KR102229653B1 - Colored photosensitive composition - Google Patents

Abstract

상기 일반식(I)의 구체적인 내용은 본 명세서에 기재한 바와 같다.The colored photosensitive composition of the present invention is a colored photosensitive composition excellent in heat resistance (a colored alkali developable photosensitive composition) and an optical filter using the colored photosensitive composition (a colored alkali developable photosensitive composition), especially without lowering the luminance, and a liquid crystal display panel, etc. To provide a color filter suitable for an image display device of, specifically, a dye (A) composed of a compound represented by the following general formula (I), a polymerizable compound (B) having an ethylenically unsaturated bond, and a photopolymerization initiator (C It is to provide a colored photosensitive composition containing) and a color filter for a display device using the same.

The specific content of the general formula (I) is as described in the present specification.

Description

Colored photosensitive composition TECHNICAL FIELD

The present invention relates to a colored photosensitive composition that is polymerizable by energy rays, and a color filter using the colored photosensitive composition, using a dye designed in a desired color and having improved solvent resistance and heat resistance.

Compounds with high intensity absorption for specific light include recording layers of optical recording media such as CD-R, DVD-R, DVD+R, and BD-R, liquid crystal displays (LCDs), plasma display panels (PDPs). , An electroluminescent display (ELD), a cathode tube display (CRT), a fluorescent display tube, and an optical element of an image display device such as a field emission type display.

300 to 1100 nm in optical filters for image display devices such as liquid crystal display (LCD), plasma display panel (PDP), electroluminescent display (ELD), cathode tube display (CRT), fluorescent display tube, and field emission type display. Various compounds that absorb light of the wavelength of are used as light absorbers.

These light absorbers are required to have a particularly steep light absorption, that is, to have a small half width of λmax, and to not lose their function due to light or heat.

An optical filter mainly used in a liquid crystal display (LCD) includes a color filter. In general, three primary colors of RGB have been used for color filters, but it is difficult to have pure RGB colors as a single color material, so efforts have been made to approximate pure RGB colors by using a plurality of color materials. For this reason, color materials such as yellow, orange, and purple are also required, not RGB.

Organic and/or inorganic pigments have been used as light absorbers used in color filters depending on the height of heat resistance, but since they are pigments, there is a problem that the luminance as a display device is lowered, and this problem has been solved by increasing the luminance of the light source. . However, in accordance with the flow of low power consumption, the development of color filters using dyes is becoming more active.

In addition, in recent years, in a color filter used for a solid-state imaging device, from the viewpoint of image quality improvement, thinning of a colored pattern is required, and in order to make a thin film, it is necessary to increase the dye concentration in terms of color density. Further, even when the molar absorption light coefficient of the dye is low, it is necessary to add a large amount of dye.

However, if the dye concentration is increased, the elution or precipitation of the dye from the pixels formed after the film formation is observed, or in the case of heat treatment (post bake) after film formation, between adjacent pixels or between the upper and lower layers in the stacked structure. It is a problem that the color mixture is easy to occur.

In Patent Documents 1 and 2, colored resin compositions for color filters containing a triarylmethane-based dye having a specific structure are disclosed.

However, the triarylmethane-based dye described in these documents was not satisfactory in terms of heat resistance.

Japanese Patent Application Publication No. 2010-204132 Japanese Patent Application Publication No. 2012-017425

Accordingly, an object of the present invention is to provide a colored photosensitive composition (colored alkali developable photosensitive composition) excellent in heat resistance. Another object of the present invention is to provide an optical filter using the colored photosensitive composition (a colored alkali developable photosensitive composition), particularly a color filter suitable for an image display device such as a liquid crystal display without lowering the luminance.

As a result of repeated intensive studies, the inventors of the present invention discovered that a compound having a specific structure is excellent in heat resistance and excellent in solvent resistance in a colored photosensitive composition (a colored alkali developable photosensitive composition), and the colored photosensitive composition (colored Alkaline developable photosensitive composition) found that it was suitable for a color filter for image display devices, such as a liquid crystal display panel, without lowering the luminance of an optical filter (especially a color filter), and arrived at this invention.

The present invention was made based on the above findings, and coloring containing a dye (A) consisting of a compound represented by the following general formula (I), a polymerizable compound having an ethylenically unsaturated bond (B), and a photopolymerization initiator (C) It is to provide a photosensitive composition.

[Formula 1]

(In the formula, R ₁ , R ₂ , R ₃ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ are each independently a hydrogen atom or a halogen atom Or substituted with a cyano group, a nitro group, a hydroxyl group or a halogen atom, or substituted with an unsubstituted alkyl group having 1 to 8 carbon atoms, a halogen atom, or substituted with an unsubstituted aryl group having 6 to 12 carbon atoms or a halogen atom Or an unsubstituted arylalkyl group having 7 to 20 carbon atoms or a substituent represented by -XY, X represents an oxygen atom or a sulfur atom, and Y is a halogen atom substituted or an unsubstituted alkyl group having 1 to 8 carbon atoms , A halogen atom substituted or unsubstituted aryl group having 6 to 12 carbon atoms or a halogen atom substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms,

R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ each independently represent a hydroxyl group or a halogen atom, are substituted with a cyano group, a nitro group, a hydroxyl group or a halogen atom, or have an unsubstituted number of carbon atoms 1 Represents an alkyl group of ~8, is substituted with an alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, or a vinyl group, or is substituted with an unsubstituted phenyl group or an alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, or a vinyl group. Or represents an unsubstituted benzyl group, and R ₄ and R ₅ , R ₆ and R ₇ , and R ₈ and R ₉ may be linked to form a 3- to 6-membered heterocycle,

At least two of R ₁ , R ₂ and R ₃ are substituents other than a hydrogen atom,

An ^{q -} represents a q-valent anion, q represents 1 or 2, and p represents a coefficient that keeps the charge neutral.)

In addition, in the present invention, as a preferred form of the colored photosensitive composition, as the polymerizable compound (B) having an ethylenically unsaturated bond, a polymerizable compound (B') having an ethylenically unsaturated bond having alkali developability is used. It is to provide a colored photosensitive composition (colored alkali developable photosensitive composition) having alkali developability.

Further, the present invention is to provide a cured product of the colored photosensitive composition (a colored alkali developable photosensitive composition) and a color filter for a display device comprising the cured product.

The colored photosensitive composition (colored alkali developable photosensitive composition) of the present invention containing a compound having a specific structure is excellent in heat resistance. In addition, the cured product is suitable for a color filter for display devices.

