TWI652315B - Novel compounds and color-sensitive photosensitive compositions - Google Patents

Abstract

The present invention provides a novel compound which is excellent in solvent resistance and heat resistance and which is excellent in waveform controllability in a light absorption spectrum, is suitable for dyes, and a color-sensitive photosensitive composition using the compound (dye) (colored alkali-developed photosensitive light) a composition) and a color filter which is a compound represented by the following formula (1), wherein one or both of R ⁴ and R ⁷ in the formula (1) are a hydroxyl group or a halogen atom, Or a compound having 1 to 8 carbon atoms substituted by a halogen atom or an alkoxy group having 1 to 8 carbon atoms which may be substituted by a halogen atom is used as a dye.

The specific content of the general formula (1) is as described in the present specification.

Description

Novel compounds and color-sensitive photosensitive compositions

The present invention relates to a novel compound suitable for dyes which is designed to have a desired hue, has good properties as a light absorbing agent, and has improved heat resistance. Further, the present invention relates to a colored photosensitive composition which can be polymerized by an energy ray using the dye, and a color filter using the colored photosensitive composition.

A compound having a strong absorption for a specific light can be used as a recording layer of an optical recording medium such as CD-R, DVD-R, DVD+R, BD-R, or a liquid crystal display device (LCD) or a plasma display panel ( Optical elements of an image display device such as a PDP), an electroluminescent display (ELD), a cathode tube display device (CRT), a fluorescent display tube, and a field emission display.

Optical filter for image display devices such as liquid crystal display (LCD), plasma display panel (PDP), electroluminescent display (ELD), cathode tube display (CRT), fluorescent display tube, field emission display, etc. In the sheet, various compounds which absorb light of a wavelength of 300 to 1100 nm can be used as a light absorber. For such light absorbing agents, it is required that the light absorption is particularly impatient, that is, the half value width of λmax is small, and the waveform controllability is excellent, and the function is not lost due to light or heat.

Optical filters used in liquid crystal display devices (LCDs) mainly have color filters. Color filters usually use three primary colors of RGB. If it is a separate color material, it is difficult to have a pure RGB hue. Therefore, efforts have been made to use a plurality of color materials to approach a pure RGB hue. Therefore, yellow, orange, purple, and the like are also required instead of RGB.

The light absorber used in the color filter is used according to the heat resistance. Organic and/or inorganic pigments, but because of the pigment, there is a problem that the brightness of the display device is lowered, and the problem has been solved by increasing the brightness of the light source. However, with the trend of low power consumption, the development of color filters using dyes has become popular.

In addition, in the color filter used in the solid-state imaging device, in order to improve the image quality, the coloring pattern is required to be thinned, and in order to achieve thinning, it is necessary to increase the dye concentration in terms of color density. . Moreover, in the case where the molar absorption coefficient of the dye is low, a large amount of dye must also be added.

However, if the dye concentration is increased, there is a problem in that the pigment is eluted or precipitated from the formed pixel after film formation, or in the case of performing heat treatment (post-baking) after film formation, in the case of adjacent pixels or in a laminated structure. It is easy to produce color mixture between the upper and lower layers.

Patent Document 1 discloses a dye monomer and a polymer thereof, and Patent Document 2 discloses a hologram recording material containing a polymer having a polymerizable group, and Patent Document 3 discloses a dye containing a polymerizable group. In the two-photon light-absorbing recording material, Patent Document 4 discloses a photosensitive coloring composition containing a triarylmethane-based coloring matter monomer having an anionic polymerizable group. However, the compound having a polymerizable group described in these documents is not satisfactory in terms of solvent resistance and heat resistance.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. Hei 11-246627

Patent Document 2: US Patent Publication No. 2007/070481

Patent Document 3: US Patent Publication No. 2009/088490

Patent Document 4: Japanese Patent No. 4266627

Therefore, an object of the present invention is to provide a novel compound which is excellent in solvent resistance and heat resistance and which is excellent in waveform controllability in a light absorption spectrum and is suitable for a dye. Again, this Another object of the invention is to provide a coloring photosensitive composition (colored alkali-developable photosensitive composition) using the above dye. Moreover, another object of the present invention is to provide an optical filter using the above colored photosensitive composition (colored alkali-developable photosensitive composition), and more particularly to provide an image suitable for a liquid crystal display panel without lowering the brightness. A color filter for the display device.

As a result of intensive studies, the inventors of the present invention have obtained the following findings: a compound having a specific structure is excellent in heat resistance, and is excellent in solvent resistance in a coloring photosensitive composition (colored alkali-developable photosensitive composition), and is light-absorbing. The coloring photosensitive composition (coloring alkali-developing photosensitive composition) does not lower the brightness of an optical filter (especially a color filter), and is suitable for an image such as a liquid crystal display panel. The color filter is used for the display device; thereby achieving the present invention.

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

(wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a halogen atom, or represent a cyano group or a nitro group; a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a halogen or a halogen atom, or a substituted or unsubstituted alkoxy group having 1 to 8 carbon atoms, substituted or unsubstituted by a halogen atom An aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms substituted or unsubstituted by a halogen atom, an arylthio group having 6 to 20 carbon atoms substituted or unsubstituted by a halogen atom, An aralkenyl group having 8 to 20 carbon atoms which is substituted or unsubstituted by a halogen atom, or an aralkyl group having 7 to 20 carbon atoms which is substituted or unsubstituted by a halogen atom, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group or a nitro group, or a nitro group, a carboxyl group, a sulfonic acid group, a hydroxyl group or a halogen atom, or a carboxyl group ester or a sulfonate. a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a halogen atom, and a cyanogen group, a salt of an acid group, a salt of a carboxyl group or a salt of a sulfonic acid group. a phenyl group substituted with a vinyl group, a nitro group, a carboxyl group, a sulfonic acid group or a hydroxy group, or a salt of a carboxyl group, an ester of a sulfonic acid group, a salt of a carboxyl group or a salt of a sulfonic acid group, and a number of carbon atoms 1 to 4 alkyl, halogen atom, cyano group, vinyl group, nitro group, carboxyl group, sulfonic acid group or hydroxy group, or substituted with an ester of a carboxyl group, an ester of a sulfonic acid group, a salt of a carboxyl group or a salt of a sulfonic acid group Or unsubstituted benzyl; R ¹ and R ¹¹ , R ² and R ¹² , R ⁵ and R ¹³ , R ⁶ and R ¹⁴ , R ⁹ and R ¹⁵ and R ¹⁰ and R ¹⁶ may be bonded to form a 6-membered ring. R ¹¹ and R ¹² , R ¹³ and R ¹⁴ and R ¹⁵ and R ¹⁶ may be bonded to form a heterocyclic ring of 3 to 6 membered rings, and R ³ and R ⁴ and R ⁷ and R ⁸ may be via a single bond, an oxygen atom, A sulfur atom, a selenium atom, CR ¹⁷ R ¹⁸ , CO, NR ¹⁹ , PR ²⁰ or SO _{2 are} bonded to form a ring, and X represents a single bond, an oxygen atom, a sulfur atom, a selenium atom, CR ¹⁷ R ¹⁸ , CO, NR ¹⁹ , PR ²⁰ or SO ₂ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom-substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or substituted or unsubstituted by a halogen atom. number of carbon atoms of the alkoxy group having 1 to 8, An ^q- represents a q The anion, q represents 1 or 2, p represents the neutral charge retention coefficient; ^{wherein, R 11, R 12, R} 13, R 14, R ¹⁵ and R ¹⁶ to any one of a hydrogen atom become more) and, according to the present The present invention provides a coloring photosensitive composition comprising a dye (A) containing the above compound, a polymerizable compound (B) having an ethylenically unsaturated bond, and a photopolymerization initiator (C).

