KR20170116565A - Novel compound and colored photosensitive composition - Google Patents

Abstract

The present invention relates to a novel compound suitable for dyes and a colored photosensitive composition (a colored alkali developable photosensitive composition) using the above compound (dye) and a color filter which is excellent in solvent resistance and heat resistance and excellent in waveform control in a light absorption spectrum, And the compound represented by the following general formula (1), in particular, one or both of R ⁴ and R ⁷ in the general formula (1) is a hydroxyl group or a halogen atom, or a halogen atom-substituted one having 1 to 8 carbon atoms An alkyl group or an alkoxy group having 1 to 8 carbon atoms which may be substituted with a halogen atom is used as a dye. The specific contents of the general formula (1) are as described in this specification.

Description

NOVEL COMPOUND AND COLORED PHOTOSENSITIVE COMPOSITION [0002]

The present invention relates to a novel compound which is designed in a desired color, has good performance as a light absorber, and is suitable for a dye having improved heat resistance. Further, the present invention relates to a colored photosensitive composition capable of being polymerized by an energy ray using the dye, and a color filter using the colored photosensitive composition.

The compound having a strong absorption against a specific light may be a recording layer of an optical recording medium such as a CD-R, a DVD-R, a DVD + R or a BD-R, a liquid crystal display (LCD), a plasma display panel , An electroluminescence display (ELD), a cathode ray tube display (CRT), a fluorescent display tube, an field emission display, and the like.

In an optical filter for an image display device such as a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode ray tube display (CRT), a fluorescent display tube, Various compounds absorbing light having a wavelength of ~ 1100 nm have been used as a light absorber. These light absorbers are required to have excellent wave controllability such as light absorbance which is particularly sharp, that is, a half width of? Max is small, and that the function is not lost by light, heat, or the like.

An optical filter mainly used for a liquid crystal display (LCD) has a color filter. In general, three primary colors of RGB have been used for color filters. However, it has been difficult to obtain pure RGB colors as a single color material, and efforts have been made to use pure color RGB colors by using a plurality of color materials. Therefore, color materials such as yellow, orange, and purple are required instead of RGB.

Organic and / or inorganic pigments have been used in light absorbers for use in color filters depending on their high heat resistance. However, since they are pigments, there is a problem of lowering the luminance of a display device and solving this problem by increasing the luminance of the light source come. However, with the trend toward lower power consumption, the development of color filters using dyes has become active.

In recent years, in the color filter used in the solid-state image sensor, it is required to reduce the coloring pattern from the viewpoint of improving the image quality. In order to make it thin, it is necessary to increase the dye concentration from the viewpoint of color density. In addition, even when the dye has a low molar absorption coefficient, it is necessary to add a large amount of dye.

However, when dye concentration is increased, dissolution or precipitation of the dye from the formation pixel can be seen after film formation, or when heat treatment (post-baking) is performed after film formation, color mixing between adjacent pixels or between upper and lower layers in the lamination structure A problem that is likely to occur is becoming a problem.

Patent Document 1 discloses a dye monomer and a polymeric material thereof, Patent Document 2 discloses a hologram recording material containing a dye having a polymerizable group, and Patent Document 3 discloses a hologram recording material comprising a two-photon absorption light containing a dye having a polymerizable group And Patent Document 4 discloses a photosensitive coloring composition containing a triarylmethane dye monomer having an anionic polymerizable group. However, the compounds having a polymerizable group described in these documents are not satisfactory in terms of solvent resistance and heat resistance.

Japanese Laid-Open Patent Publication No. 11-246627 United States Patent Application Publication No. 2007/070481 United States Patent Application Publication No. 2009/088490 Patent Publication No. 4266627

Accordingly, an object of the present invention is to provide a novel compound which is excellent in solvent resistance and heat resistance, excellent in waveform controllability in a light absorption spectrum, and suitable for a dye. Another object of the present invention is to provide a colored photosensitive composition (colored alkali developing photosensitive composition) using the dye. Another object of the present invention is to provide an optical filter using the colored photosensitive composition (colored alkali developing photosensitive composition), and a color filter suitable for an image display apparatus such as a liquid crystal display panel without lowering the luminance .

As a result of intensive studies, the present inventors have found that a compound having a specific structure is excellent in heat resistance, excellent in solvent resistance in a colored photosensitive composition (colored alkali developable photosensitive composition), excellent in waveform control in light absorption spectrum And that the colored photosensitive composition (colored alkali developing photosensitive composition) is suitable for a color filter for an image display apparatus such as a liquid crystal display panel without lowering the luminance of an optical filter (particularly, a color filter) The invention has arrived.

