JP6498936B2 - Colored photosensitive composition - Google Patents

Description

  The present invention relates to an energy ray-polymerizable colored photosensitive composition using a dye designed to have a desired hue and having improved solvent resistance and heat resistance, and a color filter using the colored photosensitive composition. .

  Compounds having high intensity absorption for specific light include recording layers of optical recording media such as CD-R, DVD-R, DVD + R, BD-R, liquid crystal display (LCD), plasma display panel (PDP) ), Electroluminescent displays (ELDs), cathode ray tube displays (CRTs), fluorescent display tubes, field emission displays, etc.

Optical filters for image display devices such as liquid crystal display devices (LCDs), plasma display panels (PDPs), electroluminescent displays (ELDs), cathode ray tube displays (CRTs), fluorescent display tubes, field emission displays, etc. Various compounds that absorb light of a wavelength of ̃1100 nm are used as light absorbers.
For these light absorbing agents, it is required that the light absorption be particularly sharp, that is, the half width of λmax be small, and that the function be not lost by light, heat or the like.

Optical filters used mainly in liquid crystal displays (LCDs) include color filters. Although three primary colors of RGB have generally been used for color filters, it is difficult to provide pure RGB hues with a single colorant, and pure RGB hues using a plurality of colorants Efforts have been made to bring them closer to Therefore, color materials such as yellow, orange, and purple are also required instead of RGB.
Organic and / or inorganic pigments have been used as light absorbers for color filters due to their high heat resistance, but since they are pigments, they have the problem of lowering the brightness as a display device. This problem has been solved by increasing the brightness of the However, with the trend toward lower power consumption, development of color filters using dyes has become active.

Furthermore, in recent years, in color filters used in solid-state imaging devices, thinning of a colored pattern is required from the viewpoint of improving image quality, and to thin the film, it is necessary to increase 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 the dye.
However, if the dye concentration is increased, elution or precipitation of the dye from the formed pixel can be observed after film formation, or if heat treatment (post-baking) is performed after film formation, between adjacent pixels or in the laminated structure It is a problem that color mixing is likely to occur between the upper and lower layers.

Patent Documents 1 and 2 disclose colored resin compositions for color filters containing a triarylmethane dye having a specific structure.
However, the triarylmethane dyes described in these documents are not satisfactory in terms of heat resistance.

JP, 2010-204132, A JP 2012-017425 A

  Therefore, an object of the present invention is to provide a colored photosensitive composition (colored alkaline developable photosensitive composition) which is excellent in heat resistance. Another object of the present invention is also an optical filter using the above-mentioned colored photosensitive composition (colored alkaline developable photosensitive composition), which is particularly suitable for an image display device such as a liquid crystal display panel without lowering the luminance. It is to provide a color filter.

  As a result of intensive studies, the present inventor found that a compound having a specific structure is excellent in heat resistance, and excellent in solvent resistance in a colored photosensitive composition (colored alkaline developable photosensitive composition). In addition, the above-mentioned colored photosensitive composition (colored alkaline developable photosensitive composition) is suitable for a color filter for an image display device such as a liquid crystal display panel without reducing the brightness of an optical filter (particularly a color filter). The present invention has been achieved.

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

（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₂₀、Ｒ₂₁、Ｒ₂₂、Ｒ₂₃、Ｒ₂₄、Ｒ₂₅、Ｒ₂₆、Ｒ₂₇及びＲ₂₈は、それぞれ独立に、水素原子若しくはハロゲン原子、シアノ基、ニトロ基、水酸基、ハロゲン原子で置換されている若しくは無置換の炭素原子数１〜８のアルキル基、ハロゲン原子で置換されている若しくは無置換の炭素原子数６〜１２のアリール基、ハロゲン原子で置換されている若しくは無置換の炭素原子数７〜２０のアリールアルキル基又は−Ｘ−Ｙで表される置換基を表し、Ｘは酸素原子又は硫黄原子を表し、Ｙは、ハロゲン原子で置換されている若しくは無置換の炭素原子数１〜８のアルキル基、ハロゲン原子で置換されている若しくは無置換の炭素原子数６〜１２のアリール基又はハロゲン原子で置換されている若しくは無置換の炭素原子数７〜２０のアリールアルキル基を表し、
Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈及びＲ₉は、それぞれ独立に、水酸基若しくはハロゲン原子、シアノ基、ニトロ基、水酸基若しくはハロゲン原子で置換されている若しくは無置換の炭素原子数１〜８のアルキル基、炭素原子数１〜４のアルキル基、ハロゲン原子、シアノ基若しくはビニル基で置換されている若しくは無置換のフェニル基、炭素原子数１〜４のアルキル基、ハロゲン原子、シアノ基若しくはビニル基で置換されている若しくは無置換のベンジル基を表し、Ｒ₄とＲ₅、Ｒ₆とＲ₇、及びＲ₈とＲ₉は、連結して３〜６員環の複素環を形成していてもよく、
Ｒ₁、Ｒ₂及びＲ₃のうち少なくとも２つは水素原子以外の置換基であり、
Ａｎ^q-はｑ価のアニオンを表し、ｑは１又は２を表し、ｐは電荷を中性に保つ係数を表す。）