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

First, the colored photosensitive composition of the present invention will be described. In the following description, as appropriate, a colored photosensitive composition or a colored alkaline developable composition described later is described as a colored composition.

The coloring composition of the present invention comprises a dye (A) comprising a compound represented by the general formula (I) (hereinafter, also referred to as dye (A)), a polymerizable compound (B) having an ethylenic unsaturated bond (alkali developability). Including a polymerizable compound (B') having an ethylenically unsaturated bond having an alkali-soluble substituent to be imparted), and a photoinitiator (C), if necessary, at least one colorant (however, the general formula (I)) (D) is contained except for the dye consisting of the compound represented by. Hereinafter, each component will be described in order.

<Dye (A)>

The dye (A) used in the present invention should just contain at least one kind of the compound represented by the general formula (I), and can be used alone or in combination of plural kinds. In addition, it is also possible to use a known dye other than the compound represented by the general formula (I) for the dye (A). Known dyes include, for example, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes , Quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, and cyanine dyes, and the like, and a plurality of these may be used in combination.

_{When R 1} , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ in the general formula (I) and R ₁ , R ₂ and R ₃ are represented by -XY, Y The unsubstituted alkyl group having 1 to 8 carbon atoms represented by is methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl, and the like. There is,

A halogen atom represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ , a cyano group, a nitro group, an alkyl group having 1 to 8 carbon atoms substituted with a hydroxyl group Is a group in which a part or all of the hydrogen atoms in the alkyl group having 1 to 8 carbon atoms is substituted with a halogen atom, a cyano group, a nitro group, or a hydroxyl group,

When R ₁ , R ₂ and R ₃ and R ₁ , R ₂ and R ₃ are represented by -XY, the unsubstituted aryl group having 6 to 12 carbon atoms represented by Y is phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl , 4-methylphenyl, 4-vinylphenyl, 3-iso-propylphenyl, 4-iso-propylphenyl, 4-butylphenyl, 4-iso-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4- Cyclohexylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, (1,1 '-Biphenyl)-4-yl, 2,4,5-trimethylphenyl, ferrocenyl, etc. are mentioned,

When R ₁ , R ₂ and R ₃ and R ₁ , R ₂ and R ₃ are represented by -XY, the unsubstituted arylalkyl group having 7 to 20 carbon atoms represented by Y is benzyl, phenethyl, 2-phenylpropane-2 -Yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, ferrocenylmethyl, ferrocenylpropyl, and the like.

An alkyl group having 1 to 8 carbon atoms represented _{by R 1} , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ in the general formula (I) _{, and R 4} , R ₅ As the halogen atom substituted for the phenyl group or the benzyl group represented by _{R 6} , R ₇ , R ₈ and R _{9, fluorine, chlorine, bromine, and iodine may be mentioned,}

Examples of the alkyl group having 1 to 4 carbon atoms replacing the phenyl group or benzyl group represented by R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R _{9 include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl,} tert-butyl, iso-butyl, and the like.

In the general formula (I), as a _{3-6 membered heterocycle formed by connecting R 4} and R ₅ , R ₆ and R ₇ , and R ₈ and R ₉ , a piperidine ring, a piperazine ring , Pyrrolidine ring, morpholine ring, thiomorpholine ring, pyridine ring, pyrazine ring, pyrimidine ring, quinoline ring, isoquinoline ring, imidazole ring, oxazole ring, imidazolidine ring, pyrazolidine ring, isoxazoli A din ring, an isothiazolidine ring, and the like, and these rings may be condensed with or substituted with other rings.

In the compound represented by the general formula (I), _{at least two of R 1} , R ₂ and R ₃ are substituents other than a hydrogen atom.

^{Examples of the anion represented by An q-} in the general formula (I) are monovalent and include halide ions such as chloride ions, bromide ions, iodide ions, and fluoride ions; Inorganic anions such as perchlorate ions, chlorate ions, thiocyanate ions, hexafluorophosphate ions, hexafluoroantimonate ions, and tetrafluoroborate ions; Methanesulfonic acid ion, dodecylsulfonic acid ion, benzenesulfonic acid ion, toluenesulfonic acid ion, trifluoromethanesulfonic acid ion, naphthalenesulfonic acid ion, diphenylamine-4-sulfonic acid ion, 2-amino-4-methyl-5-chlorobenzenesulfonic acid ion , 2-amino-5-nitrobenzenesulfonic acid ion, Japanese Patent Laid-Open No. Hei 10-235999, Japanese Laid-Open Patent No. Hei 10-337959, Japanese Laid-Open Patent No. 11-102088, Japanese Laid-Open Patent 2000-108510, Japanese Laid-Open Patent Patent 2000-168223, Japanese Patent Application Publication No. 2001-209969, Japanese Patent Application Publication No. 2001-322354, Japanese Patent Application Publication No. 2006-248180, Japanese Patent Application Publication No. 2006-297907, Japanese Patent Application Publication No. Hei 8-253705, Japan Organic sulfonic acid-based anions such as sulfonic acid ions described in Publication Patent Publication No. 2004-503379, Japanese Patent Publication No. 2005-336150, and International Publication No. 2006/28006; Organic phosphoric acid such as octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2'-methylenebis(4,6-di-t-butylphenyl)phosphonic acid ion, etc. Anion, bistrifluoromethylsulfonylimide ion, bisperfluorobutanesulfonylimide ion, perfluoro-4-ethylcyclohexanesulfonic acid ion, tetrakis(pentafluorophenyl)borate ion, tris(fluoroalkylsulfonyl) Carbonanion etc. are mentioned, As a divalent thing, a benzene disulfonic acid ion, a naphthalene disulfonic acid ion, etc. are mentioned, for example. In addition, anionic groups such as carboxyl groups, phosphonic acid groups, and sulfonic acid groups are added to a quencher anion or cyclopentadienyl ring that has a function of deexciting (quenching) active molecules in an excited state. Eggplants can also be used if necessary, such as metallocene compound anions such as ferrocene and lutenocene. Further, p is selected so that the charge is neutral throughout the molecule.