Moreover, the present invention provides a cured product of the colored photosensitive composition and a color filter for a display device in which at least a part of the colored photosensitive composition is provided.

The compound of the present invention is excellent in solvent resistance and heat resistance, and is excellent in wave controllability in a light absorption spectrum, and is suitable as a dye. In addition, the coloring photosensitive composition (colored alkali-developable photosensitive composition) which is a dye of the present invention is suitable as a color filter of an image display device such as a liquid crystal display panel without lowering the brightness.

Fig. 1 is a ¹ H-NMR chart showing the compound No. 13 which is a compound of the present invention synthesized in Example 1.

Fig. 2 is a ¹ H-NMR chart showing the compound No. 25 which is a compound of the present invention synthesized in Example 1.

Fig. 3 is a ¹ H-NMR chart showing the compound No. 26 which is a compound of the present invention synthesized in Example 1.

Fig. 4 is a ¹ H-NMR chart showing the compound No. 35 which is a compound of the present invention synthesized in Example 1.

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

The present invention is a novel compound represented by the above formula (I).

In the compound represented by the above formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a halogen atom. Or an alkyl group having 1 to 8 carbon atoms which is substituted or unsubstituted by a cyano group, a nitro group, a hydroxyl group or a halogen atom, and an alkoxy group having 1 to 8 carbon atoms which is substituted or unsubstituted by a halogen atom. a halogen atom-substituted or unsubstituted aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms substituted or unsubstituted by a halogen atom, or a carbon atom substituted or unsubstituted by a halogen atom An arylthio group of 6 to 20, an aralkenyl group having 8 to 20 carbon atoms which is substituted or unsubstituted by a halogen atom, or an aralkyl group having 7 to 20 carbon atoms which is substituted or unsubstituted by a halogen atom.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogen atoms in the following description are also identical.

Examples of the unsubstituted alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a tert-butyl group, an isobutyl group, and a pentyl group. , isoamyl, third amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, third geng Base, 1-octyl, isooctyl, third octyl, and the like.

The alkyl group having 1 to 8 carbon atoms which is substituted by a cyano group, a nitro group, a hydroxyl group or a halogen atom, and a part or all of the hydrogen atoms in the alkyl group having 1 to 8 carbon atoms are selected from a cyano group. a group substituted with one or more of a nitro group, a hydroxyl group or a halogen atom.

Examples of the unsubstituted alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, a second butoxy group, a third butoxy group, and an isobutyl group. Oxyl, pentyloxy, isopentyloxy, third pentyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy Base, 2-heptyloxy, 3-heptyloxy, isoheptyloxy, third heptyloxy, 1-octyloxy, isooctyloxy, third octyloxy and the like.

Examples of the alkoxy group having 1 to 8 carbon atoms which are substituted by a halogen atom include the above carbons. A group in which one or all of the hydrogen atoms in the alkoxy group having 1 to 8 atoms are substituted with a halogen atom.

Examples of the unsubstituted aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.

The aryl group having 6 to 20 carbon atoms which is substituted by a halogen atom may, for example, be a group in which one or all of the hydrogen atoms in the unsubstituted aryl group having 6 to 20 carbon atoms are substituted with a halogen atom.

Examples of the unsubstituted aryloxy group having 6 to 20 carbon atoms include a phenoxy group and a naphthyloxy group.

The aryloxy group having 6 to 20 carbon atoms which is substituted by a halogen atom may, for example, be a group in which one or all of the hydrogen atoms in the unsubstituted aryloxy group having 6 to 20 carbon atoms are substituted with a halogen atom.

Examples of the unsubstituted arylthio group having 6 to 20 carbon atoms include a phenylthio group and a naphthylthio group.

The arylthio group having 6 to 20 carbon atoms which is substituted by a halogen atom may, for example, be a group in which one or all of the hydrogen atoms in the unsubstituted arylthio group having 6 to 20 carbon atoms are substituted with a halogen atom.

Examples of the unsubstituted aralkenyl group having 8 to 20 carbon atoms include a benzyl group, a phenethyl group, a diphenylmethyl group, and a trityl group.

The aralkenyl group having 8 to 20 carbon atoms which is substituted by a halogen atom may, for example, be a group in which one or all of the hydrogen atoms in the unsubstituted arylalkenyl group having 8 to 20 carbon atoms are substituted with a halogen atom.

Examples of the unsubstituted aralkyl group having 7 to 20 carbon atoms include a styryl group and a phenylallyl group.

The aralkyl group having 7 to 20 carbon atoms which is substituted by a halogen atom may be a part or all of a hydrogen atom in the unsubstituted aralkyl group having 7 to 20 carbon atoms. The base of the atom substitution.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group or a nitro group, or represent a nitro group, a carboxyl group, a sulfonic acid group, a hydroxyl group or a halogen atom. a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms which is substituted or unsubstituted with a carboxyl group ester, an ester of a sulfonic acid group, a salt of a carboxyl group or a salt of a sulfonic acid group, and an alkyl group having 1 to 4 carbon atoms. a phenyl group substituted with a halogen atom, a cyano group, a vinyl group, a nitro group, a carboxyl group, a sulfonic acid group or a hydroxy group, or a salt of a carboxyl group, an ester of a sulfonic acid group, a salt of a carboxyl group or a salt of a sulfonic acid group. , substituted by an alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, a vinyl group, a nitro group, a carboxyl group, a sulfonic acid group or a hydroxyl group, or an ester of a carboxyl group, an ester of a sulfonic acid group, a salt of a carboxyl group or a sulfonate. A benzyl group substituted or unsubstituted with a salt of an acid group.

Here, any one or more of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ must be a hydrogen atom.

Examples of the unsubstituted alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a third butyl group, an isobutyl group, and a pentyl group. Isoamyl, third amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, third heptyl , 1-octyl, isooctyl, third octyl, and the like.

Some or all of the above alkyl groups may be substituted by a nitro group, a carboxyl group, a sulfonic acid group, a hydroxyl group or a halogen atom, or may be substituted by a carboxyl group ester, an sulfonic acid group ester, a carboxyl group salt or a sulfonic acid group salt. .

Examples of the ester of a carboxyl group include esters having 1 to 4 carbon atoms such as methyl ester, ethyl ester, isopropyl ester and butyl ester.

Examples of the salt of a carboxyl group or a salt of a sulfonic acid group include an alkali metal salt such as a lithium salt, a sodium salt or a potassium salt; and an amine salt such as an ammonium salt, an ethanolamine salt, a diethanolamine salt or a triethanolamine salt.

Some or all of the above phenyl and benzyl groups may be substituted by a halogen atom, a cyano group, a vinyl group, a nitro group, a carboxyl group or a sulfonic acid group, or may be an ester of a carboxyl group, an ester of a sulfonic acid group, a salt of a carboxyl group or a sulfonic acid group. Substituted by the salt. Examples of the ester and the salt include the above examples.