The present invention is based on the above finding, and provides a compound represented by the following general formula (1).

[Chemical 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,

A cyano group, a nitro group, a hydroxyl group or an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms which is substituted with a halogen atom,

An unsubstituted or substituted alkoxy group having 1 to 8 carbon atoms,

An aryl group having 6 to 20 carbon atoms which is unsubstituted or substituted with a halogen atom,

An aryloxy group having 6 to 20 carbon atoms which is unsubstituted or substituted with a halogen atom,

An arylthio group substituted with a halogen atom or an unsubstituted carbon atom number of 6 to 20,

An arylalkenyl group having 8 to 20 carbon atoms which is substituted with a halogen atom or is unsubstituted or

An arylalkyl group of 7 to 20 carbon atoms which is substituted with a halogen atom or which is unsubstituted,

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,

An alkyl group having 1 to 8 carbon atoms which is substituted with a nitro group, a carboxyl group, a sulfonic acid group, a hydroxyl group or a halogen atom, or 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 with 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 substituted or unsubstituted phenyl group,

Substituted with 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, Or an unsubstituted benzyl group.

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 connected to form a 6-membered ring,

R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , and R ¹⁵ and R ¹⁶ may be connected to form a 3- to 6-membered heterocyclic ring,

R ³ and R ⁴ and R ⁷ and R ⁸ may form a ring through a single bond, an oxygen atom, a sulfur atom, a selenium atom, CR ¹⁷ R ¹⁸ , CO, NR ¹⁹ , PR ²⁰ or SO ₂ ,

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 represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms or a halogen atom-substituted or unsubstituted carbon atom having 1 to 8 carbon atoms An alkoxy group,

An ^{q -} represents an anion of q, q represents 1 or 2, and p represents a coefficient for keeping the charge neutral.

Provided that at least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is a hydrogen atom).

The present invention also provides a colored photosensitive composition comprising a dye (A) containing the above compound, a polymerizable compound (B) having an ethylenically unsaturated bond and a photopolymerization initiator (C).

The present invention also provides a color filter for a display device comprising at least a part of the cured product of the colored photosensitive composition and the cured product.

The compound of the present invention is excellent in solvent resistance and heat resistance, and is excellent in waveform controllability in a light absorption spectrum and is suitable as a dye. Further, the colored photosensitive composition (colored alkali developing photosensitive composition) containing the compound of the present invention as a dye is suitable as a color filter of an image display device such as a liquid crystal display panel without lowering the luminance.

1 is a ¹ H-NMR chart of Compound No. 13, which is a compound of the present invention synthesized in Example 1.
2 is a ¹ H-NMR chart of Compound No. 25 which is a compound of the present invention synthesized in Example 1.
3 is a ¹ H-NMR chart of the compound No. 26 of the present invention synthesized in Example 1.
4 is a ¹ H-NMR chart of the compound No. 35 of the present invention synthesized in Example 1. Fig.

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

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

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the compound represented by the general formula (I) are each independently a hydrogen atom or a halogen atom Or,

A cyano group, a nitro group, a hydroxyl group or an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms which is substituted with a halogen atom,

An unsubstituted or substituted alkoxy group having 1 to 8 carbon atoms,

An aryl group having 6 to 20 carbon atoms which is unsubstituted or substituted with a halogen atom,

An aryloxy group having 6 to 20 carbon atoms which is unsubstituted or substituted with a halogen atom,

An arylthio group substituted with a halogen atom or an unsubstituted carbon atom number of 6 to 20,

An arylalkenyl group having 8 to 20 carbon atoms, which is substituted with a halogen atom or is unsubstituted,

Or an arylalkyl group of 7 to 20 carbon atoms which is unsubstituted or substituted with 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 all the same.

Examples of the unsubstituted alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, heptyl group, 3-heptyl group, iso-heptyl group, tert-heptyl group, 3-hexyl group, Butyl group, 1-octyl group, iso-octyl group, tert-octyl group and the like.

As the alkyl group having 1 to 8 carbon atoms and substituted with a cyano group, a nitro group, a hydroxyl group or a halogen atom, the alkyl group having 1 to 8 carbon atoms is preferably selected from the group consisting of a cyano group, a nitro group, a hydroxyl group or a halogen atom Or a group substituted with one or more of the above groups.

