactants include fluorosurfactants such as perfluoroalkyl phosphates and perfluoroalkylcarboxylates, anionic surfactants such as higher fatty acid alkali salts, alkylsulfonates and alkylsulfates, and higher amines. Cationic surfactants such as halides and quaternary ammonium salts, polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, nonionic surfactants such as fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

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

As the melamine compound, (poly)methylolmelamine, (poly)methylolglycoluril, (poly)methylolbenzoguanamine, (poly)methylolurea, etc., all or part of the active methylol group (CH ₂ OH group) in the nitrogen compound. Examples thereof include compounds in which (at least two) are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same or different from each other. Further, the non-alkyl etherified methylol group may be self-condensed within one molecule, or may be condensed 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 are preferable.

The photosensitive composition and the colored photosensitive composition, a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing, by known means such as dipping, soda glass, quartz glass, semiconductor substrate, metal It can be applied on a supporting substrate such as paper, paper or plastic. Further, once applied on a supporting substrate such as a film, it can be transferred onto another supporting substrate, and its application method is not limited.

Moreover, as a light source of active light used when curing the above-mentioned photosensitive composition and colored photosensitive composition, a light source that emits light with a wavelength of 300 to 450 nm can be used. Steam arc, carbon arc, xenon arc, etc. can be used.

Furthermore, by using laser light as the exposure light source, the laser direct writing method, which directly forms an image from digital information from a computer without using a mask, improves not only productivity but also resolution and positional accuracy. It is also useful because the laser light is preferably light having a wavelength of 340 to 430 nm, and it is visible to infrared region such as argon ion laser, helium neon laser, YAG laser, and semiconductor laser. The one that emits the light of is also used. When these lasers are used, a sensitizing dye that absorbs in the visible to infrared region is added to the photosensitive composition and the colored photosensitive composition.

The photosensitive composition and the colored photosensitive composition of the present invention can also be patterned through a double patterning process in which two photosensitive compositions or a colored photosensitive composition are used to perform patterning in two steps.

The above-mentioned photosensitive composition and colored photosensitive composition (or a cured product thereof) are used for photocurable paints or varnishes, photocurable adhesives, printed circuit boards, color televisions, PC monitors, personal digital assistants, digital cameras, etc. Color filter for liquid crystal display panel for color display, color filter for CCD image sensor, photo spacer, black column spacer, electrode material for plasma display panel, touch panel, touch sensor, powder coating, printing ink, printing plate, adhesive, dentistry Composition, stereolithography resin, gel coat, photoresist for electronics, electroplating resist, etching resist, both liquid and dry film, solder resist, for producing color filters for various display applications or plasma Resists for forming structures in the manufacturing process of display panels, electroluminescent displays, and LCDs, compositions for encapsulating electrical and electronic components, solder resists, magnetic recording materials, micromechanical components, waveguides, optical switches , Plating masks, etching masks, color test systems, glass fiber cable coatings, screen printing stencils, materials for producing three-dimensional objects by stereolithography, holographic recording materials, image recording materials, fine electronic circuits, decolorization 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 image systems, and sequential printed circuit boards It can be used for various applications such as a photoresist material used for forming a dielectric layer in lamination, a photoresist material for 3D mounting, or a protective film, and the application is not particularly limited.

By curing the photosensitive composition of the present invention, it can be used as a transparent conductive film, a reflective film, a polarizing plate, a protective film, etc., and the above-mentioned layers are sequentially applied to a transparent substrate to have a predetermined pattern shape. It can be used as a transparent laminate in which active light is irradiated through a mask, the exposed film is developed with a developing solution, and the developed film is heated to form a laminate. Examples of the transparent laminate include a transparent substrate in which transparent thin film layers and metal thin film layers made of a composite oxide of indium oxide and cerium oxide are alternately arranged. A photosensitive composition containing the compound of the present invention as a latent additive may be used in each of the above-mentioned layers, or the photosensitive composition may be used in any one or more layers. The transparent layered product of the present invention is used suitably for a display device.

The photosensitive composition of the present invention can be used as a transparent structure by curing. Examples of the transparent structure include pillar-shaped objects called photo spacers (PS) and column spacers (CS); (nano) imprint fine patterns; manufacturing of large advertising billboards, color filters for liquid crystal displays and alignment films. Examples thereof include an inkjet receiving layer used for manufacturing electronic devices such as printing. The transparent structure of the present invention is suitably used for a display device.