(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 or a halogen atom , A cyano group, a nitro group, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or substituted by a halogen atom A halogen atom-substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms or a substituent represented by -X-Y, X represents an oxygen atom or a sulfur atom, and Y represents a halogen A substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, which is substituted or unsubstituted with a halogen atom or a halogen atom; Replacement charcoal Represents an arylalkyl group having 7 to 20 atomic atoms,
Each of R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently represents a hydroxyl group or a halogen atom, a cyano group, a nitro group, a hydroxyl group, or a substituted or unsubstituted carbon atom number An alkyl group of 1 to 8, an alkyl group of 1 to 4 carbon atoms, a halogen atom, a phenyl group substituted or unsubstituted with cyano group or vinyl group, an alkyl group of 1 to 4 carbon atoms, a halogen atom, R ₄ and R ₅ , R ₆ and R ₇ , and R ₈ and R ₉ are linked to form a 3- to 6-membered heterocyclic ring, each of which represents a substituted or unsubstituted benzyl group substituted with a cyano group or a vinyl group May form a
At least two of R ₁ , R ₂ and R ₃ are substituents other than hydrogen atom,
An ^q- represents a q-valent anion, q represents 1 or 2, and p represents a coefficient for keeping the charge neutral. )

  Further, according to the present invention, as a preferred embodiment of the colored photosensitive composition, a polymerizable compound having an ethylenically developable bond (having an alkali developability as a polymerizable compound (B) having the above-mentioned ethylenic unsaturated bond ( It provides a colored photosensitive composition (colored alkaline developable photosensitive composition) having alkali developability using B ').

  The present invention also provides a cured product of the above-mentioned colored photosensitive composition (colored alkaline developable photosensitive composition) and a color filter for a display device formed using the cured product.

  The colored photosensitive composition (colored alkaline developable photosensitive composition) of the present invention containing a compound having a specific structure is excellent in heat resistance. Moreover, 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, a colored photosensitive composition or a colored alkali-developable composition to be described later will be appropriately described as a colored composition.

  The coloring composition of the present invention comprises a dye (A) (hereinafter also referred to as a dye (A)) comprising a compound represented by the above general formula (I), and a polymerizable compound (B) having an ethylenically unsaturated bond (B) A polymerizable compound (B ′) having an ethylenically unsaturated bond, which has an alkali-soluble substituent that gives alkali developability, and a photopolymerization initiator (C), and, if necessary, a coloring material (however, the above-mentioned Containing one or more (D) of (a) (except for dyes consisting of a compound represented by formula (I)). Hereinafter, each component will be described in order.

<Dye (A)>
The dye (A) used in the present invention may contain at least one compound represented by the above general formula (I), and can be used singly or in combination of two or more. Moreover, it is also possible to use a well-known dye other than the compound represented by said general formula (I) for dye (A). Examples of known dyes include 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 And dyes such as phthalocyanine dyes and cyanine dyes, and the like, and a plurality of these may be mixed and used.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ and R ₁ , R ₂ and R _{3 in the} above general formula (I) are represented by -X-Y As the unsubstituted alkyl group having 1 to 8 carbon atoms represented by Y, 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 etc. is mentioned,
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, a carbon number of 1 to 4 carbon atoms substituted by a hydroxyl group Examples of the alkyl group of 8 include groups in which part or all of hydrogen atoms in the above-mentioned alkyl group having 1 to 8 carbon atoms are 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 each represented by -X-Y, examples of the unsubstituted aryl group having 6 to 12 carbon atoms represented by Y include phenyl and 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 and the like.
When R ₁ , R ₂ and R ₃ and R ₁ , R ₂ and R ₃ are each represented by -X-Y, examples of the unsubstituted arylalkyl group having 7 to 20 carbon atoms represented by Y include benzyl, There may be mentioned phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, ferrocenylmethyl, ferrocenylpropyl and the like.

The 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 above general formula (I), and R ₄ As a halogen atom which substitutes the phenyl group or benzyl group represented by R ₅ , R ₆ , R ₇ , R ₈ and R ₉ , fluorine, chlorine, bromine and iodine can be mentioned,
The _{R 4, R 5, R 6} , R 7, alkyl group having 1 to 4 carbon atoms substituted phenyl group or a benzyl group represented by R ₈ and R _9, methyl, ethyl, propyl, iso- propyl , Butyl, sec-butyl, tert-butyl, iso-butyl and the like.

In the above general formula (I), as a 3- to 6-membered heterocyclic ring which can be formed by linking 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, isoxazolidine ring, isothiazolidine ring, etc. These rings may be fused or substituted with other rings.

In the compounds represented by the above general formula (I), at least two of R ₁ , R ₂ and R ₃ are substituents other than hydrogen atoms.

Examples of the anion represented by An ^{q −} in the above general formula (I) include, as monovalent ions, halide ions such as chloride ion, bromide ion, iodide ion and fluoride ion; Inorganic anions such as acid ion, chlorate ion, thiocyanate ion, hexafluorophosphate ion, hexafluoroantimonate ion and tetrafluoroborate ion; methanesulfonate ion, dodecylsulfonate ion, benzenesulfonate ion, Toluene sulfonate ion, trifluoromethane sulfonate ion, naphthalene sulfonate ion, diphenylamine-4-sulfonate ion, 2-amino-4-methyl-5-chlorobenzene sulfonate ion, 2-amino-5-nitrobenzene sulfonate ion, JP 10-235 999, JP H 0-337959, JP-A-11-102088, JP-A-2000-108510, JP-A-2000-168223, JP-A-2001-209969, JP-A-2001-322354, JP-A-2006-248180, JP-A-2006-297907, JP-A-8- Organic sulfonic acid-based anions such as sulfonic acid ions described in JP-A-253705, JP-A-2004-503379, JP-A-2005-336150, WO2006 / 28006, etc .; octyl phosphate ion, dodecyl phosphate Organophosphate anions such as acid ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphonate ion, bistri Fluoromethylsulfonylimide ion Examples thereof include bisperfluorobutanesulfonylimide ion, perfluoro-4-ethylcyclohexanesulfonic acid ion, tetrakis (pentafluorophenyl) borate ion, tris (fluoroalkylsulfonyl) carbanion and the like, and examples of divalent ones include And benzene disulfonate ion and naphthalene disulfonate ion. In addition, a quencher anion having a function of de-exciting (quenching) an active molecule in an excited state, and ferrocene having an anionic group such as a carboxyl group, a phosphonic acid group or a sulfonic acid group in a cyclopentadienyl ring A metallocene compound anion such as luteothene can also be used if necessary. Also, p is chosen such that the charge is neutral throughout the molecule.