Examples of the unsubstituted alkoxy group having 1 to 8 carbon atoms include methyloxy, ethyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, iso-butyloxy, Amyloxy group, 2-hexyloxy group, 3-hexyloxy group, cyclohexyloxy group, 4-methylcyclohexyloxy group, heptyloxy group, 2- Heptyloxy group, heptyloxy group, 3-heptyloxy group, iso-heptyloxy group, tert-heptyloxy group, 1-octyloxy group, iso-octyloxy group and tert-octyloxy group.

Examples of the alkoxy group having 1 to 8 carbon atoms substituted with a halogen atom include a group in which a part or all of the hydrogen atoms in the alkoxy group having 1 to 8 carbon 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.

Examples of the aryl group having 6 to 20 carbon atoms substituted with a halogen atom include a group in which a part 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 phenyloxy group and a naphthyloxy group.

Examples of the aryloxy group having 6 to 20 carbon atoms which is substituted with a halogen atom include a group in which a part 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.

Examples of the arylthio group having 6 to 20 carbon atoms and substituted with a halogen atom include groups in which some or all of the hydrogen atoms in the arylthio group having 6 to 20 carbon atoms in the unsubstituted group are substituted with halogen atoms.

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

Examples of the arylalkenyl group having 8 to 20 carbon atoms which is substituted with a halogen atom include a group in which a part 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 arylalkyl group having 7 to 20 carbon atoms include a styryl group and a cinnamyl group.

Examples of the arylalkyl group having 7 to 20 carbon atoms which is substituted with a halogen atom include a group in which a part or all of the hydrogen atoms in the unsubstituted arylalkyl group having 7 to 20 carbon atoms are substituted with 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,

An alkyl group having 1 to 8 carbon atoms which is substituted with a nitro group, a carboxyl group, a sulfonic acid group, a hydroxyl group or a halogen atom, 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 with 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 substituted or unsubstituted phenyl group,

Substituted with 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, Or an unsubstituted benzyl group.

Provided that at least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is 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 sec-butyl group, a tert-butyl group, an isobutyl group, Heptyl group, 3-hexyl group, cyclohexyl group, cyclohexyl group, 1-methylcyclohexyl group, heptyl group, 2-heptyl group, 3-heptyl group, iso-heptyl group, tert- , 1-octyl group, iso-octyl group, tert-octyl group and the like.

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

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

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

The phenyl group and the benzyl group may be partially or wholly substituted with a halogen atom, a cyano group, a vinyl group, a nitro group, a carboxyl group, a sulfonic acid group, or 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 may be substituted. Examples of the esters and salts include the above-mentioned 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 connected to form a 6-membered ring,

R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , and R ¹⁵ and R ¹⁶ may be connected to form a 3- to 6-membered heterocyclic ring,

R ³ and R ⁴ and R ⁷ and R ⁸ may be linked through a single bond, an oxygen atom, a sulfur atom, a selenium atom, CR ¹⁷ R ¹⁸ , CO, NR ¹⁹ , PR ²⁰ or SO ₂ to form a ring.

Examples of the 6-membered ring which can be formed by linking include a piperidine ring, a pyridine ring, a pyrimidine ring, a quinoline ring and an isoquinoline ring,

Examples of the 3- to 6-membered heterocyclic ring which can be formed by linking include a piperidine ring, piperazine ring, pyrrolidine ring, morpholine ring, thiomorpholine ring, pyridine ring, pyrazine ring, pyrimidine ring, quinoline ring, An isoquinoline ring, an imidazole ring, an oxazole ring, an imidazolidine ring, a pyrazolidine ring, an isoxazolidine ring, an isothiazolidine ring and the like. These 6-membered rings or heterocyclic rings may 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 ,

R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms or a halogen atom-substituted or unsubstituted carbon atom having 1 to 8 carbon atoms An unsubstituted alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms which is substituted with a halogen atom, an alkoxy group having 1 to 8 carbon atoms and an unsubstituted carbon atom or a carbon atom having 1 to 8 carbon atoms substituted with a halogen atom Examples of the alkoxy group include the above-mentioned examples.