R ¹ and R ¹¹ , R ² and R ¹² , R ⁵ and R ¹³ , R ⁶ and R ¹⁴ , R ⁹ and R ¹⁵ and R ¹⁰ and R ¹⁶ may be bonded to form a 6-membered ring, R ¹¹ and R ¹² , R ¹³ and R ¹⁴ and R ¹⁵ and R ¹⁶ may be bonded to form a heterocyclic ring of 3 to 6 membered rings, and R ³ and R ⁴ and R ⁷ and R ⁸ may be via a single bond, an oxygen atom, a sulfur atom, a selenium atom, or CR ¹⁷ R ¹⁸ , CO, NR ¹⁹ , PR ²⁰ or SO _{2 are} bonded to form a ring.

Examples of the 6-membered ring which can be formed by the above-mentioned connection include a piperidine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, and an isoquinoline ring, and the heterocyclic ring of the 3 to 6 membered ring which can be formed as described above. Can be enumerated: piperidine ring, pipe Ring, pyrrolidine ring, Porphyrin ring, thio Chloride ring, pyridine ring, pyridyl Ring, pyrimidine ring, quinoline ring, isoquinoline ring, imidazole ring, Oxazole ring, imidazolidinium ring, pyrazolidine ring, different Zolidine ring, isotetrahydrothiazole ring and the like. The 6-membered ring or heterocyclic ring may also be condensed or substituted with other rings.

X represents a single bond, an oxygen atom, a sulfur atom, a selenium atom, CR ¹⁷ R ¹⁸ , CO, NR ¹⁹ , PR ²⁰ or SO ₂ , and R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom and a halogen atom. a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms substituted or unsubstituted by a halogen atom, as an unsubstituted alkyl group having 1 to 8 carbon atoms An alkyl group having 1 to 8 carbon atoms substituted by a halogen atom, an alkoxy group having 1 to 8 carbon atoms which are not substituted, or an alkoxy group having 1 to 8 carbon atoms substituted by a halogen atom, List the above examples.

In the above formula (I), pAn ^q- represents an anion of q valence, q represents 1 or 2, and p represents a coefficient which maintains a charge neutral. Examples of the anion represented by An ^q- include, for example, a halide ion such as a chloride ion, a bromide ion, an iodide ion or a fluoride ion; a perchlorate ion, a chlorate ion, and a thiocyanate; An inorganic anion such as an acid ion, a hexafluorophosphate ion, a hexafluoroantimonate ion or a tetrafluoroborate ion; a mesylate ion, a dodecylsulfonate ion, a benzenesulfonate ion, a tosylate ion, and a trifluoro Methanesulfonate ion, naphthalenesulfonate ion, diphenylamine-4-sulfonate ion, 2-amino-4-methyl-5-chlorobenzenesulfonate ion, 2-amino-5-nitrobenzenesulfonate Acid ion, phthalocyanine sulfonate ion, sulfonate ion having a polymerizable substituent, Japanese Patent Laid-Open No. Hei 10-235999, Japanese Patent Laid-Open No. Hei 10-337959, Japanese Patent Laid-Open No. Hei 11-102088, Japanese Patent Laid-Open No. 2000-108510 Japanese Patent Laid-Open No. 2000-168223, Japanese Patent Laid-Open No. 2001-209969, Japanese Patent Laid-Open No. 2001-322354, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. , Japanese Patent Special Table 2004- An organic sulfonic acid anion such as a sulfonate ion disclosed in Japanese Laid-Open Patent Publication No. 2005-336150, and the International Publication No. 2006/28006, etc.; an octyl phosphate ion, a dodecyl phosphate ion, and ten Organic phosphate such as octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2'-methylenebis(4,6-di-t-butylphenyl)phosphonate ion Anion; bistrifluoromethylsulfonimide ion, bisperfluorobutanesulfonimide ion, perfluoro-4-ethylcyclohexanesulfonate ion, tetrakis(pentafluorophenyl)borate ion, tris(fluorine) Examples of the divalent ones include a benzenedisulfonate ion and a naphthalene disulfonate ion.

Further, it may be used as needed: a quenching anion having a function of de-exciting (quenching) an active molecule in an excited state, or an anion having a carboxyl group or a phosphonic acid group or a sulfonic acid group on the cyclopentadienyl ring. An anion such as a metallocene compound such as ferrocene or ferrocene.

Further, p is selected such that the charge of the entire molecule becomes neutral.

The above-mentioned quenching anion is exemplified by, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. ,Japanese Patent Special Open 9-309886 Japanese Laid-Open Patent Publication No. Hei 9-323478, Japanese Patent Laid-Open No. Hei 10-45767, Japanese Patent Laid-Open No. Hei 11-208118, Japanese Patent Laid-Open No. 2000-168237, and Japanese Patent Laid-Open No. 2002-201373 An anion disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 2002-206061, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

The anion represented by An ^q- in the above formula (I) is preferably a monovalent organic sulfonic acid anion, a bistrifluoromethylsulfonimide ion, or a diperfluorocarbon in terms of heat resistance. Butasulfonium iodide ion, perfluoro-4-ethylcyclohexanesulfonate ion, benzenedisulfonate ion, naphthalene disulfonate ion, and further preferably bistrifluoromethylsulfonimide ion.

Among the compounds represented by the above formula (I), the following is preferable in terms of excellent wave controllability in the light absorption spectrum.

That is, it is preferred that either or both of R ⁴ and R ⁷ are a hydroxyl group, a halogen atom, an alkyl group having 1 to 8 carbon atoms substituted by a halogen atom, or a carbon atom number 1 to 8 which may be substituted by a halogen atom. The alkoxy group is more preferably a halogen atom, an alkyl group having 1 to 8 carbon atoms which is substituted by a halogen atom, and further preferably a halogen atom.

The group other than the hydrogen atom of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is preferably a polar group, particularly a hydroxy group substituted or unsubstituted carbon atom, in terms of solvent solubility. A number of 1 to 8 alkyl groups.

As X, an oxygen atom or a sulfur atom is preferred in terms of ease of availability.

Specific examples of the cationic moiety of the compound represented by the above formula (I) of the present invention include the following compounds No. 1 to No. 36.

The method for producing the compound represented by the above formula (I) is not particularly limited. For example, when X in the above formula (I) is an oxygen atom, it can be produced according to the following reaction formula.

Further, when X is other than an oxygen atom, it may be produced according to the following production method. Further, it can also be produced according to a known method described in Journal of Organic Chemistry (2009), 74 (8), and 3183-3185.

(wherein R ¹ to R ¹⁶ , An ^q- , p and q are the same as the above formula (I))

The compound represented by the above formula (I) can be used as an optical filter for use in a display or an optical lens, a photosensitive material for silver salt photography, and the like, in addition to the color-developing photosensitive composition described below. Dyestuffs, coatings, optical recording pigments, etc.

Next, the colored photosensitive composition of the present invention will be described. In the following description, the colored photosensitive composition or the following colored alkali-developable composition is referred to as a colored composition as appropriate.

The colored photosensitive composition of the present invention contains: a dye (A) (hereinafter also referred to as dye (A)) containing a compound of the present invention, and a polymerizable compound (B) having an ethylenically unsaturated bond (including having an alkali-developing property) a base soluble substituent, a polymerizable compound (B') having an ethylenically unsaturated bond, and a photopolymerization initiator (C), if necessary, a color material (excluding the above formula (I) One or more (D) of the dyes of the compounds indicated.