Examples of the quencher anion include Japanese Laid-Open Patent Publication No. 60-234892, Japanese Laid-Open Patent Publication No. Hei 5-43814, Japanese Laid-Open Patent Publication No. Hei 5-305770, and Japanese Laid-Open Patent Publication Hei 6 -239028, Japanese Laid-Open Patent Publication No. Hei 9-309886, Japanese Laid-Open Patent Publication No. Hei 9-323478, Japanese Laid-Open Patent Publication No. Hei 10-45767, Japanese Laid-Open Patent Publication No. Hei 11-208118, Japan Unexamined Patent Publication No. 2000-168237, Japanese Unexamined Patent Publication 2002-201373, Unexamined Japanese Patent 2002-206061, Unexamined Japanese Patent 2005-297407, Japanese Unexamined Patent Publication No. Hei 7-96334, international Anions as described in Unexamined Publication No. 98/29257 and the like can be mentioned.

^{Examples of the anion represented by An q -} in the general formula (I) include monovalent organic sulfonic acid anion, bistrifluoromethylsulfonylimide ion, bisperfluorobutanesulfonylimide ion, and perfluoro-4-ethylcyclohexane. Sulfonic acid ions, benzene disulfonic acid ions, and naphthalenedisulfonic acid ions are preferable from the viewpoint of heat resistance, and bistrifluoromethylsulfonylimide ions are more preferable.

Specific examples of the cation moiety of the compound represented by the general formula (I) of the present invention include compounds No. 1 to No. 29 below.

[Formula 2]

[Formula 3]

[Formula 3A]

Among the compounds represented by the general formula (I), the following are preferable.

In _{terms of heat resistance, R 1} , R ₂ and R ₃ are preferably selected from a halogen atom, a halogen atom substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituent represented by -XY, and R ₁ , R _{It is particularly preferable that any two or more of 2} and R ₃ are substituted with a halogen atom or a halogen atom, or are selected from unsubstituted alkyl groups having 1 to 8 carbon atoms.

In _{terms of solvent solubility, R 4} , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are preferably substituted with a hydroxyl group or an unsubstituted alkyl group having 1 to 8 carbon atoms.

The method for producing the compound represented by the general formula (I) is not particularly limited, but can be prepared according to, for example, the following reaction formula.

[Formula 4]

(In the formula, R ₁ to R ₉ are the same as in the general formula (I).)

In the dye (A) used in the present invention, the compound represented by the general formula (I) can be used alone or in combination, and the total content is preferably 50 to 100% by mass, more Preferably it is 70-100 mass %. When the content of the compound represented by the general formula (I) of the present invention is less than 50% by mass, the solubility in the solvent may decrease or the heat resistance may decrease.

In the coloring composition of the present invention, the content of the dye (A) is preferably 0.01 to 50 mass%, more preferably 0.1 to 30 mass% in the coloring composition of the present invention. If the content of the dye (A) is less than 0.01% by mass, the color of the desired concentration may not be obtained in the cured product of the colored composition of the present invention. If it is greater than 50% by mass, the dye (A) in the colored composition Precipitation may occur.

<Polymerizable compound (B) having an ethylenically unsaturated bond>

The polymerizable compound (B) having an ethylenically unsaturated bond is not particularly limited, and those conventionally used in the photosensitive composition may be used. For example, ethylene, propylene, butylene, isobutylene, vinyl chloride, vinyl chloride Unsaturated aliphatic hydrocarbons such as leadene, vinylidene fluoride, and tetrafluoroethylene; (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 Carboxy groups and hydroxyl groups at both ends of mono [2-(meth)acryloyloxyethyl], phthalate mono[2-(meth)acryloyloxyethyl], and ω-carboxypolycaprolactone mono(meth)acrylate Branches of the polymer are mono (meth) acrylate, 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)acrylate having a meth)acryloyl group; (Meth)acrylate-2-hydroxyethyl, (meth)acrylate-2-hydroxypropyl, (meth)acrylate glycidyl, the following compounds No.A1 to No.A4, (meth)methyl acrylate, (meth)acrylic acid Butyl, (meth) isobutyl acrylate, (meth) acrylate-t-butyl, (meth) acrylate cyclohexyl, (meth) acrylate n-octyl, (meth) acrylate isooctyl, (meth) acrylate isononyl, (meth) ) Stearyl acrylate, (meth) lauryl acrylate, (meth) acrylate methoxyethyl, (meth) acrylate dimethylaminomethyl, (meth) acrylate dimethylaminoethyl, (meth) acrylate aminopropyl, (meth) acrylate dimethylaminopropyl , (Meth)acrylate ethoxyethyl, (meth)acrylate poly(ethoxy)ethyl, (meth)acrylate butoxyethoxyethyl, (meth)acrylate ethylhexyl, (meth)acrylate phenoxyethyl, (meth)acrylate tetra Hydrofuryl, (meth) vinyl 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, trimethylol ethane tri (meth) Acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate , Esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols such as tricyclodecanedimethyloldi(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; Maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3 -Acid anhydrides of unsaturated polybasic acids such as cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, and methylhymic anhydride; (Meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriaminetris(meth)acrylamide, xylylenebis(meth)acrylamide, α-chloroacrylamide, N-2-hydroxyethyl ( Amides of unsaturated monobasic acids and polyvalent amines such as meth)acrylamide; Unsaturated aldehydes such as acrolein; Unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; Styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid Unsaturated aromatic compounds such as vinyl benzyl methyl ether and vinyl benzyl glycidyl ether; Unsaturated ketones such as methyl vinyl ketone; Unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, and vinylpiperidine; Vinyl alcohols such as allyl alcohol and crotyl alcohol; 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; Vinylcloid, vinylidenecloid, divinylsuccinic acid, diallylphthalate, triallyl phosphate, triallyl isocyanurate, vinylthioether, vinylimidazole, vinyloxazoline, vinylcarbazole, vinylpyrrolidone, Polyfunctional acrylates containing hydroxyl groups such as vinyl pyridine, hydroxyl group-containing vinyl monomers and vinyl urethane compounds of polyisocyanate compounds, hydroxyl group-containing vinyl monomers and polyepoxy compounds of vinyl epoxy compounds, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. Reaction products of polyfunctional isocyanates such as tolylene diisocyanate and hexamethylene diisocyanate, hydroxyl group-containing polyfunctional acrylates such as pentaerythritol triacrylate, dipentaerythritol pentaacrylate, succinic anhydride, phthalic anhydride, tetrahydro phthalic anhydride, etc. 2 And polyfunctional acrylates having an acid value, which is a reactant of a basic acid anhydride.