PAn ^{q -} in the general formula (I) represents an anion of q, q represents 1 or 2, and p represents a coefficient for keeping the charge neutral. Examples of the anion represented by An ^{q -} include halide ions such as a chloride ion, a bromide ion, an iodide ion, and a fluoride ion; Inorganic anions such as perchlorate ion, chlorate ion, thiocyanate ion, hexafluorophosphate ion, hexafluoroantimonate ion and tetrafluoroborate ion; Sulfonic acid ion such as methanesulfonic acid ion, dodecylsulfonic acid ion, benzenesulfonic acid ion, toluenesulfonic acid ion, trifluoromethanesulfonic acid ion, naphthalenesulfonic acid ion, diphenylamine-5-sulfonic acid ion, Ion, a 2-amino-5-nitrobenzenesulfonic acid ion, a phthalocyanine sulfonic acid ion, a sulfonic acid ion having a polymerizable substituent, JP-A 10-235999, JP-A 10-337959, Japanese Patent Application Laid-Open Nos. 2000-108510, 2000-168223, 2001-209969, 2001-322354, 2006-248180, 2006-297907, and 08-253705 , Organic sulfonic acid anions such as sulfonic acid ions described in Japanese Patent Publication Nos. 2004-503379, 2005-336150, and 2006/28006; Organophosphoric acid based compounds such as octylphosphoric acid ion, dodecylphosphoric acid ion, octadecylphosphoric acid ion, phenylphosphoric acid ion, nonylphenylphosphoric acid ion and 2,2'-methylenebis (4,6-di- (Pentafluorophenyl) borate ion, tris (fluoro-4-ethylcyclohexyl) sulfonate ion, bis (trifluoromethylsulfonyl) imide ion, bis Carboxymethyl, carboxymethyl, cyclohexyloxycarbonyl, cyclohexyloxycarbonyl,

Examples of the divalent group include benzene disulfonic acid ion and naphthalene disulfonic acid ion.

It is also possible to use a quenching agent anion having a function of releasing (exciting) the active molecule in an excited state, a ferrocene having an anionic group such as a carboxyl group, a phosphonic acid group or a sulfonic acid group in a cyclopentadienyl ring, And a metallocene compound anion such as ruthenocene can also be used as needed. Also, p is selected such that charge is neutral throughout the molecule.

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

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

Among the compounds represented by the above general formula (I), the following are preferable from the viewpoint of the waveform controllability particularly in the light absorption spectrum.

It is preferable that either or both of R ⁴ and R ⁷ is a hydroxyl group, a halogen atom, an alkyl group having 1 to 8 carbon atoms which is substituted with a halogen atom, or an alkoxy group having 1 to 8 carbon atoms which may be substituted with a halogen atom, , More preferably an alkyl group having 1 to 8 carbon atoms substituted with a halogen atom, and still more preferably a halogen atom.

As the groups other than the hydrogen atom, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are preferably an alkyl group having 1 to 8 carbon atoms which is substituted with a polar group, .

X is preferably an oxygen atom or a sulfur atom from the viewpoint of availability.

Specific examples of the cation moiety of the compound represented by the general formula (I) of the present invention include the following compounds No. 1-14.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

The method for producing the compound represented by the above general formula (I) is not particularly limited, and for example, when X in the general formula (I) is an oxygen atom, it can be prepared according to the following reaction formula. On the other hand, when X is other than an oxygen atom, it can be produced according to the following production method. It can also be produced according to a known method described in Journal of Organic Chemistry (2009), 74 (8), 3183-3185.

[Chemical Formula 6]

(Wherein R ¹ to R ¹⁶ , An ^{q -} , p and q are the same as in the general formula (I)).

The compound represented by the general formula (I) can be used not only as a colored alkali developable photosensitive composition described below but also as an optical filter used in a display or an optical lens, a photosensitive material for silver halide photography, Is used.

Next, 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 described below is appropriately described as a coloring composition.

The colored photosensitive composition of the present invention is a colored photosensitive composition comprising a dye (A) (hereinafter also referred to as a dye (A)) containing the compound of the present invention, a polymerizable compound (B) having an ethylenically unsaturated bond (B ') having an ethylenically unsaturated bond and having a substituent, a photopolymerization initiator (C) and, if necessary, a colorant (wherein the dye is a compound represented by the general formula (I) (D).

The dye (A) used in the present invention may contain at least one compound of the present invention, and may be used singly or in combination. In addition to the compounds of the present invention, known dyes may be used for the 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, indanamine dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, and the like, and a plurality of these 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 50 to 100% by mass, and more preferably 70 to 100% by mass. When the content of the compound of the present invention is less than 50% by mass, the solubility in a 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) in the coloring composition of the present invention is preferably 0.01 to 50 mass%, more preferably 0.1 to 30 mass%. When the content of the dye (A) is less than 0.01% by mass, a desired concentration of color can not be obtained in the cured product of the coloring composition of the present invention. When the content is more than 50% by mass, May precipitate.