The dye (A) used in the present invention may be used singly or in combination of plural kinds as long as it contains at least one compound of the present invention. Further, as the dye (A), a known dye other than the compound of the present invention can be used. Examples of known dyes include azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, dibenzopyran dyes, alizarin dyes, acridine dyes, anthraquinone dyes, thiazole dyes, and naphthol dyes. Quinoline dye, nitro dye, indamine dye, Dyes, phthalocyanine dyes, dyes such as cyanine dyes, etc., may be used in combination.

In the dye (A) used in the present invention, the content of the compound of the present invention is preferably from 50 to 100% by mass, more preferably from 70 to 100% by mass. When the content of the compound of the present invention is less than 50% by mass, the solubility in the solvent may be lowered or the heat resistance may be lowered.

In the coloring composition of the present invention, the content of the dye (A) is preferably from 0.01 to 50% by mass, more preferably from 0.1 to 30% by mass, based on the coloring composition of the present invention. When the content of the dye (A) is less than 0.01% by mass, there is a case where the cured product of the coloring composition of the present invention cannot obtain a color of a desired concentration, and if it is more than 50% by mass, the dye (A) is caused to be colored in combination. The situation of precipitation.

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

The polymerizable compound (B) having an ethylenically unsaturated bond is not particularly limited, and those used in the photosensitive composition can be used, and examples thereof include ethylene, propylene, butylene, isobutylene, and vinyl chloride. Unsaturated aliphatic hydrocarbons such as vinylidene chloride, vinylidene fluoride and tetrafluoroethylene; (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, methyl maleic acid, and anti Butenedioic acid, bicycloheptene dicarboxylic acid, crotonic acid, methacrylic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, hexadienoic acid, methyl fumaric acid, succinic acid mono [2-(methyl) ) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene methoxyethyl] ester, ω-carboxy polycaprolactone mono (meth) acrylate equivalent to carboxyl group at both ends Mono(meth) acrylate, hydroxyethyl (meth) acrylate, maleate, hydroxypropyl (meth) acrylate, maleate, dicyclopentane Alkene/maleate or polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acrylonitrile groups And polybasic acid; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, the following compounds No.A1~No.A4, (A) Methyl acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate , isooctyl (meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, (methyl) ) dimethylaminomethyl acrylate, dimethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, dimethyl aminopropyl (meth) acrylate, (methyl) Ethoxyethyl acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, (meth)acrylic acid Phenoxyethyl ester, tetrahydrofuran (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylic acid , triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1 ,6-hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate , dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, isocyanuric acid three [(A Unsaturated monobasic acid such as acrylamidoethyl]ester or polyester (meth) acrylate oligomer, and ester of polyhydric or polyphenol; zinc (meth) acrylate, magnesium (meth) acrylate, etc. a saturated polybasic acid metal salt; maleic anhydride, itaconic anhydride, methyl maleic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydroortylene Dicarboxylic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-cis Adicarboxylic anhydride adduct, ten An acid anhydride of an unsaturated polybasic acid such as a vinyl succinic anhydride or a methyl biscycloheptylene dimethyl anhydride; (meth) acrylamide, methylene bis(methyl) acrylamide, diethylene triamine Unsaturated monobasic acids and polyamines such as (meth)acrylamide, benzyldimethyl(meth)acrylamide, α-chloropropenylamine, N-2-hydroxyethyl(meth)acrylamide Anthracene; unsaturated aldehyde such as acrolein; unsaturated nitrile such as (meth)acrylonitrile, α-chloroacrylonitrile, dicyanethylene, allyl cyanide; styrene, 4-methylstyrene , 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, Unsaturated aromatic compound such as 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether or vinylbenzyl glycidyl ether; unsaturated ketone such as methyl vinyl ketone; vinylamine, allylamine, N-vinylpyrrole An unsaturated amine compound such as ketone or vinyl piperidine; vinyl alcohol such as allyl alcohol or crotyl alcohol; vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl ethylene a vinyl ether such as allyl glycidyl ether; an unsaturated quinone imine such as maleimide, N-phenyl maleimide or N-cyclohexylmethyleneimine; Anthraquinones such as hydrazine and 1-methylhydrazine; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, poly(methyl) methacrylate, Poly(meth)acrylate n-butyl ester, polyoxyalkylene oxide is equivalent to a macromonomer having a mono(meth)acrylonitrile group at the end of the polymer molecular chain; vinyl chloride, vinylidene chloride, divinyl succinate , diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl sulfide, vinyl imidazole, vinyl Oxazoline, vinylcarbazole, vinylpyrrolidone, vinylpyridine, vinyl urethane compound of hydroxyl group-containing vinyl monomer and polyisocyanate compound, hydroxyl group-containing vinyl monomer and polyepoxy a reaction of a vinyl epoxy compound of a compound, a hydroxyl group-containing polyfunctional acrylate such as pentaerythritol triacrylate or dipentaerythritol pentaacrylate with a polyfunctional isocyanate such as toluene diisocyanate or hexamethylene diisocyanate, as pentaerythritol triacrylate A reaction product of a hydroxyl group-containing polyfunctional acrylate such as dipentaerythritol pentaacrylate and a dibasic acid anhydride such as succinic anhydride, phthalic anhydride or tetrahydrophthalic anhydride, and having a polyfunctional acrylate having an acid value.

These polymerizable compounds may be used singly or in combination of two or more kinds. When two or more kinds are used in combination, these may be used in advance as a copolymer.

Further, in the coloring composition of the present invention, a polymerizable compound (B') having an ethylenically unsaturated bond having an alkali-soluble substituent imparting alkali developability is used (hereinafter, also referred to as having an ethylenically unsaturated bond) The alkali-developable compound (B')) is a coloring alkali-developable photosensitive composition of the present invention. As the alkali-developable compound (B') having an ethylenically unsaturated bond, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, or propyl (meth)acrylate can be used. , isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid Phenyl ester, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylic acid (meth)acrylates such as esters, 2-hydroxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate; N-vinylpyrrolidone; styrene and its derivatives, α-methyl Styrene such as styrene; (meth) acrylamide, hydroxymethyl (meth) acrylamide, alkoxy hydroxymethyl (meth) acrylamide, diacetone (meth) acrylamide, etc. Acrylamides; other vinyl compounds such as (meth)acrylonitrile, ethylene, propylene, butylene, vinyl chloride, vinyl acetate, and polymethyl methacrylate macromonomers, polystyrene macromonomers, etc. Monomeric, tricyclodecane skeleton monomethacrylate, N-phenyl maleimide, methacryloxymethyl-3-ethyloxetane, etc. Copolymer of acrylic acid and a copolymer of (meth)acrylic acid obtained by reacting the isocyanate compound having an unsaturated bond such as KARENZ MOI or AOI manufactured by Showa Denko Co., Ltd., or phenol And/or cresol novolac epoxy resin, novolak epoxy resin having biphenyl skeleton, naphthalene skeleton, bisphenol A novolac epoxy compound, A novolac type epoxy compound such as a dicyclopentadiene novolak type epoxy compound, a polyphenylmethane type epoxy resin having a polyfunctional epoxy group, an epoxy compound represented by the following formula (II), or the like A resin obtained by reacting an epoxy group with an unsaturated monobasic acid and further with a polybasic acid anhydride. These monomers may be used alone or in combination of two or more. Further, the alkali-developable compound (B') having an ethylenically unsaturated bond preferably contains 0.2 to 1.0 equivalent of an unsaturated group.