These polymerizable compounds may be used alone or in combination of two or more, and when two or more kinds are used in combination, they may be copolymerized in advance and used as a copolymer.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

Further, in the coloring composition of the present invention, as the polymerizable compound (B) having an ethylenically unsaturated bond, a polymerizable compound having an ethylenically unsaturated bond (B') having an alkali-soluble substituent imparting alkali developability. ) (Hereinafter, also referred to as an alkali developable compound (B′) having an ethylenically unsaturated bond) is used, the colored photosensitive composition of the present invention becomes a colored alkaline developable photosensitive composition. As the alkali developable compound (B') having an ethylenically unsaturated bond, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl ( (Meth)acrylic acid esters such as meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate Ryu; N-vinylpyrrolidone; Styrene, such as styrene and its derivatives, and α-methylstyrene; Acrylamides such as (meth)acrylamide, methylol (meth)acrylamide, alkoxymethylol (meth)acrylamide, and diacetone (meth)acrylamide; Other vinyl compounds such as (meth)acrylonitrile, ethylene, propylene, butylene, vinyl chloride and vinyl acetate, and macromonomers such as polymethyl methacrylate macromonomer and polystyrene macromonomer, and monometh of tricyclodecane skeleton Copolymers of (meth)acrylic acid, such as acrylate, N-phenylmaleimide, methacryloyloxymethyl-3-ethyloxetane, etc., and unsaturated such as Carenz MOI and AOI manufactured by Showa Denko Co., Ltd. Copolymer of (meth)acrylic acid reacted with an isocyanate compound having a bond, a phenol and/or cresol novolac epoxy resin, a biphenyl skeleton, a novolac epoxy resin having a naphthalene skeleton, a bisphenol A novolak type epoxy compound, dicyclo An unsaturated monobasic acid is reacted with an epoxy group such as a novolak type epoxy compound such as a pentadiene novolak type epoxy compound, a polyphenylmethane type epoxy resin having a polyfunctional epoxy group, and an epoxy compound represented by the following general formula (1), In addition, a resin obtained by reacting a polybasic acid anhydride can be used. These monomers may be used alone or in combination of two or more. Moreover, it is preferable that the said alkali developable compound (B') which has an ethylenic unsaturated bond contains 0.2-1.0 equivalent of an unsaturated group.

[Formula 9]

(In the formula, X ¹ is a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O-, -S-, -SO ₂ -, -SS- , -SO-, -CO-, -OCO- or a substituent represented by the following formula (a), (b) or (c), the alkylidene group may be substituted with a halogen atom, R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or a halogen atom, and the alkyl group, the alkoxy group and The alkenyl group may be substituted with a halogen atom, and r is an integer of 0-10.)

[Formula 10]

(In the formula, Z ¹ is a phenyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a carbon source which may be substituted with an alkoxy group having 1 to 10 carbon atoms. Embroidery 3-10 represents a cycloalkyl group or a hydrogen atom, Y ¹ represents a C1-C10 alkyl group, a C1-C10 alkoxy group, a C2-C10 alkenyl group or a halogen atom, and the Y alkyl group in the ^1, an alkoxy group and alkenyl group is optionally substituted with a halogen atom, b is an integer of 0-5.)

[Formula 11]

[Formula 12]

(In the formula, Y ² and Z ² are each independently an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, and 6 to carbon atoms which may be substituted with a halogen atom. 20 aryloxy group, an arylthio group having 6 to 20 carbon atoms which may be substituted with a halogen atom, an arylalkenyl group having 8 to 20 carbon atoms which may be substituted with a halogen atom, an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom, A heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom, a group obtained by combining a plurality of these groups, or a halogen atom is represented, and the methylene group in the alkyl group and arylalkyl group in ^{Y 2} and Z ^{2 is an unsaturated bond, -O- or} -S- may be interrupted, and Z ² may form a ring between adjacent Z ¹² , p represents an integer of 0 to 4, q represents an integer of 0 to 8, and r represents an integer of 0 to 4 It represents an integer, s represents an integer of 0-4, and the sum of the number of r and s is an integer of 2-4.)

Examples of the unsaturated monobasic acid acting on the epoxy group of the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate maleate, and the like. Hydroxyethyl acrylate maleate, hydroxypropyl methacrylate maleate, hydroxypropyl acrylate maleate, dicyclopentadiene maleate, etc. are mentioned.

In addition, as the polybasic acid anhydride that is made to act after the unsaturated monobasic acid is reacted, biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic anhydride, ethylene glycol bisanehydrotrimellitate, glycerol trisanehydrotrimellitate, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic acid ) Anhydride, methylnadic acid anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxyl Acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methylhymic anhydride, and the like.

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows. That is, in an epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound, with respect to one hydroxyl group of the epoxy adduct, the acid of the polybasic acid anhydride It is preferable to make the ratio of 0.1 to 1.0 anhydride structures.

The reaction of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride can be carried out according to a conventional method.

In order to improve the developability of the colored composition of the present invention which is a colored alkali developable photosensitive composition by adjusting the acid value, a monofunctional or polyfunctional epoxy compound can be used together with the alkali developable compound having an ethylenically unsaturated bond. The alkali developable compound having an ethylenically unsaturated bond is preferably in the range of 5 to 120 mgKOH/g, and the amount of monofunctional or polyfunctional epoxy compound is preferably selected to satisfy the acid value.

As the monofunctional epoxy compound, 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 glyci Dyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glyci Dyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, 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, cyclo Hexene oxide, propylene oxide, the above compounds No.A2, No.A3, etc. are mentioned.

As the polyfunctional epoxy compound, if at least one selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers is used, a colored alkali developable photosensitive composition having even better properties can be obtained. As the bisphenol-type epoxy compound, in addition to the epoxy compound represented by the general formula (1), for example, a bisphenol-type epoxy compound such as a hydrogenated bisphenol-type epoxy compound may 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, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyl Oxymethyl)propane, 1,1,1-tri(glycidyloxymethyl)ethane, 1,1,1-tri(glycidyloxymethyl)methane, 1,1,1,1-tetra(glycidyl) Oxymethyl)methane.

In addition, novolac-type epoxy compounds such as phenol novolak-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; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1- Alicyclic epoxy compounds such as epoxyethyl-3,4-epoxycyclohexane; Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalic acid, and glycidyl dimer; Glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidyl-P-aminophenol, and 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, dicyclopentadiene-type epoxy compounds, and the like can also be used.