<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 a photosensitive composition may be used. Examples thereof include ethylene, propylene, butylene, isobutylene, vinyl chloride, Unsaturated aliphatic hydrocarbons such as vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (Meth) acrylic acid,? -Chloroacryl, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymamic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allylic acetic acid, cinnamic acid, sorbic acid, (Meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals such as (meth) acryloyloxyethyl] phthalate mono [2- (meth) acryloyloxyethyl], omega -carboxylic polycaprolactone mono (Meth) acrylate maleate, hydroxypropyl (meth) acrylate maleate, dicyclopentadiene maleate or one carboxyl group and two or more (meth) acryloyl groups Unsaturated polybasic acids such as polyfunctional (meth) acrylates; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (Meth) acrylate, isobutyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl Stearyl acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, methylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, dimethylaminopropyl (Meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, ethylhexyl (Meth) acrylate, (meth) acrylate, (Meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethyleneglycol di (meth) acrylate, triethyleneglycol di Trimethylol ethane tri (meth) acrylate, trimethylol propane tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecanedimethyloly (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa Unsaturated monobasic acids and polyhydric alcohols such as tri (meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomer, or the like Esters of phenol; Metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; Maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) Acid anhydrides of unsaturated polybasic acids such as cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl anhydride succinic anhydride, and methyl anhydride; (Meth) acrylamide, methylenebis- (meth) acrylamide, diethylenetriamintris (meth) acrylamide, xylidenebis (meth) acrylamide,? -Chloroacrylamide, N-2-hydroxyethyl Amides of unsaturated monobasic acids and polyamines such as methacrylamide; Unsaturated aldehydes such as acrolein; Unsaturated nitriles such as (meth) acrylonitrile,? -Chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; Vinylbenzene sulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, and vinylbenzenesulfonic acid. Unsaturated aromatic compounds such as vinylbenzyl methyl ether and vinyl benzyl glycidyl ether; Unsaturated ketones such as methyl vinyl ketone; Unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone and vinylpiperidine; Vinyl alcohols such as allyl alcohol and crotyl alcohol; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and aryl glycidyl ether; Unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; Indene such as indene and 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane; Vinyl pyrrolidone, vinyl pyrrolidone, vinyl pyrrolidone, vinyl pyrrolidone, vinyl pyrrolidone, vinyl pyrrolidone, vinyl pyrrolidone, vinyl pyrrolidone, vinyl pyrrolidone, Containing vinyl monomers and vinyl epoxide compounds of polyepoxy compounds, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and other hydroxyl group-containing polyfunctional acrylics such as vinylpyridine, vinylpyridine, hydroxyl group-containing vinyl monomers and polyisocyanate compounds, A reaction product of a multifunctional isocyanate such as toluene diisocyanate and hexamethylene diisocyanate, a reaction product of a hydroxyl group-containing polyfunctional acrylate such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate, anhydride succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, etc. Of A polyfunctional acrylate having an acid value which is a reactant of dibasic acid anhydride.

These polymerizable compounds may be used alone or in admixture of two or more. When two or more of them are mixed and used, they may be used in the form of a copolymer in advance.

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the coloring composition of the present invention, the polymerizable compound (B ') having an ethylenically unsaturated bond having an alkali-soluble substituent imparting alkali developability ((B')) having an ethylenically unsaturated bond (Hereinafter also referred to as an alkali developing compound (B ') having an ethylenically unsaturated bond), the colored photosensitive composition of the present invention becomes a colored alkali developable photosensitive composition. Examples of the alkali developing compound (B ') having an ethylenically unsaturated bond include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (Meth) acrylate, cyclohexyl (meth) acrylate, isobutyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate such as 2-ethylhexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and tetrahydrofurfuryl Acrylic acid esters; N-vinylpyrrolidone; Styrene and its derivatives, styrene such as? -Methylstyrene; Acrylamides such as (meth) acrylamide, methylol (meth) acrylamide, alkoxymethylol (meth) acrylamide and diacetone (meth) acrylamide; (Meth) acrylonitrile, other vinyl compounds such as ethylene, propylene, butylene, vinyl chloride, and vinyl acetate, and macromonomers such as polymethyl methacrylate macromonomers and polystyrene macromonomers, monomers such as monometalates of tricyclodecane skeleton (Meth) acrylate, and copolymers of these with methacryloyloxymethyl-3-ethyloxetane, and unsaturated (meth) acrylates such as carlens MOI and AOI manufactured by Showa Denko Co., A copolymer of (meth) acrylic acid having an isocyanate compound bonded thereto, a copolymer of phenol and / or cresol novolac epoxy resin, a biphenyl skeleton, a novolac epoxy resin having a naphthalene skeleton, a bisphenol A novolak type epoxy compound, Novolak type epoxy compounds such as pentadiene novolak type epoxy compounds, polyphenylmethane type epoxy resins having polyfunctional epoxy groups, , An epoxy compound such as an epoxy compound represented by the following general formula (1) or (2). These monomers may be used singly or in combination of two or more. The alkali developing compound (B ') having an ethylenically unsaturated bond preferably contains 0.2 to 1.0 equivalent of an unsaturated group.