(wherein X ¹ represents a direct bond, a methylene group, an alkylene 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), which may be substituted by a halogen atom, R ³¹ , R ³² , R ³³ and R ³⁴ 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 above alkyl group , alkoxy and alkenyl may be substituted by a halogen atom, m is an integer from 0 to 10)

(wherein Y ² 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 a carbon number of 1 a cycloalkyl group having 3 to 10 carbon atoms or a hydrogen atom substituted by an alkoxy group of ~10, Y ¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon atom 2 to 10 alkenyl or halogen atom, the alkyl group, alkoxy group and alkenyl group of the above Y ¹ may be substituted by a halogen atom, and b is an integer of 0 to 5)

(wherein Y ³ and Y ⁴ each independently represent an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted by a halogen atom, and may be substituted by a halogen atom; An aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms which may be substituted by a halogen atom, an aralkenyl group having 8 to 20 carbon atoms which may be substituted by a halogen atom, may be substituted by a halogen atom number of carbon atoms of the aralkyl group having 7 to 20, carbon atoms and may be substituted with a halogen atom heterocyclic group of 2 to 20, the plurality of kinds of the combination of group such group, or a halogen atom, Y ³ and Y above ⁴ alkyl group and aralkyl group of the methylene group may be an unsaturated bond, -O- or -S- is interrupted, the adjacent ⁴ Y Y ⁴ may form a ring, n-represents an integer of 0 to 4, q represents An integer from 0 to 8, r represents an integer from 0 to 4, s represents an integer from 0 to 4, and the sum of the numbers of r and s is an integer from 2 to 4.

The unsaturated monobasic acid which acts on the epoxy group of the above epoxy compound may, for example, be acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, hexadienoic acid, hydroxyethyl methacrylate or maleate. Wait. Examples thereof include hydroxyethyl acrylate/maleate, hydroxypropyl methacrylate ‧ maleate, hydroxypropyl acrylate ‧ maleate, dicyclopentadiene ‧ butene Diacid esters and the like.

Further, examples of the polybasic acid anhydride which acts by the action of the unsaturated monobasic acid include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, and partial Pyromellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic anhydride, ethylene glycol double-dehydrated trimellitate, glycerol tri-dehydrated trimellitate, Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, acid anhydride, methylic acid anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5-( 2,5-dioxotetrahydrofuranyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, Dodecenyl succinic anhydride, methyl bicycloheptylene anhydride, and the like.

The reaction molar of the above epoxy compound, the above unsaturated monobasic acid and the above polybasic acid anhydride is preferably as follows. That is, in the epoxy adduct having a structure in which 0.1 to 1.0 of the carboxyl group of the unsaturated monobasic acid is added to one epoxy group of the epoxy compound, it is preferred to form a ratio as follows: The acid anhydride structure of the polybasic acid anhydride is 0.1 to 1.0 in one hydroxyl group of the epoxy adduct.

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 usual method.

In order to adjust the acid value and improve the developability of the chromophore-developing photosensitive composition of the present invention, a monofunctional or polyfunctional epoxy compound may be further used together with the above-described alkali-developable compound having an ethylenically unsaturated bond. The acid value of the solid content component of the alkali-developable compound having an ethylenically unsaturated bond is preferably in the range of 5 to 120 mgKOH/g, and the amount of the monofunctional or polyfunctional epoxy compound is preferably used to satisfy the above acid value. Choose the way.

Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, and the like. Butyl glycidyl ether, tert-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, decyl glycidyl ether, ten Monoalkyl glycidyl ether, lauryl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-B Hexyl hexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxyglycidyl ether, p-butyl phenol glycidol Ether, cresyl glycidyl ether, 2-methyltolyl glycidyl ether, 4-mercaptophenyl glycidyl ether, benzyl glycidyl ether, p-cumyl phenyl glycidyl ether, trityl shrinkage Glycerol ether, methacrylic acid 2 , 3-glycidyl ester, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinyl cyclohexoxide, 1,2-epoxy-4-vinylcyclohexane, benzene oxide Ethylene, decene oxide, methyl styrene oxide, cyclohexene oxide, propylene oxide, the above-mentioned compounds No. A2, No. A3, and the like.

When one or more selected from the group consisting of a bisphenol type epoxy compound and a glycidyl ether are used as the polyfunctional epoxy compound, a color base-developable photosensitive composition having better properties can be obtained, and thus it is preferred. . In addition to the epoxy compound represented by the above formula (I), a bisphenol epoxy compound such as a hydrogenated bisphenol epoxy compound can be used as the bisphenol epoxy compound. Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,6-hexanediol diglycidyl ether. 8-octanediol diglycidyl ether, 1,10-nonanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, three Ethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexane dimethanol diglycidyl ether, 1,1,1-tris (glycidol) Oxymethyl)propane, 1,1,1-tris(glycidoxymethyl)ethane, 1,1,1-three (shrink) Glycidoxymethyl)methane, 1,1,1,1-tetrakis(glycidoxymethyl)methane.

In addition, a phenol novolac type epoxy compound, a biphenol novolak type epoxy compound, a cresol novolac type epoxy compound, a bisphenol A novolak type epoxy compound, a dicyclopentadiene novolac type A novolac type epoxy compound such as an epoxy compound; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-ring An alicyclic epoxy compound such as oxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or 1-epoxyethyl-3,4-epoxycyclohexane; diglycidyl phthalate Glycidyl esters such as esters, diglycidyl tetrahydrophthalate, glycidyl dimerates; tetraglycidyldiaminediphenylmethane, triglycidyl-p-aminophenol, N,N- a glycidylamine such as diglycidylaniline; a heterocyclic epoxy compound such as 1,3-diglycidyl-5,5-dimethylhydantoin or triglycidyl isocyanurate; A dioxide such as dicyclopentadiene dioxide; a naphthalene type epoxy compound, a triphenylmethane type epoxy compound, a dicyclopentadiene type epoxy compound, or the like.

In the above-mentioned polymerizable compound (B) having an ethylenically unsaturated bond (including the above-mentioned alkali-developable compound (B') having an ethylenically unsaturated bond), in terms of compatibility, alkali developability and heat resistance, Good: unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene; (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, Maleic acid, methyl maleic acid, fumaric acid, bicycloheptylene dicarboxylic acid, crotonic acid, methacrylic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, hexadienoic acid or methyl counter Butenoic acid, succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene oxyethyl ester] or ω-carboxyl polymerization Caprolactone mono(meth)acrylate is equivalent to a mono(meth)acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals, or a hydroxyethyl (meth)acrylate/maleate, (meth) Hydroxypropyl acrylate ‧ maleate, dicyclopentadiene ‧ maleate and one carboxyl group and two or more (meth) acrylonitrile groups An unsaturated monobasic acid such as a polyfunctional (meth) acrylate; a resin obtained by reacting an epoxy group such as an epoxy compound represented by the above formula (III) with an unsaturated monobasic acid and further reacting with a polybasic acid anhydride; Acidic polyfunctional acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, ( Isobutyl methacrylate, tert-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxy (meth) acrylate Ethyl ethyl ester, 2-ethylhexyl (meth)acrylate, (meth)acrylic acid A (meth) acrylate such as an ester, 2-hydroxyethyl (meth)acrylate or tetrahydrofurfuryl (meth)acrylate, more preferably an unsaturated aliphatic hydrocarbon or an unsaturated monobasic acid.