Among the polymerizable compounds (B) having an ethylenically unsaturated bond (including the alkali developable compound (B') having an ethylenically unsaturated bond), in terms of compatibility, alkali developability and heat resistance, an unsaturated aliphatic hydrocarbon, Unsaturated polybasic acids, polyfunctional acrylates having an acid value, and (meth)acrylic esters are preferable, and unsaturated aliphatic hydrocarbons and unsaturated polybasic acids are more preferable.

In the coloring composition of the present invention, the content of the polymerizable compound (B) having an ethylenically unsaturated bond (including the alkali developable compound (B') having an ethylenically unsaturated bond) is contained in the coloring composition of the present invention. , 30 to 99% by mass, particularly preferably 60 to 95% by mass. When the content of the polymerizable compound (B) having an ethylenically unsaturated bond is less than 30% by mass, cracks occur due to insufficient mechanical strength of the cured product, or alkali developability occurs, and poor development occurs. If it is larger than 99% by mass, tackiness occurs due to insufficient curing by exposure, or if it has alkali developability, the interval during development becomes longer and the cured portion may also cause film damage with alkali.

<Photopolymerization initiator (C)>

As the photoinitiator (C), it is possible to use a conventionally known compound, for example, benzophenone, phenylbiphenylketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethyl Ketal, 1-benzyl-1-dimethylamino-1-(4'-morpholinobenzoyl)propane, 2-morpholyl-2-(4'-methylmercapto)benzoylpropane, thioxanthone, 1-chloro- 4-propoxycytoxanthone, isopropylthioxanthone, diethylthioxanthone, ethylanthraquinone, 4-benzoyl-4'-methyldiphenylsulfide, benzoinbutyl ether, 2-hydroxy-2-benzoylpropane , 2-hydroxy-2-(4'-isopropyl)benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis(9'-acridinyl ) Heptane, 9-n-butyl-3,6-bis(2'-morpholinoisobutyloyl)carbazole, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2 -Phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-naphthyl-4,6-bis(trichloromethyl)-s-triazine, 2,2-bis(2-chlorophenyl )-4,5,4',5'-tetraphenyl-1-2'-biimidazole, 4,4-azobisisobutylonitrile, triphenylphosphine, camphor quinone, benzoyl peroxide, etc. Examples of commercially available products include N-1414, N-1717, N-1919, PZ-408, NCI-831, NCI-930 (made by ADEKA Co., Ltd.), IRGACURE369, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02 (product of BASF Co., Ltd.), etc. are mentioned.

Among the photoinitiators (C), in terms of sensitivity and color tone, 2-morpholyl 2-(4'-methylmercapto)benzoylpropane, 9-n-butyl-3,6-bis(2'-morpholinoiso Butyloyl)carbazole is preferred, and 2-morpholyl 2-(4'-methylmercapto)benzoylpropane is more preferred.

In the colored composition of the present invention, the content of the photoinitiator (C) is preferably 0.1 to 30% by mass, particularly 0.5 to 10% by mass, in the colored composition of the present invention. When the content of the photopolymerization initiator (C) is less than 0.1% by mass, hardening by exposure may be insufficient, and when it is greater than 30% by mass, the initiator (C) may be precipitated in the resin composition.

The coloring composition of the present invention may further contain a coloring material (D). These coloring materials may be used alone or in combination of two or more.

As the colorant (D), a dye or a pigment may be used. For example, a nitroso compound, a nitro compound, an azo compound, a diazo compound, a xanthene compound, a quinoline compound, an anthraquinone compound, a coumarin compound, a phthalocyanine compound, iso Indolinone compound, isoindoline compound, quinacridone compound, antantrone compound, perinone compound, perylene compound, diketopyrrolopyrrole compound, thioindigo compound, dioxazine compound, triphenylmethane compound, quinophthalone compound , 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 was adjusted and coated with an epoxy resin, the carbon black was previously dispersed with a resin in a solvent to adsorb 20 to 200 mg/g of the resin, and the carbon black was treated with an acidic or alkaline surface. , Having an average particle diameter of 8 nm or more and a DBP oil absorption of 90 ml/100 g or less, and having a total amount of oxygen calculated from _{CO and CO 2} in volatile components at 950° C. of 9 mg or more per ^{100 m 2 of carbon black surface area;} 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, ferrocyanide, phosphate ultramarine, royal blue, ultramarine, cerulean blue, pyridine, emerald green, lead sulfate, yellow Inorganic or organic pigments such as lead, zinc sulfur, iron dan (red iron oxide (III)), cadmium red, synthetic iron black, and amber can be used.

As the color material (D), 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. are mentioned.

As the color material (D), it is also possible to use a known dye. Known dyes include, for example, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes , Nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, and dyes such as cyanine dyes.

In the coloring composition of the present invention, the content of the coloring material (D) is preferably 0 to 350 parts by mass, more preferably 0 to 100 parts by mass of the polymerizable compound (B) having an ethylenically unsaturated bond. It is 250 parts by mass. When it exceeds 350 parts by mass, the light transmittance of the colored composition of the present invention, particularly the cured product using the colored alkaline developable photosensitive composition, and the color filter for a display device decreases, and the luminance of the display device decreases, which is not preferable.

A solvent can also be added to the coloring composition of this invention. As the solvent, a solvent capable of dissolving or dispersing each of the above components (such as dye (A) made of the compound of the present invention) as necessary, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone , Ketones such as 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, acetate-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; 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, and amyl alcohol; 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, etc. Ether ester solvent; BTX-based solvents such as benzene, toluene, and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; Terpene hydrocarbon oils such as terepin oil, D-limonene, and pinene; Paraffin-based solvents such as mineral spirit, Swasol #310 (Cosmo Matsuyama Sekiyu Co., Ltd.), and Solvesso #100 (Equson 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 solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water, etc. These solvents can be used as one type or a mixed solvent of two or more. Among these, ketones, ether ester solvents, and the like, especially propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, and the like are preferable because of good compatibility between the resist and the photopolymerization initiator (C) in the coloring composition.

In the coloring composition of the present invention, the concentration of the composition other than the solvent is preferably 5 to 30% by mass, and when it is less than 5% by mass, it is difficult to thicken the film thickness, so that the desired wavelength light can be obtained. It is not preferable because it cannot be sufficiently absorbed, and when it is larger than 30% by mass, the preservability of the composition due to precipitation of the composition decreases, or the handling of the composition decreases because the viscosity improves.