(11)

(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 the formula (a) represents a substituent represented by the formula (B) or (C), and optionally wherein the alkylidene group is substituted with 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, Group may be substituted with a halogen atom, and m is an integer of 0 to 10.)

[Chemical Formula 12]

(Wherein Y ² is an alkyl group having 1 to 10 carbon atoms or a phenyl group optionally substituted with an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms Y ¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, The alkyl group, alkoxy group and alkenyl group in Y ¹ may be substituted with a halogen atom, and b is an integer of 0 to 5.)

[Chemical Formula 13]

[Chemical Formula 14]

(Wherein Y ³ and Y ⁴ each independently represent an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, a carbon atom 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, an arylalkenyl group having 8 to 20 carbon atoms and may be substituted with a halogen atom, an arylalkyl group having 7 to 20 carbon atoms and may be substituted with a halogen atom, A heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom, a group obtained by combining a plurality of these groups, or a halogen atom, the methylene group in the alkyl group and the arylalkyl group in the Y ³ and Y ⁴ is an unsaturated bond, -S-, Y ⁴ may form a ring of adjacent Y ⁴ groups, n represents an integer of 0 to 4, q represents an integer of 0 to 8, r Represents an integer of 0 to 4, 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.)

Examples of the unsaturated monobasic acid acting as an epoxy group of the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate malate and the like. Hydroxyethyl acrylate maleate, hydroxypropyl methacrylate maleate, hydroxypropyl acrylate maleate, dicyclopentadiene maleate, and the like.

Examples of the polybasic acid anhydride to be reacted after the action of the unsaturated monobasic acid may include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, anhydrous amber acid, maleic anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, 2'-3,3'-benzophenonetetracarboxylic anhydride, ethylene glycol bisanhydrotrimellitate, glycerol trisanhydrotrimellitate, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic acid anhydride, methylnadic acid Hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride, Phthalic anhydride-maleic anhydride adduct, dodecenyl anhydride succinic anhydride, and methyl anhydride anhydride.

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows. That is, an epoxy adduct having a structure in which the carboxyl group of the unsaturated monobasic acid is added in an amount of 0.1 to 1.0 per epoxy group of the epoxy compound, wherein the amount of the acid of the polybasic acid anhydride And the ratio of the anhydride structure is 0.1 to 1.0.

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

In order to improve the developability of the colored alkali developable photosensitive composition of the present invention by adjusting the acid value, a monofunctional or polyfunctional epoxy compound may be used together with the alkali developable compound having an ethylenically unsaturated bond. The alkali developing compound having an ethylenically unsaturated bond preferably has an acid value of 5 to 120 mg KOH / g as the solid content, and the amount of the monofunctional or polyfunctional epoxy compound to be used is preferably selected so as to satisfy the acid value .

Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl Ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl Dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, aryl glycidyl ether, Propylglycidyl ether, p-methoxyethylglycidyl ether, phenylglycidyl ether, p-methoxyglycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether , 2-methylcresol glycidyl ether, 4 - nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumyl phenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, Vinyl cyclohexane monoxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, Compound No. A.A2, No.A3 .

As the polyfunctional epoxy compound, use of at least one selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers is preferable because a colored colored alkali-developable photosensitive composition having better characteristics can be obtained. As the bisphenol type epoxy compound, for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can be used besides the epoxy compound represented by the above general formula (I). Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8- Octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol Diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxy Methyl) propane, 1,1,1-tri (glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1-tetra Methyl) methane.