  Examples of the quencher anions described above include, for example, JP-A-60-234892, JP-A-5-43814, JP-A-5-305770, JP-A-6-239028 and JP-A-9-309886. JP-A-9-323478, JP-A-10-45767, JP-A-11-208118, JP-A-2000-168237, JP-A-2002-201373, JP-A-2002-206061, The anion as described in Unexamined-Japanese-Patent No. 2005-297407, Japanese Patent Publication No.7-96334, international publication 98/29257 etc. is mentioned.

As the anion represented by An ^q- in the above general formula (I), a monovalent organic sulfonic acid type anion, bis trifluoromethyl sulfonyl imide ion, bis perfluoro butane sulfonyl imide ion, perfluoro -4- From the viewpoint of heat resistance, ethylcyclohexanesulfonic acid ion, benzenedisulfonic acid ion and naphthalenedisulfonic acid ion are preferable, and bistrifluoromethylsulfonylimide ion is more preferable.

  As specific examples of the cation moiety of the compound represented by the above general formula (I) of the present invention, the following compound Nos. 1 to No. 29 can be mentioned.

Among the compounds represented by the above general formula (I), the following are preferable.
R ₁ , R ₂ and R _{3 each} are, from the viewpoint of heat resistance, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituent represented by —X—Y Is particularly preferable, and any two or more of R ₁ , R ₂ and R ₃ are preferably a halogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.
From the viewpoint of solvent solubility, R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are preferably a hydroxyl-substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.

  Although the manufacturing method of the compound represented by said general formula (I) is not specifically limited, For example, it can manufacture according to the following reaction formula.

（式中、Ｒ₁〜Ｒ₉は、上記一般式（Ｉ）と同じである。）

(Wherein, R _{1 to} R ₉ are the same as in the above general formula (I)).

  In the dye (A) used in the present invention, one or more of the compounds represented by the above general formula (I) can be used in combination, and the total content thereof is preferably 50 to 100% by mass. And more preferably 70 to 100% by mass. When the content of the compound represented by the above general formula (I) of the present invention is less than 50% by mass, the solubility in a solvent may be reduced, or the heat resistance may be reduced.

  In the coloring composition of the present invention, the content of the dye (A) is preferably 0.01 to 50% by mass, more preferably 0.1 to 30% by mass, in the coloring composition of the present invention. When 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, and when it is more than 50% by mass, the colored composition Precipitation of the dye (A) may occur therein.

<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 photosensitive compositions can be used, and examples thereof include ethylene, propylene, butylene and isobutylene. And unsaturated aliphatic hydrocarbons such as vinyl chloride, vinylidene chloride, 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, mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl] phthalate And carboxy groups and hydroxyl groups at both ends of ω-carboxypolycaprolactone mono (meth) acrylate etc. Polymers of mono (meth) acrylate, hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or one carboxyl group and two or more (meth) acryloyl groups Unsaturated polybasic acids such as multifunctional (meth) acrylates; (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, glycidyl (meth) acrylic acid, compound No. 1 below. A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate ( (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 ) Ethyl hexyl acrylate, (meth) acrylic acid Phenoxyethyl, 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 triol (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloyl ethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Polyhydric alcohol or ester of polyhydric phenol; Metal salt of unsaturated polybasic acid such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrofuran Phthalic anhydride-anhydrous Acid anhydride of unsaturated polybasic acid such as leic acid adduct, dodecenyl succinic anhydride, methyl hymic acid anhydride; (meth) acrylamide, methylene bis (meth) acrylamide, diethylene triamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyhydric amines; 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 and biphenyl Unsaturated aromatic compounds such as 2-phenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allylamine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl alcohols such as allyl alcohol, crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; maleimide, N-phenyl maleimide, N -Unsaturated imides such as cyclohexyl maleimide; Indens such as indene and 1-methyl indene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene Macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane; vinyl chloride, vinylidene chloride, divinyls 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 monomers and vinyl epoxy compounds of polyepoxy compounds, hydroxyl group-containing polyfunctional monomers such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate Reactants of polyfunctional isocyanates such as tolylene diisocyanate and hexamethylene diisocyanate; hydroxyl group-containing polyfunctional acrylates such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate; and succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, etc. The polyfunctional acrylate which has an acid value which is a reaction product of a dibasic acid anhydride is mentioned.

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

  In addition, 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 having an alkali-soluble substituent which imparts alkali developability (B The colored photosensitive composition of the present invention becomes a colored alkali-developable photosensitive composition by using (') (hereinafter, also referred to as an alkali-developable compound (B') having an ethylenically unsaturated bond). Examples of the alkali developable compound (B ′) having an ethylenically unsaturated bond include (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) acrylate, 2-ethylhexyl ( (Meth) acrylic esters such as meta) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate; N-vinylpyrrolidone; styrene and derivatives thereof Bodies, styrenes such as α-methylstyrene; (meth) acrylamides, methylol (meth) acrylamides, alkoxy methylol (meth) acrylamides, acrylamides such as diacetone (meth) acrylamides; (meth) acrylonitriles, ethylene, propylene, butylenes, Other vinyl compounds such as vinyl chloride and vinyl acetate, macromonomers such as polymethyl methacrylate macromonomer and polystyrene macromonomer, monomethacrylate of tricyclodecane skeleton, N-phenyl maleimide, methacryloyl oxymethyl 3-ethyl oxetane and the like And a copolymer of (meth) acrylic acid and an isocyanate compound having an unsaturated bond such as Karenz MOI and AOI manufactured by Showa Denko K. K. Novolak epoxy compounds such as copolymers of hydrofluoric acid, phenol and / or cresol novolac epoxy resin, novolac epoxy resin having biphenyl skeleton and naphthalene skeleton, bisphenol A novolac epoxy compound, dicyclopentadiene novolac epoxy compound, and the like Obtained by reacting an unsaturated monobasic acid with an epoxy group such as a polyphenylmethane type epoxy resin having a functional epoxy group, an epoxy compound represented by the following general formula (I), and further causing a polybasic acid anhydride to act Resin can be used. These monomers can be used alone or in combination of two or more. Moreover, it is preferable that the alkali developable compound (B ') which has the said ethylenically unsaturated bond contains 0.2-1.0 equivalent of unsaturated groups.