The coloring composition of the present invention can 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; Lamellar clay minerals, milori blue, calcium carbonate, magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide , Platinum, gold, silver, copper, and the like. Among these, titanium oxide, silica, layered clay minerals, and silver are preferable. In the coloring composition of the present invention, the content of the inorganic compound is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the polymerizable compound (B) having an ethylenically unsaturated bond. And, these inorganic compounds may be used alone or in combination of two or more.

These inorganic compounds are used, for example, as fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, repellent ink agents, and the like.

In the coloring composition of the present invention, when using a pigment and/or an inorganic compound, a dispersant can be added. As the dispersant, any dispersing agent capable of dispersing and stabilizing pigments and inorganic compounds may be used, and commercially available dispersants, such as, for example, manufactured by Vicchemy, BYK series, may be used. A polymer dispersant composed of urethane, having a nitrogen atom as a basic functional group, a functional group having a nitrogen atom is an amine and/or a quaternary salt thereof, and an amine value of 1 to 100 mgKOH/g is suitably used.

In addition, in the colored composition of the present invention, if necessary, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, and phenothiazine; Plasticizer(可塑劑); Adhesion promoter; Filler; Antifoam; Leveling agents; Surface modifiers; Antioxidants, ultraviolet absorbers; Dispersion aid; Anti-aggregation agent; catalyst; Effect promoters; Crosslinking agent; Conventional additives such as thickeners can be added.

In the coloring composition of the present invention, optional components other than the dye (A), the polymerizable compound (B) having an ethylenically unsaturated bond, and a photoinitiator (C) (however, the coloring material (D) and the solvent are excluded) The content of) is appropriately selected depending on the intended use and is not particularly limited, but is preferably 50 parts by mass or less in total based on 100 parts by mass of the content of the polymerizable compound (B) having an ethylenically unsaturated bond.

In the coloring composition of the present invention, by using another organic polymer together with the polymerizable compound (B) having an ethylenically unsaturated bond, the properties of the cured product made of the coloring composition of the present invention can 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-methylmeth Acrylate 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, polyacrylic Amides, saturated polyesters, phenolic resins, phenoxy resins, polyamideimide resins, polyamic acid resins, epoxy resins, and the like. Among these, polystyrene, (meth)acrylic acid-methylmethacrylate copolymer, and epoxy resin desirable.

When using other organic polymers, the amount used is preferably 10 to 500 parts by mass based on 100 parts by mass of the polymerizable compound (B) having an ethylenically unsaturated bond.

In the coloring composition of the present invention, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound, and the like can be used in combination.

As the 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-mercaptoethane Sulfonic 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-mercaptobenzoimidazole, 2-mercapto-3-pyridinol, Mercapto compounds such as 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropanetris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and the above mercapto compounds Iodide alkyl compounds such as disulfide compounds obtained by oxidation, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid, trimethylolpropane tris (3-mercaptoisobutylate), butanediol Bis(3-mercaptoisobutylate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediolbisthiopropionate, butanediolbisthioglycolate, ethylene glycolbisthioglycolate, trimethyl Allpropanetristhioglycolate, butanediolbisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropanetristhioglycolate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, trishydride Aliphatic polyfunctional thiol compounds such as oxyethyltrithiopropionate, compounds represented by the following compound No.C1, trimercaptopropionate tris (2-hydroxyethyl) isocyanurate, and Carens MT manufactured by Showa Denko BD1, PE1, NR1, etc. are mentioned.

[Formula 13]

Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphate and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, higher amine halogenates, and quaternary ammonium salts. Nonionic surfactants such as cationic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides, amphoteric surfactants, and surfactants such as silicone surfactants can be used, and combinations thereof You may use it.

As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, a silane couple having an isocyanate group, a methacryloyl group, or an epoxy group, such as KBE-9007, KBM-502, KBE-403, etc. Ring agents are suitably used.

_{As the melamine compound, an active methylol group (CH 2} OH group) in a nitrogen compound such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylolurea. All or part of (at least two) are alkyl etherified compounds. Here, the alkyl group constituting the alkyl ether includes a methyl group, an ethyl group, or a butyl group, and may be the same or different from each other. Moreover, the methylol group which is not alkyl-etherified 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 melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.

The colored composition of the present invention is a support substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic, etc. by known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing and dipping. Can be applied above. In addition, after applying to a support substrate such as a film once, it may be transferred onto another support substrate, and the application method is not limited.

In addition, as a light source of active light used when curing the colored composition of the present invention, one emitting light having a wavelength of 300 to 450 nm can be used. For example, ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, etc. Can be mentioned.

In addition, by using laser light as an exposure light source, the laser direct drawing method, which forms an image directly from digital information such as a computer, without using a mask, can improve not only productivity but also resolution and positional accuracy. It is useful, and as the laser light, light having a wavelength of 340 to 430 nm is suitably used. Argon ion lasers, helium neon lasers, YAG lasers, and semiconductor lasers are also used that emit light in the visible to infrared region. When these lasers are used, a sensitizing dye that absorbs light in the visible to infrared region is added.

The colored composition (or cured product thereof) of the present invention is a photocurable paint or varnish, a photocurable adhesive, a printed circuit board or a color television, a PC monitor, a portable information terminal, or a liquid crystal display panel for color display such as a digital camera. Color filter, CCD image sensor color filter, electrode material for plasma display panel, powder coating, printing ink, printing plate, adhesive, dental composition, resin for photolithography, gel coat, photoresist for electronic engineering, To form a structure in the manufacturing process of an electroplating resist, an etching resist, a liquid and dry film, a solder resist, a resist for manufacturing a color filter for various display purposes, or a plasma display panel, an electroluminescent display, and an LCD Resist, composition for encapsulating electrical and electronic parts, solder resist, magnetic recording material, micro-mechanical parts, waveguide, optical switch, plating mask, etching mask, color test system, fiberglass cable Coatings, stencils for screen printing, materials for manufacturing three-dimensional objects by stereolithography, materials for holographic recording, image recording materials, microelectronic circuits, decolorization materials, decolorization materials for image recording materials, image recording materials using microcapsules It can be used for various purposes such as decolorization materials for dragons, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, photoresist materials used for dielectric layer formation in sequential lamination of printed circuit boards, or protective films. And there is no particular limitation on its use.

When the colored composition of the present invention is a colored alkali developable photosensitive composition, it is used for the purpose of forming a pixel of a color filter, and in particular, to form a color filter for a display device for an image display device such as a liquid crystal display panel and an organic EL. It is useful as a photosensitive composition for.