The 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.

In the color filter for a display device, (1) a step of forming a coating film of the colored photosensitive composition on a substrate, (2) irradiating the coating film with active light through a mask having a predetermined pattern shape. It is preferably formed by the step, (3) developing the exposed film with a developing solution, and (4) heating the developed film. The colored photosensitive composition of the present invention is also useful as an inkjet type colored photosensitive composition having no development step.
A multi-tone mask such as a halftone mask or a gray scale mask can be used as the mask.

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

[Examples 1-1 to 1-3] Compound No. 1-No. Synthesis of 3 To a solution of 1 equivalent of a phenol compound in ethyl acetate (3 times the theoretical yield), 0.2 equivalent of 4-dimethylaminopyridine was added at room temperature, and 5 equivalents of di-tert-butyl dicarbonate was added dropwise at 10°C or lower. Then, the mixture was stirred at room temperature for 2 hours under a nitrogen atmosphere. Oil-water separation was performed, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the deduction component was removed by silica gel, followed by crystallization. The obtained solid was dried under reduced pressure at 60° C. for 3 hours to obtain the target products. It was confirmed by ¹ H-NMR and IR that the obtained solid was the target product. The results are shown in [Table 1] to [Table 2].

[Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-2] Photosensitive composition No. 1-No. 3 and comparative photosensitive composition No. 1-No. Preparation of 2 SPC-1000 (manufactured by Showa Denko KK, PGMEA solution having a solid content of 29%) 50.9 g, Aronix M-450 (manufactured by Toagosei Co., Ltd.) 11.9 g, OXE-01 (manufactured by BASF) 1.04 g, 34.0 g of PGMEA, 2.9 g of FZ2122 (manufactured by Toray Dow Corning, PGMEA solution having a solid content of 1%) and 0.81 g of the compound described in [Table 3] were mixed, and the mixture was stirred until the insoluble matter disappeared. Item No. 1-No. 3 and comparative photosensitive composition No. 1-No. Got 2. Comparative photosensitive composition No. Comparative compound No. 1 used in Example 1. 1 is the following comparative compound No. Represents 1.

@0021

@0021

[Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-2] Colored photosensitive composition No. 1-No. 3 and comparative colored photosensitive composition No. 3 1-No. Preparation of 3 SPC-1000 (Showa Denko KK, PGMEA solution with a solid content of 29%) 1.26 g, Aronix M-450 (Toagosei KK) 0.30 g, OXE-01 (BASF KK) 0.03 g, 0.85 g of PGMEA, 0.08 g of FZ2122 (manufactured by Toray Dow Corning, PGMEA solution having a solid content of 1%) and 0.02 g of the latent additive described in [Table 3A] were mixed, and stirred until insoluble matter disappeared. .. Furthermore, 0.95 g of PGMEA was added to 0.05 g of the coloring agent described in [Table 3A], and the coloring agent solution which was dissolved by stirring was added and stirred until uniform. 1-No. 3 and comparative colored photosensitive composition No. 3 1-No. Got 3.

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

[Evaluation Examples 1-1 to 1-3 and Comparative Evaluation Examples 1-1 to 1-2] Evaluation of Heat Resistance by Firing Photosensitive composition No. 1 prepared in Examples 2-1 to 2-3. 1-No. 3 and Comparative Photosensitive Composition No. 3 prepared in Comparative Examples 2-1 and 2-2. 1-No. 2 was 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/cm ² ) with an ultra-high pressure mercury lamp. The coating film after exposure was baked under the condition of 230° C.×30 min. The transmittance of the coating film after baking at 400 nm was measured and evaluated. The results are shown in [Table 4].

From the above results, the photosensitive composition containing the compound of the present invention as a latent additive maintains high transparency after firing as compared with the comparative photosensitive composition containing a comparative compound as a latent additive. And the heat resistance of the comparative photosensitive composition No. Comparative photosensitive composition No. 1 equivalent to Better than 2.

[Evaluation Examples 2-1 to 2-3 and Comparative Evaluation Example 2-1] Solubility Measurement Compound No. 1-No. 3 and comparative compound No. For 1, the solubility of propylene glycol-1-monomethyl ether-2-acetate (PGMEA) was measured. The results are shown in [Table 5].