（式中、Ｘ¹は直接結合、メチレン基、炭素原子数１〜４のアルキリデン基、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（イ）、（ロ）若しくは（ハ）で表される置換基を表し、該アルキリデン基はハロゲン原子で置換されていてもよく、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸及びＲ¹⁹は、それぞれ独立に、水素原子、炭素原子数１〜５のアルキル基、炭素原子数１〜８のアルコキシ基、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、上記アルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されていてもよく、ｒは０〜１０の整数である。）

(Wherein, X ¹ represents 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 (i), (ro) or (ha), and the alkylidene group may be substituted by a halogen atom R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or an alkenyl of 2 to 5 carbon atoms Represents a group 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 to 10.)

（式中、Ｚ¹は、炭素原子数１〜１０のアルキル基若しくは炭素原子数１〜１０のアルコキシ基により置換されてもよいフェニル基、炭素原子数１〜１０のアルキル基若しくは炭素原子数１〜１０のアルコキシ基により置換されてもよい炭素原子数３〜１０のシクロアルキル基、又は、水素原子を表し、Ｙ¹は炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、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、上記Ｙ¹におけるアルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されていてもよく、ｂは０〜５の整数である。）

(Wherein, Z ¹ represents a phenyl group which may be substituted by 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 1 carbon atom And a cycloalkyl group having 3 to 10 carbon atoms which may be substituted by an alkoxy group of 10 to 10, or a hydrogen atom; Y ¹ is an alkyl group having 1 to 10 carbon atoms, an alkoxy having 1 to 10 carbon atoms R2 represents an alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the alkyl group, alkoxy group and alkenyl group in Y ¹ may be substituted by a halogen atom, and b is an integer of 0 to 5; )

（式中、Ｙ²及びＺ²は、それぞれ独立して、ハロゲン原子で置換されてもよい炭素原子数１〜１０のアルキル基、ハロゲン原子で置換されてもよい炭素原子数６〜２０のアリール基、ハロゲン原子で置換されてもよい炭素原子数６〜２０のアリールオキシ基、ハロゲン原子で置換されてもよい炭素原子数６〜２０のアリールチオ基、ハロゲン原子で置換されてもよい炭素原子数８〜２０のアリールアルケニル基、ハロゲン原子で置換されてもよい炭素原子数７〜２０のアリールアルキル基、ハロゲン原子で置換されてもよい炭素原子数２〜２０の複素環基、これらの基を複数組み合わせた基、又はハロゲン原子を表し、上記Ｙ²及びＺ²におけるアルキル基及びアリールアルキル基中のメチレン基は不飽和結合、−Ｏ−又は−Ｓ−で中断されていてもよく、Ｚ²は、隣接するＺ¹²同士で環を形成していてもよく、ｐは０〜４の整数を表し、ｑは０〜８の整数を表し、ｒは０〜４の整数を表し、ｓは０〜４の整数を表し、ｒとｓの数の合計は２〜４の整数である。）

(Wherein, 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, or an aryl having 6 to 20 carbon atoms which may be substituted with a halogen atom Group, an aryloxy group having 6 to 20 carbon atoms which may be substituted with a halogen atom, an arylthio group having 6 to 20 carbon atoms which may be substituted with a halogen atom, the number of carbon atoms which may be substituted with a halogen atom 8-20 arylalkenyl groups, arylalkyl groups having 7 to 20 carbon atoms which may be substituted with halogen atoms, heterocyclic groups having 2 to 20 carbon atoms which may be substituted with halogen atoms, these groups multiple combined group, or a halogen atom, a methylene group of the alkyl group and in the arylalkyl group in the Y ² and Z ² are interrupted by an unsaturated bond, -O- or -S- May have, Z ² may form a ring with the adjacent Z ¹² each other, p represents an integer of 0 to 4, q represents an integer of 0 to 8, r is 0 to 4 integer S represents an integer of 0 to 4, and the sum of the numbers of r and s is an integer of 2 to 4.)

As said unsaturated monobasic acid made to act on the epoxy group of the said epoxy compound, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, a hydroxyethyl methacrylate malate etc. are mentioned. Examples thereof include hydroxyethyl acrylate malate, hydroxypropyl methacrylate malate, hydroxypropyl acrylate malate, dicyclopentadiene malate and the like.
Moreover, as said polybasic acid anhydride made to act after making said unsaturated monobasic acid act, biphenyl tetracarboxylic acid dianhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride are mentioned. , Pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic acid anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride Acid, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2- Dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride Maleic anhydride adduct, dodecenyl succinic anhydride, and anhydride and methyl high Mick acid.

It is preferable that the reaction molar ratio of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride be as follows. That is, in an epoxy adduct having a structure in which 0.1 to 1.0 carboxyl group of the unsaturated monobasic acid is added to one epoxy group of the epoxy compound, the hydroxyl group 1 of the epoxy adduct Preferably, the ratio of the number of acid anhydride structures of the polybasic acid anhydride to the number of pieces thereof is 0.1 to 1.0.
The reaction of the above epoxy compound, the above unsaturated monobasic acid and the above polybasic acid anhydride can be carried out according to a conventional method.