Further, the color filter for a display device of the present invention may have optical elements of red, green, blue, orange, purple and black in addition to the cured product of the present invention.

The color filter for a display device is activated through (1) a step of forming a coating film of the colored composition of the present invention (especially a colored alkali developable photosensitive composition) on a substrate, and (2) a mask having a predetermined pattern shape on the coating film. It is preferably formed by a step of irradiating light, (3) a step of developing a film after exposure with a developer (especially an alkali developer), and (4) a step of heating the film after development. Moreover, the coloring composition of this invention is useful also as a coloring composition of an inkjet system and a transfer system without a developing process.

Production of a color filter for use in a liquid crystal display panel or the like can be produced by using the present invention or a coloring composition other than that, repeating the steps of the above (1) to (4), combining two or more colors of patterns.

Example

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

Examples 1-1 to 1-8 show preparation examples of colored alkali developable photosensitive compositions No. 1 to No. 8, which are colored photosensitive compositions of the present invention, and Comparative Examples 1-1 and 1-2 are comparative colored alkali developed Preparation examples of photosensitive compositions No. 1 and No. 2 are shown.

In Evaluation Examples 1-1 to 1-8, the heat resistance of the colored alkali developable photosensitive compositions No. 1 to No. 8 obtained in Examples 1-1 to 1-8 was evaluated, and Comparative Evaluation Examples 1-1 and 1-2 In the following, the heat resistance of the comparative colored alkali developable photosensitive compositions No. 1 and No. 2 obtained in Comparative Examples 1-1 and 1-2 was evaluated.

[Examples 1-1 to 1-8 and Comparative Examples 1-1 and 1-2] Of colored alkali developable photosensitive compositions No.1 to No.8 and comparative colored alkali developable photosensitive compositions No.1 and No.2 pharmacy

<Step 1> Preparation of alkali developable photosensitive composition

(B) 30.33g of ACA Z251 (manufactured by Daicel Cytech) and 11.04g of Aaronix M-450 (manufactured by Toagosei) as a component, (C) 1.93g of Irgacure 907 (manufactured by BASF) as a component, ( E) 36.60 g of PGMEA and 20.08 g of cyclohexanone as a component, and 0.01 g of FZ2122 (manufactured by Toray Dow Corning) as other components are mixed and stirred until the insoluble matter disappears to prepare an alkali developable photosensitive composition. Got it.

<Step 2> Preparation of dye solutions No.1 to No.8 and comparative dye solutions No.1 and No.2

(A) As a component, the bis(trifluoromethanesulfonyl) of compounds No.2 to No.4, No.17, No.18 and No.20 to No.22, and comparative compounds No.1 and No.2 is already present. 0.10 g of de-salt and 1.90 g of dimethylacetamide were added, stirred, and dissolved to obtain dye solutions No. 1 to No. 8 and comparative dye solutions No. 1 and No. 2.

<Step 3> Preparation of colored alkali developable photosensitive compositions No.1 to No.8 and comparative colored alkaline developable photosensitive compositions No.1 and No.2

5.0 g of each alkali developable photosensitive composition obtained in step 1 and 1.0 g of each dye solution of the corresponding No. obtained in step 2 are each mixed and stirred until uniform, and colored alkali developable photosensitive compositions No. 1 to 1 are mixed. No. 8 and comparative colored alkali developable photosensitive compositions No. 1 and No. 2 were obtained.

[Formula 14]

[Evaluation Examples 1-1 to 1-8 and Comparative Evaluation Examples 1-1 to 1-2] Heat resistance evaluation by firing

Colored alkali developable photosensitive compositions No.1 to No.8 obtained in Examples 1-1 to 1-8, and comparative colored alkaline developable photosensitive compositions No.1 and No. 2 was coated on a glass substrate under the conditions of 410 rpm x 7 seconds, and dried (90°C, 90 seconds) on a hot plate. The obtained coating film was exposed (150 mJ/cm ² ) with an ultra-high pressure mercury lamp. The coating film after exposure was fired under conditions of 230°C x 30 min. When the absorbance of the coating film before firing (after exposure) and the absorbance of the coating film after firing was measured at the maximum absorption wavelength (λmax) of the compound (dye) used, and the absorbance of the coating film before firing (after exposure) was 100. It was evaluated as relative strength. On the other hand, the closer the absorbance of the coating film after firing is to 100, the higher the heat resistance. Moreover, the color difference (ΔE _{ab *} ) before and after firing was investigated. The results are shown in [Table 1].

[Evaluation Examples 2-1 to 2-8 and Comparative Evaluation Examples 2-1 to 2-2] Solubility Evaluation

For each 0.1 g of compounds No.2 to 4, No.17, No.18 and No.20 to No.22, and comparative compounds No.1 and No.2, propylene glycol-1-monomethylether-2-acetate was added. The concentration when it was added dropwise and completely dissolved while stirring was evaluated as the solubility.

From the above results, in the colored alkali developable photosensitive composition using the compound according to the present invention as a dye, the compound used as the dye is at the position corresponding to _{R 1} , R ₂ and R _{3 in formula (I), and a substituent other than hydrogen} Since it has at least two places, there is little change in color difference and high heat resistance.

On the other hand, in the colored alkali developable photosensitive composition using Comparative Compound No. 1 as a dye, the compound also used as a dye has one substituent other than hydrogen at the positions corresponding to _{R 1} , R ₂ and R _{3 in formula (I).} Because it only has it, heat resistance is inferior.

In addition, in the colored alkali developable photosensitive composition using Comparative Compound No. 2 as a dye, the compound used as the dye has _two substituents other than hydrogen at the positions corresponding to _{R 1} , R 2 and R _{3 in Formula (I).} But it has poor solubility.

Therefore, the colored photosensitive composition of the present invention, which is a colored alkali developable photosensitive composition using the compound according to the present invention as a dye, is useful for a color filter for a display device.

Claims (6)

A colored photosensitive composition containing a dye (A) comprising a compound represented by the following general formula (I), a polymerizable compound (B) having an ethylenically unsaturated bond, and a photoinitiator (C).