In addition, novolak type epoxy compounds such as phenol novolak type epoxy compounds, biphenyl novolak type epoxy compounds, cresol novolak type epoxy compounds, bisphenol A novolak type epoxy compounds and dicyclopentadiene novolak epoxy compounds; Epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl- Alicyclic epoxy compounds such as 3,4-epoxycyclohexane; Glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester and dimeric acid glycidyl ester; Glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol and N, N-diglycidylaniline; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; A dioxide compound such as dicyclopentadiene dioxide; Naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclopentadiene type epoxy compounds, and the like.

Among the above polymerizable compounds (B) having an ethylenically unsaturated bond (including the alkali-developable compound (B ') having an ethylenically unsaturated bond), from the viewpoints of compatibility, alkali developability and heat resistance, , Unsaturated aliphatic hydrocarbons such as butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (Meth) acrylic acid,? -Chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymamic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid or mesaconic acid, (Meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals, such as (meth) acryloyloxyethyl] phthalate mono [2- (meth) acryloyloxyethyl] or omega -carboxypolycaprolactone mono (Meth) acrylate maleate, hydroxypropyl (meth) acrylate maleate, dicyclopentadiene maleate, and one carboxyl group and two or more (meth) acryloyl groups Unsaturated monobasic acids such as polyfunctional (meth) acrylates; A polyfunctional acrylate having an acid value such as a resin obtained by reacting an unsaturated monobasic acid with an epoxy group such as an epoxy compound represented by the above general formula (III) and further reacting with a polybasic acid anhydride; Acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (Meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (Meth) acrylic esters such as acrylate, 2-hydroxyethyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate are preferable, and unsaturated aliphatic hydrocarbons and unsaturated monobasic acids are more preferable.

In the coloring composition of the present invention, the content of the polymerizable compound (B) having an ethylenically unsaturated bond (including the alkali-developable compound (B ') having an ethylenically unsaturated bond) Is preferably 30 to 99% by mass, more preferably 60 to 95% by mass. If the content of the polymerizable compound (B) having an ethylenically unsaturated bond is less than 30% by mass, there is a case where defective development occurs in the case where the mechanical strength of the cured product is insufficient to cause cracking or to have alkali developability If it is more than 99% by mass, the curing by exposure becomes insufficient and a tuck occurs, or if it has alkali developability, the development time becomes longer, and the cured portion may also cause film damage with alkali.

&Lt; Photopolymerization initiator (C) >

As the photopolymerization initiator (C), conventionally known compounds can be used, and examples thereof include benzophenone, phenylbiphenylketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethylketal, 1 1-dimethylamino-1- (4'-morpholinobenzoyl) propane, 2-morpholyl-2- (4'-methylmercapto) benzoylpropane, thioxanthone, Benzoyl-4'-methyldiphenylsulfide, benzoin butyl ether, 2-hydroxy-2-benzoyl propane, 2- Butyl benzoyl trichloromethane, 4-phenoxybenzoyl dichloromethane, methyl benzoate, methyl 1,7-bis (9'-acridinyl) heptane, (Trichloromethyl) -s-triazine, 2-phenyl-4-methyl-4,6-bis , 6-bis (trichloromethyl) -s-triazine Bis (trichloromethyl) -s-triazine, 2,2-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl- N-1717, N-1919, PZ-N, N, N'-dicyclohexylcarbodiimide, N, N'-dicyclohexylcarbodiimide, IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF Co., Ltd.), and the like can be given.

Among the photopolymerization initiators (C), 2-morpholyl 2- (4'-methylmercapto) benzoyl propane, 9-n-butyl-3,6-bis (2'- Isobutyryl) carbazole is preferable, and 2-morpholyl 2- (4'-methylmercapto) benzoyl propane is more preferable.

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

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

Examples of the colorant (D) include a nitroso compound, a nitro compound, an azo dye compound, a diazo compound, a xanthene compound, a quinoline compound, an anthraquinone compound, a coumarin compound, a phthalocyanine compound, an isoindolinone compound, Indoline compounds, quinacridone compounds, anthanthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acid; Azo dyes, metal complex compounds of cyanine dyes; Lake pigment; Carbon black obtained by a furnace method, a channel method, and a thermal method; carbon black such as acetylene black, Ketjen black or lamp black; The carbon black is coated with an epoxy resin, the carbon black is dispersed in a solvent in advance in a solvent to adsorb a resin of 20 to 200 mg / g, an acidic or alkaline surface-treated carbon black , An average particle diameter of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, a total oxygen amount calculated from CO and CO ₂ in a volatile fraction at 950 ° C of 9 mg or more per 100 m 2 of the surface area of carbon black; Graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon airgel, fullerene; Cobalt blue, cobalt blue, manganese based, ferrocyanide, phosphate, ultramarine, cerulean blue, pyridian, pyranthrone, aniline black, black pigment 7, titanium black, hydrophobic resin, chromium oxide green, Inorganic pigments or organic pigments such as emerald green, lead sulfate, yellow lead, zinc sulfur, red iron oxide (III), cadmium red, synthetic iron black and amber may be used.