In the coloring composition of the present invention, the content of the above polymerizable compound (B) having an ethylenically unsaturated bond (including the above-mentioned alkali-developable compound (B') having an ethylenically unsaturated bond) is in the color combination of the present invention. The amount is preferably from 30 to 99% by mass, particularly preferably from 60 to 95% by mass. 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, or when the alkali developability occurs, development failure occurs. When the amount is more than 99% by mass, there is a case where the curing is insufficient by the exposure, the tackiness is insufficient, or the developing time is long when the alkali developability is caused, and the hardened portion is also caused to have a film defect due to the alkali.

<Photopolymerization initiator (C)>

As the photopolymerization initiator (C), a previously known compound can be used, and examples thereof include benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoguanidinocyclohexane, benzoin, and benzyl. Dimethyl ketal, 1-benzyl-1-dimethylamino-1-(4'- Polinylbenzylidene)propane, 2- Lolinyl-2-(4'-methylindenyl) benzhydrylpropane, 9-oxosulfur 1-chloro-4-propoxy-9-oxosulfur Isopropyl-9-oxosulfur Diethyl-9-oxosulfur , ethyl hydrazine, 4-benzylidene-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzylidene propane, 2-hydroxy-2-(4'-iso Propyl)benzhydrylpropane, 4-butylbenzylidenetrichloromethane, 4-phenoxybenzhydryldichloromethane, methyl benzylidenecarboxylate, 1,7-bis (9' -Acridine)heptane, 9-n-butyl-3,6-bis (2'- Olinoisobutyl hydrazino) oxazole, 2-methyl-4,6-bis(trichloromethyl)-all three , 2-phenyl-4,6-bis(trichloromethyl)-all three 2-naphthyl-4,6-bis(trichloromethyl)-all three , 2,2-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1-2'-biimidazole, 4,4-azobisisobutyronitrile, triphenylphosphine , camphor sputum, benzoyl peroxide, etc., as commercially available products, may be listed as: N-1414, N-1717, N-1919, PZ-408, NCI-831, NCI-930 (made by ADEKA Co., Ltd.) ), IRGACURE 369, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF).

Among the above photopolymerization initiators (C), in terms of sensitivity and color tone, it is preferably 2- Lolinyl-2-(4'-methylindenyl) benzhydrylpropane, 9-n-butyl-3,6-bis (2'- Orolinylisobutylhydrazino)carbazole, further preferably 2- Orolinyl-2-(4'-methylindenyl) benzhydrylpropane.

In the coloring composition of the present invention, the content of the photopolymerization initiator (C) is preferably from 0.1 to 30% by mass, particularly preferably from 0.5 to 10% by mass, based on the coloring composition of the present invention. When the content of the photopolymerization initiator (C) is less than 0.1% by mass, there is a case where hardening by exposure is insufficient, and if it is more than 30% by mass, the initiator (C) is present in the resin combination. The situation of precipitation.

The coloring material (D) other than the compound of the present invention may be further contained in the coloring composition of the present invention. These color materials may be used alone or in combination of two or more.

As the color material (D), for example, a nitroso compound, a nitro compound, an azo compound, a diazo compound, a dibenzopyran compound, a quinoline compound, an anthraquinone compound, a coumarin compound, or a hydrazine can be used. Cyanine compound, isoindolinone compound, isoporphyrin compound, quinacridone compound, indolinone compound, benzalkonone compound, anthraquinone compound, diketopyrrolopyrrole compound, thioindigo compound, two a compound, a triphenylmethane compound, a quinophthalone compound, a naphthalenetetracarboxylic acid; an azo dye, a metal complex of a cyanine dye; a lake pigment; a carbon black obtained by a furnace method, a channel method, a thermal method or Carbon black such as acetylene black, ketjen black or lamp black; if the carbon black is adjusted and coated with an epoxy resin, the carbon black is dispersed in a solvent in advance in a solvent to adsorb 20 to 200 mg/g. In the case of the resin, the carbon black is subjected to an acidic or alkaline surface treatment, and the average particle diameter is 8 nm or more, and the DBP oil absorption is 90 ml/100 g or less. The volatile matter at 950 ° C is calculated from CO and CO _{2 .} The total oxygen amount is 9 mg or more per 100 m ² with respect to the surface area of carbon black; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, spiral carbon fiber, carbon nano angle, carbon aerogel, rich Anthene; aniline black, pigment black 7, titanium black; hydrophobic resin, chrome oxide green, milorie blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate green, iron blue, ultramarine blue, sky blue Color, chrome green, emerald green, lead sulfate, yellow dan, zinc yellow, iron dan (red oxidation (III)), cadmium red, synthetic iron black, umber inorganic or organic pigment.

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

As the color material (D), a known dye can also be used. Examples of known dyes include azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, dibenzopyran dyes, alizarin dyes, acridine dyes, thiazole dyes, naphthol dyes, and naphthol dyes. Quinoline dye, nitro dye, indamine dye, Dyes, phthalocyanine dyes, dyes such as cyanine dyes, etc.

In the coloring composition of the present invention, the content of the color material (D) is preferably from 0 to 350 by mass based on 100 parts by mass of the polymerizable compound (B) having an ethylenically unsaturated bond. More preferably, it is 0 to 250 parts by mass. When the amount is more than 350 parts by mass, the cured product using the colored composition of the present invention, particularly the colored base-developing photosensitive composition, and the color filter of the display device are lowered, and the brightness of the display device is lowered. It is not good.

Further, a solvent may be added to the coloring composition of the present invention. As the solvent, a solvent which can dissolve or disperse the above respective components (dye (A) or the like containing the compound of the present invention) is usually used, and examples thereof include methyl ethyl ketone, methyl amyl ketone, and diethyl ether. Ketones such as ketone, acetone, methyl isopropanone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; diethyl ether, An ether solvent such as an alkane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, acetic acid An ester solvent such as isopropyl ester, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate or TEXANOL; a cellulosic solvent such as ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; Alcohol solvent such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol or pentanol; ethylene glycol monoacetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-B An ester ester solvent such as an ester (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate or ethoxyethyl propionate; a BTX solvent such as benzene, toluene or xylene; , an aliphatic hydrocarbon solvent such as heptane, octane or cyclohexane; a lanthanide hydrocarbon oil such as turpentine, D-limonene or decene; mineral spirits, Swazol # 310 (Cosmo pine oil (share)), Solvesso # Paraffin solvent such as 100 (Exon Chemical); halogenated aliphatic hydrocarbon solvent such as carbon tetrachloride, chloroform, trichloroethylene, dichloromethane, 1,2-dichloroethane; halogenated aromatic chlorobenzene Hydrocarbon solvent; carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-A The pyrrolidone, dimethyl hydrazine, water, and the like may be used alone or in combination of two or more. Among these, ketones, ether ester solvents, etc., especially propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc., in coloring compositions, resisting agents and photopolymerization initiators (C) It is preferred because it has good compatibility.

In the coloring composition of the present invention, the solvent is preferably used in an amount such that the solvent is When the concentration of the composition is 5 to 30% by mass, when the amount is less than 5% by mass, it is difficult to increase the thickness of the composition, and it is not possible to sufficiently absorb the light of a desired wavelength, which is not preferable, and when it is more than 30% by mass, In the case where the composition is precipitated, the preservability of the composition is lowered, or the viscosity is increased, so that the handleability is lowered.