  In order to adjust the acid value and improve the developability of the colored composition of the present invention which is a colored alkali-developable photosensitive composition, a monofunctional or polyfunctional epoxy is further added together with the alkali-developable compound having an ethylenically unsaturated bond. Compounds can be used. The acid value of the solid content of the alkali developable compound having an ethylenically unsaturated bond is preferably in the range of 5 to 120 mg KOH / g, and the amount of use of the monofunctional or polyfunctional epoxy compound satisfies the acid value. It is preferable to select as follows.

  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-vinyl Cyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide; A2, No. A3 etc. are mentioned.

It is preferable to use one or more selected from the group consisting of bisphenol type epoxy compounds and glycidyl ethers as the above-mentioned polyfunctional epoxy compound, since a colored alkaline developable photosensitive composition having better properties can be obtained. As the bisphenol type epoxy compound, in addition to the epoxy compound represented by the above general formula (I), 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, , 10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-tri (g Glycidyl oxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) include methane.
In addition, novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds, etc .; 3,4-epoxy-6-methyl; Alicyclic epoxy such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane and the like Compounds; Glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester; tetraglycidyl diamino acid Glycidyl amines such as phenylmethane, triglycidyl-p-aminophenol, N, N-diglycidyl aniline, etc .; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate; Dioxide compounds such as cyclopentadiene 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), from the viewpoint of compatibility, alkali developability and heat resistance, Unsaturated aliphatic hydrocarbons, unsaturated polybasic acids, polyfunctional acrylates having an acid value, (meth) acrylic esters are preferred, and unsaturated aliphatic hydrocarbons and unsaturated polybasic acids are more preferred.

  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 the content of the present invention. In the coloring composition, 30 to 99% by mass, particularly 60 to 95% by mass is preferable. When the content of the polymerizable compound (B) having an ethylenically unsaturated bond is less than 30% by mass, the mechanical strength of the cured product is insufficient to cause cracking, and when it has alkali developability, development failure occurs. If it is more than 99% by weight, curing by exposure may be insufficient and tack may occur, or if it has alkali developability, development time may be prolonged and cured parts may be damaged by alkali. May.

<Photoinitiator (C)>
As the photopolymerization initiator (C), conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethyl ketal, 1-benzyl- 1-Dimethylamino-1- (4'-morpholinobenzoyl) propane, 2-morpholine-2- (4'-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl Anthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4'-isopropyl) benzoylpropane, 4-butyl Benzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9'-acridinyl) heptane, 9-n-butyl-3,6-bis (2'-morpholinoisobutyroyl) 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-azobisisobutyronitrile, triphenylphosphine, Camphor quinone, benzoyl peroxide and the like can be mentioned, and as commercial products, N-1414, N-1717, N-1919, PZ-4 8, (manufactured by (Corporation) ADEKA Corporation) NCI-831, NCI-930, IRGACURE369, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02 (BASF (Co.) Co., Ltd.).

  Among the above-mentioned photopolymerization initiators (C), 2-morpholine 2- (4'-methylmercapto) benzoylpropane, 9-n-butyl-3,6-bis (2'-morpholino isopyte) in terms of sensitivity and color tone. (Royl) carbazole is preferred, and 2-morpholine 2- (4'-methylmercapto) benzoylpropane is more preferred.

  In the coloring composition of the present invention, the content of the photopolymerization initiator (C) in the coloring composition of the present invention is preferably 0.1 to 30% by mass, and more preferably 0.5 to 10% by mass. When the content of the photopolymerization initiator (C) is less than 0.1% by mass, curing by exposure may be insufficient, and when it is more than 30% by mass, the initiator (C) in the resin composition May precipitate out.

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

As the coloring material (D), dyes or pigments may be used. For example, nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone Compound, isoindoline compound, quinacridone compound, anthrone compound, perinone compound, perylene compound, diketopyrrolopyrrole compound, thioindigo compound, dioxazine compound, triphenylmethane compound, quinophthalone compound, naphthalenetetracarboxylic acid; metal of azo dye, cyanine dye Complex compounds; lake pigments; carbon black obtained by the furnace method, channel method, thermal method, or acetylene black, ketjen black or lamp black Carbon black prepared by coating the above carbon black with an epoxy resin, coated with the carbon black in advance in a solvent, and adsorbed with a resin of 20 to 200 mg / g, acidic or alkaline surface of the carbon black Treated, with an average particle diameter of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, CO in volatiles at 950 ° C., total oxygen amount calculated from CO ₂ 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 micro coil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin, chromium oxide green, miloli blue ,cobalt Cobalt blue, Manganese, Ferrocyanide, Phosphate blue, Ultramarine, Cerulean blue, Pyridian, Emerald green, Lead sulfate, Yellow lead, Zinc yellow, Red iron oxide (red iron oxide (III)), Cadmium red Inorganic pigments or organic pigments such as synthetic iron black and amber can be used.

  Commercially available pigments can also be used as the coloring material (D), 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, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; pigment oranges 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, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 22, 24, 56, 175, 180, 185; 60, 61, 62, 64; pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50 and the like.

  As the coloring material (D), it is also possible to use a known dye. Examples of known dyes include 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, Dyes, such as a phthalocyanine dye and a cyanine dye, etc. are mentioned.