From the above results, it is clear that the compound of the present invention has high solubility and has good handling property 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 baking of colored photosensitive compositions Colored photosensitive compositions prepared in Examples 3-1 to 3-3 No. 1-No. Comparative coloring photosensitive composition No. 3 prepared in Comparative Examples 3-1 to 3-3. 1-No. 3 was coated on a glass substrate under the conditions of 410 rpm×7 sec and dried (90° C., 90 sec) on a hot plate. The obtained coating film was exposed (150 mJ/cm ² ) with an ultra-high pressure mercury lamp. The exposed coating film was baked under the conditions of 230° C.×30 min, and the color difference (ΔE _{ab *} ) before and after baking was examined. The results are shown in [Table 6].

From the above results, the colored photosensitive composition containing the compound of the present invention as a latent additive shows less change in chromaticity after firing as compared with the comparative photosensitive composition containing the same coloring agent, and the heat resistance of the coloring agent is small. It can be seen that the property remains high.

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

Claims (10)

A compound represented by the following general formula (1).

^{(Wherein, R 1, R 2, R} 3 and ^{R 4} are each independently - represents a CO-O-R ¹¹ or -CO-S-R ^12,
R ¹¹ and R ¹² are each independently, location substituent in some cases have an alkyl group having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, sometimes have a substituent A group, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently have a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or the number of carbon atoms which may have a substituent. An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may have a substituent, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, or a substituent Represents a heterocyclic group having 2 to 20 carbon atoms which may have a group ,
In some cases, a plurality of R ^{5 s} , R ^{6 s} , R ^{7 s,} and R ^{8 s} are bonded to each other 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, and
X ¹ is a direct bond, an alkylene group having 1 to 4 carbon atoms which may have a substituent, or an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent. , -O -, - S -, - SO 2 -, - SS -, - SO -, - CO -, - OCO- or the following formula (1 -1), (1 -2) or (1 -3) Represents a substituent represented,
a, b, c and d each independently represent an integer of 0 to 4, e and f are each independently Represents an integer of 0-9,
An alkyl group 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 ; The substituent for substituting 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 is an ethylenically unsaturated group, a halogen atom, an acyl group, Acyloxy group, substituted amino group, sulfonamide group, sulfonyl group, carboxyl group, cyano group, sulfo group, nitro group, mercapto group, imide group, carbamoyl group, sulfonamide group, phosphonic acid group or phosphoric acid group, or carboxyl group , Sulfo group, phosphonic acid group or phosphoric acid group. )

(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 has an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, and a substituent. In some cases, it represents an alkenyl group having 2 to 10 carbon atoms or a halogen atom,
* Represents a bond,
i is an integer of 0-4. )

(In the above formula, * represents a bond.)

(In the above formulas, R ⁷³ and R ⁷⁴ are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent, and a carbon atom number 6 which may have a substituent. To an aryl group having 6 to 20 carbon atoms, which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and a substituent. An arylalkenyl group having 6 to 20 carbon atoms which may have a substituent, an arylalkyl group having a carbon number of 7 to 20 which may have a substituent and a carbon which may have a substituent Represents a heterocyclic group having 2 to 20 atoms or a halogen atom,
* Represents a bond,
R ⁷³ may form a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring or a lactam ring between adjacent R ^{73 s} ,
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 total number of g and h is 2-4. ) The compound according to claim 1, wherein in the general formula (1), R ¹ , R ² , R ³ and R ⁴ are represented by —CO—O—R ¹¹ . A latent antioxidant comprising one or more of the compounds according to claim 1 or 2. A curable photosensitive composition containing the latent antioxidant according to claim 3. The curable photosensitive composition according to claim 4, comprising a polymerizable compound having an ethylenically unsaturated bond having an acid value and a photoradical polymerization initiator. Transparent laminate formed using the cured product of the curable photosensitive composition according to claim 4 or 5. Transparent structure formed by using a cured product of the curable photosensitive composition according to claim 4 or 5. A display device comprising at least a part of the transparent laminate according to claim 6 or the transparent structure according to claim 7 . A colored photosensitive composition containing the curable photosensitive composition according to claim 4 or 5 and a colorant. A color filter formed using the cured product of the colored photosensitive composition according to claim 9 .