Further, the colored composition of the present invention may further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, cerium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, cerium oxide, and aluminum oxide; layered clay minerals and rice. Lolita Blue, calcium carbonate, magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum citrate, calcium citrate, hydrogen Alumina, platinum, gold, silver, copper, etc., among these, titanium oxide, cerium oxide, layered clay mineral, silver, etc. 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, per 100 parts by mass of the polymerizable compound (B) having an ethylenically unsaturated bond. These inorganic compounds may be used alone or in combination of two or more.

These inorganic compounds can be used, for example, as a filler, an antireflection agent, a conductive agent, a stabilizer, a flame retardant, a mechanical strength enhancer, a special wavelength absorber, an ink repellent, and the like.

When a pigment and/or an inorganic compound is used in the coloring composition of the present invention, a dispersing agent may be added. As the dispersing agent, any coloring material or inorganic compound may be dispersed or stabilized, and any commercially available dispersing agent such as BYK series manufactured by BYK-Chemie Co., Ltd. may be used, and it may be preferably used. A polymer dispersing agent of a polyester, a polyether or a polyurethane having a basic functional group, having a nitrogen atom as a basic functional group and having a functional group of a nitrogen atom is an amine and/or a quaternary salt thereof and an amine The value is from 1 to 100 mgKOH/g.

Further, in the coloring composition of the present invention, a thermal polymerization inhibitor such as p-anisole, hydroquinone, catechol, tert-butylcatechol or thiodiphenylamine may be added as needed; plasticizing Adhesive; filler; defoamer; leveling agent; surface conditioner; antioxidant; ultraviolet absorber; dispersing aid; anticoagulant; catalyst; agonist; Additives such as adhesives.

In the coloring composition of the present invention, the dye (A), the polymerizable compound (B) having the ethylenically unsaturated bond, and the photopolymerization initiator (C) are optional components (excluding the color material (D). The content of the solvent and the solvent is not particularly limited, and is preferably 50 parts by mass based on 100 parts by mass of the polymerizable compound (B) having an ethylenically unsaturated bond. the following.

Further, the coloring composition of the present invention can improve the properties of the cured product comprising the coloring composition of the present invention by using another organic polymer together with the above polymerizable compound (B) having an ethylenically unsaturated bond. Examples of the above organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, and styrene-(meth)acrylic acid copolymer. , (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-ethylene copolymer, polyvinyl chloride resin, ABS (Acrylonitrile Butadiene Styrene, acrylonitrile-butadiene-styrene) Resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polypropylene decylamine, saturated polyester, phenol resin, phenoxy resin, polyamine Among these, a quinone imine resin, a poly phthalic acid resin, an epoxy resin, etc. are preferable, and polystyrene, a (meth)acrylic-methyl methacrylate copolymer, and epoxy resin are preferable.

In the case of using another organic polymer, the amount thereof is preferably 10 to 500 parts by mass based on 100 parts by mass of the polymerizable compound (B) having an ethylenically unsaturated bond.

Further, a chain transfer agent, a sensitizer, a surfactant, a decane coupling agent, a melamine compound or the like can be used in combination in the coloring composition of the present invention.

As the above chain transfer agent or sensitizer, a compound containing a sulfur atom can be usually used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-amidinopropyl)glycolamine Acid, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)amine-methylmethyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propyl Acid, N-(3-mercaptopropyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl(4-methylsulfanyl)phenyl ether , 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, nonylphenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2- Mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), etc. a mercapto compound, a disulfide compound obtained by oxidizing the mercapto compound, an iodide alkyl compound such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid or 3-iodopropanesulfonic acid, trihydroxyl Methylpropane tris(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylnonylbenzene, dibutyl Alcohol dithiopropionate, butanediol bis-mercaptoacetate, ethylene glycol bis-mercaptoacetate, trimethylolpropane tridecyl acetate, butanediol dithiopropionate, trishydroxyl Propane trithiopropionate, trimethylolpropane tridecyl acetate, pentaerythritol tetrasulfide Propionate, pentaerythritol tetradecyl acetate, trihydroxyethyl trithiopropionate, the following compound No. C1, tris-propionic acid tris(2-hydroxyethyl)isocyanurate and other aliphatic A functional thiol compound, KARENZ MT BD1, PE1, NR1, etc., manufactured by Showa Denko.

As the surfactant, an ionic surfactant such as a perfluoroalkyl phosphate or a perfluoroalkyl carboxylate, an anionic interfacial activity such as a higher fatty acid alkali salt, an alkyl sulfonate or an alkyl sulfate can be used. Agent, higher amine hydrohalide, quaternary ammonium salt, etc. Agents, polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides and other nonionic surfactants, amphoteric surfactants, polyfluorene surfactants, etc. Surfactants, these can be used in combination.

As the decane coupling agent, for example, a decane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among them, an isocyanate group, a methacryl oxime group or an epoxy group such as KBE-9007, KBM-502, or KBE-403 can be preferably used. Decane coupling agent.

Examples of the melamine compound include active hydroxyl groups in nitrogen compounds such as (poly)methylol melamine, (poly)hydroxymethyl glycoluril, (poly)hydroxymethylbenzene melamine, and (poly)hydroxymethylurea. A compound in which all or a portion (at least 2) of the group (CH ₂ OH group) is alkylated. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same or different from each other. Further, the methylol group which is not etherified by alkylation can be self-condensed in one molecule, or can be condensed between two molecules to form an oligomer component. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril or the like can be used. Among these, melamine which is alkyl etherified, such as hexamethoxymethyl melamine or hexabutoxymethyl melamine, is preferable.

The coloring composition of the present invention can be applied by a known method such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing, dipping, or the like. Sodium glass, quartz glass, semiconductor substrate, metal, paper, plastic and other supporting substrates. Further, it may be applied to a support substrate such as a film and then transferred to another support substrate, and the application method is not limited.

Further, as the light source for the active light used for curing the colored composition of the present invention, those emitting light having a wavelength of 300 to 450 nm can be used, and examples thereof include ultrahigh pressure mercury, mercury vapor arc, carbon arc, xenon arc, and the like.

Further, by using laser light by an exposure light source without using a mask, a direct laser direct writing method that directly forms an image based on digital information such as a computer can improve not only productivity but also analyticity or positional accuracy. And thus useful as the laser light, It is preferable to use light of a wavelength of 340 to 430 nm, and it is also possible to use an argon ion laser, a krypton laser, a YAG laser, and a semiconductor laser to emit light from the visible to the infrared region. In the case of using such lasers, a sensitizing dye that absorbs light from the visible to the infrared region is added.

The coloring composition of the present invention (or a cured product thereof) can be used for liquid crystal display of color display such as photocurable paint or varnish, photocurable adhesive, printed circuit board or color television, PC display, portable information terminal, digital camera, etc. Color filter for panel, color filter for CCD (Charge-coupled Device) image sensor, electrode material for plasma display panel, powder coating, printing ink, printing plate, adhesive, dental Composition, photo-forming resin, gel coat, electro-resistance photoresist, plating resist, etching resist, liquid and dry film, solder resist, for various display purposes a color filter or a resist for forming a structure, a composition for sealing electrical and electronic parts, in a manufacturing process of a plasma display panel, an electroluminescent display device, and an LCD (Liquid Crystal Display), Solder resist, magnetic recording material, micro mechanical parts, waveguide, optical switch, plating mask, etching mask, color test system, fiberglass cable coating, mesh Template for printing, material for manufacturing three-dimensional object by stereolithography, material for hologram recording, image recording material, fine electronic circuit, decolorizing material, decolorizing material for image recording material, use of microcapsule Decolorizing material for image recording material, photoresist material for printed wiring board, photoresist material for UV and visible laser direct image system, and dielectric layer formation in successive layers of printed circuit board The use of the photoresist material or the protective film is not particularly limited.