  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 100 parts by mass of the polymerizable compound (B) having the ethylenically unsaturated bond. Is 0 to 250 parts by mass. If it exceeds 350 parts by mass, the light transmittance of the colored composition of the present invention, in particular, the cured product using the colored alkali-developable photosensitive composition, and the color filter for display device is reduced, and the luminance of the display device is reduced. It is not preferable because it

  A solvent can be further added to the coloring composition of the present invention. As the solvent, usually, a solvent capable of dissolving or dispersing each of the above components (the dye (A) and the like comprising the compound of the present invention) as necessary, such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl Ketones such as 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; acetic acid Ester solvents such as methyl, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and texanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Cellosolv solvents such as tellurium; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl Ether ester solvents such as ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate; BTX solvents such as benzene, toluene, xylene and the like; hexane, heptane, octane Aliphatic hydrocarbon solvents such as cyclohexane, terpene hydrocarbon oils such as turpentine oil, D-limonene, pinene, etc .; mineral spirit, swasol # 310 (Cosmo Matsuyama Oil ), Paraffins solvents such as Solvesso # 100 (Exxon Chemical Co., Ltd.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane; chlorobenzene etc. Halogenated aromatic hydrocarbon solvents; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, Water and the like can be mentioned, and these solvents can be used as one or more mixed solvents. 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 compatibility between the resist and the photopolymerization initiator (C) in the coloring composition is good. .

  In the coloring composition of the present invention, the amount of the solvent used is preferably 5 to 30% by mass of the concentration of the composition other than the solvent, and if less than 5% by mass, it is difficult to increase the film thickness. If the desired wavelength light can not be absorbed sufficiently, which is not preferable, and if it is more than 30% by mass, storage stability of the composition due to precipitation of the composition may be reduced, or handling may be reduced because viscosity is improved. There is.

  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; layered clay minerals, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenide, aluminum silicate, calcium silicate, aluminum silicate, aluminum hydroxide, platinum, gold, silver, copper Among these, titanium oxide, silica, layered clay mineral, silver and the like 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 based on 100 parts by mass of the polymerizable compound (B) having the above-mentioned ethylenic unsaturated bond. It is 0.5 to 20 parts by mass, and these inorganic compounds can be used alone or in combination of two or more.

  These inorganic compounds are used, for example, as a filler, an antireflective agent, a conductive agent, a stabilizer, a flame retardant, a mechanical strength improver, a special wavelength absorber, an ink repellent agent, and the like.

  When a pigment and / or an inorganic compound is used in the coloring composition of the present invention, a dispersant can be added. Any dispersant may be used as the dispersant, as long as it can disperse and stabilize pigments and inorganic compounds, and commercially available dispersants such as BYK series manufactured by Bick Chemie Co., Ltd. can be used, and polyesters and polys having a basic functional group Polymer dispersant containing ether, polyurethane, functional group having nitrogen atom as basic functional group and functional group having nitrogen atom is amine and / or its quaternary salt, and having an amine value of 1 to 100 mg KOH / g Is preferably used.

  In the coloring composition of the present invention, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine, etc .; a plasticizer; an adhesion promoter; a filler; Leveling agents; Surface conditioners; Antioxidants; UV absorbers; Dispersion aids; Flocculation inhibitors; Catalysts; Effects accelerators; Crosslinking agents; 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 ethylenic unsaturated bond, and the photopolymerization initiator (C) (however, the coloring material (D) and The content of the solvent (not including the solvent) is appropriately selected according to the purpose of use and is not particularly limited. Preferably, the total content is 100 parts by mass of the polymerizable compound (B) having the ethylenically unsaturated bond. And 50 parts by mass or less.

The colored composition of the present invention improves the properties of the cured product of the colored composition of the present invention by using another organic polymer together with the polymerizable compound (B) having an ethylenically unsaturated bond. It can also be done. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene-(meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Polyester, phenol resin, phenoxy resin, polyamide imide resin, polyamic acid resin, epoxy resin, etc. may be mentioned. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, epoxy resin Masui.
When using another organic polymer, the amount used is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the polymerizable compound (B) having the above-mentioned ethylenic unsaturated bond.

  In the colored 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 further used in combination.

  A sulfur atom-containing compound is generally used as the chain transfer agent or 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-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- 3- Mercapto compounds such as mercapto propionates, Disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acids, iodoacetic acids, iodopropionic acids, 2-iodoethanol, 2-iodoethanesulfonic acid, iodos such as 3-iodopropanesulfonic acid Alkylated compounds, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, tris hydroxyethyl tris thiopropionate, compound No. 1 below. Examples thereof include compounds represented by C1, aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, and Kalens MT BD1, PE1, NR1 manufactured by Showa Denko K. K.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates, 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 above-mentioned silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among them, it has an isocyanate group such as KBE-9007, KBM-502, KBE-403, etc., methacryloyl group or epoxy group A silane coupling agent is preferably used.

Examples of the melamine compound, (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, all or part of the (poly) active methylol groups of the nitrogen compound such as methylol urea (CH ₂ OH groups) Mention may be made of compounds in which (at least two) are alkyletherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group or a butyl group, which may be identical to or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensing 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, alkyletherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.

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

  Moreover, as a light source of the active light used when hardening the coloring composition of this invention, what light-emits the light of wavelength 300-450 nm can be used, For example, super-high pressure mercury, mercury vapor arc, a carbon arc And xenon arc.

  Furthermore, by using a laser beam as an exposure light source, a laser direct writing method of directly forming an image from digital information of a computer or the like without using a mask improves not only productivity but also resolution and positional accuracy. It is useful because it can also be used, and light with a wavelength of 340 to 430 nm is suitably used as the laser light, but the visible to infrared region such as argon ion laser, helium neon laser, YAG laser, and semiconductor laser Are also used. When these lasers are used, sensitizing dyes that absorb light in the visible to infrared region are added.