(Wherein, R ₁ , R ₂ , R ₃ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ are each independently a hydrogen atom; a halogen atom; Cyano group, nitro group, hydroxyl group; halogen atom substituted or unsubstituted C1-C8 alkyl group; halogen atom substituted or unsubstituted C6-C12 aryl group; halogen atom substituted or non-substituted Substituted arylalkyl group having 7 to 20 carbon atoms; Or a substituent represented by -XY, X represents an oxygen atom or a sulfur atom, Y is substituted with a halogen atom or an unsubstituted alkyl group having 1 to 8 carbon atoms, halogen Represents an atom substituted or unsubstituted aryl group having 6 to 12 carbon atoms or a halogen atom substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms,
R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each independently a hydroxyl group; Halogen atom; A cyano group, a nitro group, a hydroxyl group, or a halogen atom substituted or unsubstituted alkyl group having 1 to 8 carbon atoms; An alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, or an unsubstituted phenyl group substituted with a vinyl group; Or an alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, or a vinyl group substituted or unsubstituted benzyl group, and R ₄ and R ₅ , R ₆ and R ₇ , and R ₈ and R ₉ are connected to 3 It may form a heterocycle of ~6 membered ring,
R ₁ , R ₂ and R ₃ are halogen atoms,
An ^q- represents a q-valent anion, q represents 1 or 2, and p represents a coefficient that keeps the charge neutral.) A colored photosensitive composition containing a dye (A) comprising a compound represented by the following general formula (I), a polymerizable compound (B) having an ethylenically unsaturated bond, and a photoinitiator (C).

(Wherein, R ₁ , R ₂ , R ₃ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ are each independently a hydrogen atom; a halogen atom; Cyano group, nitro group, hydroxyl group; halogen atom substituted or unsubstituted C1-C8 alkyl group; halogen atom substituted or unsubstituted C6-C12 aryl group; halogen atom substituted or non-substituted Substituted arylalkyl group having 7 to 20 carbon atoms; Or a substituent represented by -XY, X represents an oxygen atom or a sulfur atom, Y is substituted with a halogen atom or an unsubstituted alkyl group having 1 to 8 carbon atoms, halogen Represents an atom substituted or unsubstituted aryl group having 6 to 12 carbon atoms or a halogen atom substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms,
R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each independently a hydroxyl group; Halogen atom; A cyano group, a nitro group, a hydroxyl group, or a halogen atom substituted or unsubstituted alkyl group having 1 to 8 carbon atoms; An alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, or an unsubstituted phenyl group substituted with a vinyl group; Or an alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, or a vinyl group substituted or unsubstituted benzyl group, and R ₄ and R ₅ , R ₆ and R ₇ , and R ₈ and R ₉ are connected to 3 It may form a heterocycle of ~6 membered ring,
However, at least one of R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ is substituted with a cyano group, a nitro group, a hydroxyl group or a halogen atom, or is an unsubstituted alkyl group having 2 to 8 carbon atoms,
At least two of R ₁ , R ₂ and R _{3 are halogen atoms,}
An ^q- represents a q-valent anion, q represents 1 or 2, and p represents a coefficient that keeps the charge neutral.) The following compound No. 1, compound No. 2, compound No. 4, compound No. 17, compound No. 20, compound No. 21 and compound No. A colored photosensitive composition containing at least one dye selected from the group consisting of 22 (A), a polymerizable compound (B) having an ethylenically unsaturated bond, and a photoinitiator (C).

The method according to any one of claims 1 to 3,
Further, a colored photosensitive composition containing at least one color material (however, excluding a dye comprising a compound represented by the following general formula (I)) (D).

(Wherein, R ₁ , R ₂ , R ₃ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ are each independently a hydrogen atom; a halogen atom; Cyano group, nitro group, hydroxyl group; halogen atom substituted or unsubstituted C1-C8 alkyl group; halogen atom substituted or unsubstituted C6-C12 aryl group; halogen atom substituted or non-substituted Substituted arylalkyl group having 7 to 20 carbon atoms; Or a substituent represented by -XY, X represents an oxygen atom or a sulfur atom, Y is substituted with a halogen atom or an unsubstituted alkyl group having 1 to 8 carbon atoms, halogen Represents an atom substituted or unsubstituted aryl group having 6 to 12 carbon atoms or a halogen atom substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms,
R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each independently a hydroxyl group; Halogen atom; A cyano group, a nitro group, a hydroxyl group, or a halogen atom substituted or unsubstituted alkyl group having 1 to 8 carbon atoms; An alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, or an unsubstituted phenyl group substituted with a vinyl group; Or an alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, or a vinyl group substituted or unsubstituted benzyl group, and R ₄ and R ₅ , R ₆ and R ₇ , and R ₈ and R ₉ are connected to 3 It may form a heterocycle of ~6 membered ring,
R ₁ , R ₂ and R ₃ are halogen atoms,
An ^q- represents a q-valent anion, q represents 1 or 2, and p represents a coefficient that keeps the charge neutral.)

(Wherein, R ₁ , R ₂ , R ₃ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ are each independently a hydrogen atom; a halogen atom; Cyano group, nitro group, hydroxyl group; halogen atom substituted or unsubstituted C1-C8 alkyl group; halogen atom substituted or unsubstituted C6-C12 aryl group; halogen atom substituted or non-substituted Substituted arylalkyl group having 7 to 20 carbon atoms; Or a substituent represented by -XY, X represents an oxygen atom or a sulfur atom, Y is substituted with a halogen atom or an unsubstituted alkyl group having 1 to 8 carbon atoms, halogen Represents an atom substituted or unsubstituted aryl group having 6 to 12 carbon atoms or a halogen atom substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms,
R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each independently a hydroxyl group; Halogen atom; A cyano group, a nitro group, a hydroxyl group, or a halogen atom substituted or unsubstituted alkyl group having 1 to 8 carbon atoms; An alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, or an unsubstituted phenyl group substituted with a vinyl group; Or an alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, or a vinyl group substituted or unsubstituted benzyl group, and R ₄ and R ₅ , R ₆ and R ₇ , and R ₈ and R ₉ are connected to 3 It may form a heterocycle of ~6 membered ring,
However, at least one of R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ is substituted with a cyano group, a nitro group, a hydroxyl group or a halogen atom, or is an unsubstituted alkyl group having 2 to 8 carbon atoms,
At least two of R ₁ , R ₂ and R _{3 are halogen atoms,}
An ^q- represents a q-valent anion, q represents 1 or 2, and p represents a coefficient that keeps the charge neutral.) A cured product of the colored photosensitive composition according to any one of claims 1 to 3. A color filter for a display device comprising at least a part of the cured product according to claim 5.