The coloring composition of the present invention, in particular, the color-developing photosensitive photosensitive composition is used for forming a pixel of a color filter, and is particularly useful as a color filter for a display device for forming an image display device such as a liquid crystal display panel or an organic EL. A photosensitive composition of a light sheet.

Further, the 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 of the above display device can be preferably formed by the following steps: (1) a step of forming a coating film of the coloring composition of the present invention (especially a color-developing photosensitive photoactive composition) on a substrate, (2) a step of irradiating the coating film with active light through a mask having a specific pattern shape, (3) a step of developing the exposed film by a developing solution (especially an alkaline developing solution), (4) The film is heated after development. Further, the coloring composition of the present invention can also be used as a coloring composition for an inkjet method or a transfer method without a developing step.

For the production of a color filter used in a liquid crystal display panel or the like, the coloring composition of the present invention or the like can be used, and the steps (1) to (4) described above can be repeated, and a pattern of two or more colors can be combined.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples.

Example 1. Synthesis of Compound No. 13, No. 25, No. 26 and No. 35 <Step 1>

0.01 mol of the following compound S-1, 0.02 mol of monoethylaminophenol and 0.03 mol of sulfuric acid were mixed, and the mixture was stirred at 140 ° C for 8 hours. The reaction liquid was added to an aqueous sodium hydroxide solution, and the organic substance was extracted with toluene and washed with water three times, and then the solvent was distilled off from the organic layer. The residue was purified by a silica gel column chromatography (developing solvent: chloroform) to afford a colorless substance (yield: 52%).

<Step 2>

2.56 g (0.005 mol) of a colorless body obtained in the step 1, water, 19.75 g, and 3.95 g of hydrochloric acid were added and stirred, and thereafter, 9.27 g of a 35 mass% ferric chloride aqueous solution was added, and the mixture was stirred at 80 ° C for 8 hours. After cooling to room temperature, chloroform was introduced, and the aqueous layer was taken out and washed with water, and then neutralized with an aqueous sodium hydrogencarbonate solution. After 4.79 g (0.01 mol) of potassium bis(trifluoromethanesulfonyl) sulfinamide was added for salt exchange, the solvent was distilled off from the obtained organic layer. The residue was purified by silica gel column chromatography (developing solvent: chloroform: ethyl acetate = 8:2) to afford 1.5 g (yield 38%).

Compound No. 25, No. 26, and No. 35 were synthesized by the same method as the above-mentioned synthesis method. Analysis of each compound was carried out to confirm that each was a target compound. The analysis results are shown in [Table 1], [Table 2], [Fig. 1], [Fig. 2], [Fig. 3], and [Fig. 4].

Example 2 and Comparative Example 2. Preparation of colored alkali-developable photosensitive composition <Step 1> Preparation of alkali-developable photosensitive composition

30.33 g of ACA Z251 (manufactured by Daicel-Cytec Co., Ltd.) and 11.04 g of ARONIX M-450 (manufactured by Toagosei Co., Ltd.) and 1.93 g of Irgacure 907 (manufactured by BASF Corporation) as component (C) were used as (B). PGMEA 20.08g of the component E) and 0.01 g of FZ2122 (manufactured by Toray Dow Corning Co., Ltd.) as other components were mixed and stirred until the insoluble matter disappeared, whereby an alkali-developable photosensitive composition was obtained.

<Step 2> Preparation of Dye Solution

0.10 g of each of the compounds described in [Table 3] and 1.90 g of PGMEA were added as a component (A), and the mixture was stirred and dissolved to prepare a dye liquid No. 1 to No. 2 and a comparative dye liquid No. 1 to No. 2 .

<Step 3> Preparation of Colored Base-developable Photosensitive Composition

In the 5.0 g of the alkali-developable photosensitive composition obtained in the step 1, the dye liquid obtained in the step 2 and the comparative dye liquid were mixed in an amount of 1.0 g, and the mixture was stirred until uniform to obtain a colored alkali-developable photosensitive composition No. 1 to No. 2 and comparative colored alkali-developable photosensitive composition No. 1 to No. 2.

Example 3 and Comparative Example 3. Evaluation of heat resistance by calcination

The colored base-developable photosensitive compositions No. 1 and No. 2 obtained in the chromogenic base-developing photosensitive composition No. 1 and No. 2 obtained in Example 2 and Comparative Example 2 were respectively at 410 rpm × 7 It was applied to a glass substrate under the conditions of seconds, and dried with a hot plate (90 ° C, 90 seconds). The obtained coating film was exposed (150 mJ/cm ² ) with an ultrahigh pressure mercury lamp. The exposed coating film was calcined at 230 ° C for 30 min. The color difference (ΔE _ab ^* ) before and after calcination was investigated. The better the heat resistance, the higher the color difference. The results are shown in [Table 4].

Example 4 and Comparative Example 4. Waveform controllability of light absorption spectrum

The optical absorption spectra of Compound No. 13, Compound No. 26, Compound No. 35, Comparative Compound No. 1 and Comparative Compound No. 2 were measured. The solvent was measured and the machine used was as follows.

Determination of solvent: chloroform

Dilution rate: 1mol/L

Use the machine: Hitachi spectrophotometer U-3010

The half value width of the spectral waveform obtained from each compound was measured. The half value width is an absolute value of the difference between the wavelengths of the long wavelength side and the short wavelength side when the absorbance of λmax is set to 1. The smaller the half value width, the steeper the waveform, and the better the dye as the alkali-developable photosensitive composition. The results are shown in [Table 5].

Claims (5)

A compound represented by the following formula (1): (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a halogen atom, or represent a cyano group or a nitro group; a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a halogen or a halogen atom, and either or both of R ⁴ and R ⁷ represent a halogen atom, R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ and R ¹⁶ independently represents a hydrogen atom, or represents a substitution with a nitro group, a carboxyl group, a sulfonic acid group, a hydroxyl group or a halogen atom, or a salt of a carboxyl group, an ester of a sulfonic acid group, a salt of a carboxyl group or a salt of a sulfonic acid group or a substituted alkyl group having 1 to 8 carbon atoms or an unsubstituted phenyl group, and R ¹³ represents a nitro group, a carboxyl group, a sulfonic acid group, a hydroxyl group or a halogen atom, or an ester of a carboxyl group or an ester of a sulfonic acid group. a salt of a carboxyl group or a salt of a sulfonic acid group substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or an unsubstituted phenyl group, X represents an oxygen atom, An ^q- represents an anion of a q valence, and q represents 1 or 2, p represents a coefficient for maintaining the charge to be neutral; wherein any one of R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ and R ¹⁶ is a hydrogen atom). A colored photosensitive composition comprising a dye (A) containing the compound of claim 1 , a polymerizable compound (B) having an ethylenically unsaturated bond, and a photopolymerization initiator (C). The colored photosensitive composition of claim 2, which further contains one or more (D) of a color material (excluding the compound represented by the above formula (I)). A cured product which is a cured product of the colored photosensitive composition of claim 2 or 3. A color filter for a display device comprising at least a portion of a cured product as claimed in claim 4.