  The colored composition (or the cured product thereof) of the present invention is a liquid crystal display panel for color display such as a photocurable coating or varnish, a photocurable adhesive, a printed circuit board or a color television, a PC monitor, a portable information terminal, a digital camera In color filters, color filters for CCD image sensors, electrode materials for plasma display panels, powder coatings, printing inks, printing plates, adhesives, dental compositions, stereolithography resins, gel coats, photoresists for electronics, Electroplating resist, etching resist, both liquid and dry film, solder resist, for producing color filters for various display applications or forming structure in manufacturing process of plasma display panel, electric light emitting display and LCD Resists, compositions for encapsulating electrical and electronic components, solders Materials for producing three-dimensional objects by resists, magnetic recording materials, micro mechanical parts, waveguides, optical switches, plating masks, etching masks, color testing systems, glass fiber cable coatings, stencils for screen printing, stereolithography Materials for holographic recording, image recording materials, microelectronics, bleaching materials, bleaching materials for image recording materials, bleaching materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, UV and visible It can be used for various applications such as a photoresist material for a laser direct imaging system, a photoresist material used to form a dielectric layer in successive lamination of printed circuit boards, and a protective film, and the application is not particularly limited.

When the coloring composition of the present invention is a coloring alkali-developable photosensitive composition, it is used for the purpose of forming pixels of a color filter, and in particular for display devices for image display devices such as liquid crystal display panels and organic EL. It is useful as a photosensitive composition for forming a color filter.
Moreover, the color filter for display devices of this invention may have an optical element of red, green, blue, orange, purple and black other than the hardened | cured material of this invention.

The color filter for a display device comprises the steps of: (1) forming a coating of the colored composition of the present invention (in particular, a colored alkali-developable photosensitive composition) on a substrate; (2) forming a predetermined pattern on the coating (3) developing the film after exposure with a developing solution (particularly an alkali developing solution), and (4) heating the film after development. Be done. In addition, the coloring composition of the present invention is also useful as a coloring composition of an ink jet system without transfer and a transfer system.
The production of a color filter for use in a liquid crystal display panel etc. is carried out by repeating the above steps (1) to (4) using the coloring composition of the present invention or other than that, and combining two or more color patterns Can.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited to these examples.

Examples 1-1 to 1-8 are colored alkaline developable photosensitive composition No. 1 which is the colored photosensitive composition of the present invention. 1 to No. The preparation examples of No. 8 are shown, and Comparative Examples 1-1 and 1-2 are comparative colored alkaline developable photosensitive composition No. 1; 1 and No. 1 The preparation example of 2 is shown.
In Evaluation Examples 1-1 to 1-8, Colored Alkali-Developable Photosensitive Composition No. 1 obtained in Examples 1-1 to 1-8. 1 to No. The heat resistance of No. 8 was evaluated, and in Comparative Evaluation Examples 1-1 and 1-2, the comparative colored alkali-developable photosensitive composition No. 1 was obtained in Comparative Examples 1-1 and 1-2. 1 and No. 1 The heat resistance of 2 was evaluated.

[Examples 1-1 to 1-8 and Comparative Examples 1-1 and 1-2] Colored Alkali-Developable Photosensitive Composition No. 1 1 to No. 8 and Comparative Colored Alkali-Developable Photosensitive Composition No. 8 1 and No. 1 Preparation of <Step 1> Preparation of Alkali-Developable Photosensitive Composition As component (B), 30.33 g of ACA Z 251 (manufactured by Daicel-Cytec) and 11.04 g of Alonix M-450 (manufactured by Toagosei Co., ) 1.39 g of Irgacure 907 (manufactured by BASF), 36.60 g of PGMEA as the (E) component and 20.08 g of cyclohexanone, and 0.01 g of FZ 2122 (manufactured by Toray Dow Corning) as the other component. The mixture was stirred until the insoluble matter disappeared to obtain an alkali-developable photosensitive composition.

<Step 2> Dye solution No. 1 to No. 8 and comparative dye solutions No. 1 and No. 1 Preparation of Compound No. 2 as Component (A) 2-No. 4, no. 17, no. 18 and No. 20-No. No. 22, and comparative compound No. 1 and No. 1 To 0.10 g of the bis (trifluoromethanesulfonyl) imide salt of No. 2 and 1.90 g of dimethylacetamide were added and stirred to dissolve, and dye solution No. 1 was added. 1 to No. 8 and comparative dye solutions No. 1 and No. 1 It was 2.

<Step 3> Colored Alkali-Developable Photosensitive Composition No. 1 1 to No. 8 and Comparative Colored Alkali-Developable Photosensitive Composition No. 8 1 and No. 1 Preparation of No. 2 5.0 g of each alkali-developable photosensitive composition obtained in Step 1 and the corresponding No. 1 obtained in Step 2 Each 1.0 g of each dye solution is mixed and stirred until uniform, and then a colored alkali-developable photosensitive composition No. 1 is prepared. 1 to No. 8 and Comparative Colored Alkali-Developable Photosensitive Composition No. 8 1 and No. 1 I got two.

[Evaluation Examples 1-1 to 1-8 and Comparative Evaluation Examples 1-1 to 1-2] Evaluation of Heat Resistance by Firing The colored alkali-developable photosensitive composition No. 1 obtained in Examples 1-1 to 1-8. 1 to No. No. 8 and Comparative Colored Alkali-Developable Photosensitive Composition No. 1 obtained in Comparative Examples 1-1 and 1-2. 1 and No. 1 2 was applied to a glass substrate at 410 rpm × 7 seconds and dried on a hot plate (90 ° C., 90 seconds). The obtained coating film was exposed to light (150 mJ / cm ² ) using an extra-high pressure mercury lamp. The coated film after exposure was fired at 230 ° C. for 30 minutes. The absorbance of the coating before baking (after exposure) and the absorbance of the coating after baking at the maximum absorption wavelength (λmax) of the compound (dye) used were measured, and the absorbance of the coating before baking (after exposure) was 100 It evaluated as relative strength when it was set. The heat resistance is higher as the absorbance of the coating film after firing is closer to 100. In addition, the color difference (ΔE _{ab *} ) before and after firing was examined. 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 Compound No. 2 2 to 4, no. 17, no. 18 and No. 20-No. 22, the comparative compound No. 1 and No. 1 2 Propylene glycol-1-monomethyl ether-2-acetate was added dropwise to 0.1 g of each while stirring, and the concentration when completely dissolved was evaluated as the solubility.

From the above results, in the colored alkaline developable photosensitive composition using the compound according to the present invention as the dye, the compound used as the dye is at the position corresponding to R ₁ , R ₂ and R ₃ in formula (I) Since there are at least two substituents other than hydrogen, the change in color difference is small and the heat resistance is high.
On the other hand, Comparative Compound No. In the colored alkaline developable photosensitive composition in which 1 is used as a dye, the compound used also as a dye has a substituent other than hydrogen at the position corresponding to R ₁ , R ₂ and R ₃ in formula (I) Because it has only one place, it is inferior to heat resistance.
In addition, comparative compound No. The colored alkali-developable photosensitive composition in which 2 is used as a dye, the compound used as a dye has two substituents other than hydrogen at the positions corresponding to R ₁ , R ₂ and R ₃ in formula (I) Although it has a place, it has poor solubility.
Therefore, the colored photosensitive composition of the present invention, which is a colored alkaline developable photosensitive composition using the compound according to the present invention as a dye, is useful for a color filter for display devices.

Claims (6)

A colored photosensitive composition comprising a dye (A) comprising a compound represented by the following general formula (I), a polymerizable compound (B) having an ethylenically unsaturated bond, and a photopolymerization initiator (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 A cyano group, a nitro group, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; A halogen atom-substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms; or a substituent represented by -X-Y, X represents an oxygen atom or a sulfur atom, and Y represents A substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms or a halogen atom; A 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; a halogen atom; a cyano group, a nitro group, a hydroxyl group or a substituted or unsubstituted carbon atom number An alkyl group of 1 to 8; an alkyl group of 1 to 4 carbon atoms, a halogen atom, a phenyl group substituted or unsubstituted with a cyano group or a vinyl group; or an alkyl group of 1 to 4 carbon atoms, a halogen atom R ₄ and R ₅ , R ₆ and R ₇ , and R ₈ and R ₉ are linked together to form a 3- to 6-membered ring hetero It may form a 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 for keeping the charge neutral. ) A colored photosensitive composition comprising a dye (A) comprising a compound represented by the following general formula (I), a polymerizable compound (B) having an ethylenically unsaturated bond, and a photopolymerization initiator (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 A cyano group, a nitro group, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; A halogen atom-substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms; or a substituent represented by -X-Y, X represents an oxygen atom or a sulfur atom, and Y represents A substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms or a halogen atom; A 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; a halogen atom; a cyano group, a nitro group, a hydroxyl group or a substituted or unsubstituted carbon atom number An alkyl group of 1 to 8; an alkyl group of 1 to 4 carbon atoms, a halogen atom, a phenyl group substituted or unsubstituted with a cyano group or a vinyl group; or an alkyl group of 1 to 4 carbon atoms, a halogen atom R ₄ and R ₅ , R ₆ and R ₇ , and R ₈ and R ₉ are linked together to form a 3- to 6-membered ring hetero It may form a ring,
Provided that at least one of R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ is substituted or unsubstituted with a cyano group, a nitro group, a hydroxyl group or a halogen atom; 8 alkyl groups,
At least two or more 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 for keeping the charge neutral. ) The following compound No. Compound No. 1 2, the compound No. 4, the compound No. 17, the compound No. 20, the compound No. No. 21 and compound no. The coloring photosensitive composition containing 1 or more types of dye (A) selected from the group which consists of 22, a polymeric compound (B) which has an ethylenically unsaturated bond, and a photoinitiator (C).

Furthermore colorant (excluding dye comprising a compound represented by the following general formula (I)) The colored photosensitive composition according to any one of claims 1-3 containing one or more (D) of object.

(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 A cyano group, a nitro group, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; A halogen atom-substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms; or a substituent represented by -X-Y, X represents an oxygen atom or a sulfur atom, and Y represents A substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms or a halogen atom; A 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; a halogen atom; a cyano group, a nitro group, a hydroxyl group or a substituted or unsubstituted carbon atom number An alkyl group of 1 to 8; an alkyl group of 1 to 4 carbon atoms, a halogen atom, a phenyl group substituted or unsubstituted with a cyano group or a vinyl group; or an alkyl group of 1 to 4 carbon atoms, a halogen atom R ₄ and R ₅ , R ₆ and R ₇ , and R ₈ and R ₉ are linked together to form a 3- to 6-membered ring hetero It may form a 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 for keeping 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 A cyano group, a nitro group, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; A halogen atom-substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms; or a substituent represented by -X-Y, X represents an oxygen atom or a sulfur atom, and Y represents A substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms or a halogen atom; A 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; a halogen atom; a cyano group, a nitro group, a hydroxyl group or a substituted or unsubstituted carbon atom number An alkyl group of 1 to 8; an alkyl group of 1 to 4 carbon atoms, a halogen atom, a phenyl group substituted or unsubstituted with a cyano group or a vinyl group; or an alkyl group of 1 to 4 carbon atoms, a halogen atom R ₄ and R ₅ , R ₆ and R ₇ , and R ₈ and R ₉ are linked together to form a 3- to 6-membered ring hetero It may form a ring,
Provided that at least one of R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ is substituted or unsubstituted with a cyano group, a nitro group, a hydroxyl group or a halogen atom; 8 alkyl groups,
At least two or more 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 for keeping the charge neutral. )   A cured product of the colored photosensitive composition according to any one of claims 1 to 4.   A color filter for a display device, comprising at least a part of the cured product according to claim 5.