As the colorant (D), commercially available pigments may be used. For example, pigments of pigments 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 180, 184, 185, 192, 200, 202, 209, 215, 216, 169, 169, 170, 171, 177, 179, 180, 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, , 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 coloring material (D), a known dye may be used. 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, indanamine dyes, oxazine dyes, phthalocyanine dyes, and cyanine dyes.

In the coloring composition of the present invention, the content of the colorant (D) is preferably 0 to 350 parts by mass, more preferably 0 to 100 parts by mass, per 100 parts by mass of the polymerizable compound (B) having the ethylenically unsaturated bond. 250 parts by mass. When the amount exceeds 350 parts by mass, the light transmittance of the coloring composition of the present invention, particularly the cured product using a colored alkali developing photosensitive composition, and the color filter for a display device are lowered and the brightness of the display device is lowered.

A solvent may be further added to the coloring composition of the present invention. As the solvent, a solvent capable of dissolving or dispersing the respective components (the dye (A) or the like containing the compound of the present invention), for example, methyl ethyl ketone, methyl amyl ketone, diethyl Ketones such as ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; Ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and dipropylene glycol dimethyl ether; Esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol-based solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate An ether ester solvent such as sodium carbonate; BTX type solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene-based hydrocarbon oils such as terphenyl oil, D-limonene, and pinene; Paraffin solvents such as Mineral Spirit, Swazor # 310 (Kosomo Matsuyama Sekiyu Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichlorethylene, methylene chloride, and 1,2-dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; A solvent such as acetone, acetonitrile, carbon dioxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water These solvents may be used singly or as a mixed solvent of two or more kinds. Of these, ketones, ether ester solvents and the like, especially propylene glycol-1-monomethyl ether-2-acetate and cyclohexanone, are preferable because they have good compatibility with the photopolymerization initiator (C) Do.

In the coloring composition of the present invention, the amount of the solvent used is preferably from 5 to 30 mass%, more preferably from 5 to 30 mass%, of the composition other than the solvent. When the amount is less than 5 mass% It is not preferable because it can not sufficiently absorb. When it is more than 30% by mass, the storage stability of the composition due to precipitation of the composition may be deteriorated, or the viscosity may be improved or the handling may be lowered.

The coloring 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, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica and aluminum oxide; Mica, talc, kaolin, ferrocyanide, various metal sulfates, sulphides, selenides, aluminum silicates, calcium silicates, aluminum hydroxides, calcium silicate, calcium carbonate, magnesium carbonate, cobalt, manganese, , Platinum, gold, silver, copper and the like. Of 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 0.5 to 20 parts by mass, per 100 parts by mass of the polymerizable compound (B) having the ethylenically unsaturated bond These inorganic compounds may be used alone or in combination of two or more.

These inorganic compounds are used, for example, as fillers, antireflective agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbing agents,

When a pigment and / or an inorganic compound is used in the coloring composition of the present invention, a dispersant may be added. Examples of the dispersing agent include any dispersant that can disperse and stabilize a coloring material and an inorganic compound, and commercially available dispersing agents such as BYK series and BYK series can be used, and a polyester having a basic functional group, a polyether, a poly A polymer dispersant comprising urethane, a functional group having a nitrogen atom as a basic functional group, a functional group having a nitrogen atom, an amine and / or a quaternary salt thereof, and an amine value of 1 to 100 mgKOH / g are suitably used.

The coloring composition of the present invention may optionally contain thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol and phenothiazine; Plasticizers; Adhesion promoter; filler; Defoamer; Leveling agents; Surface modifiers; Antioxidants; Ultraviolet absorber; Dispersing aids; An anti-aggregation agent; catalyst; Effect promoters; A crosslinking agent; A common additive such as a thickener may be added.

In the coloring composition of the present invention, any component other than the above-mentioned dye (A), the polymerizable compound (B) having an ethylenically unsaturated bond and the photopolymerization initiator (C) (except for the colorant (D) ) Is appropriately selected depending on the purpose of use and is not particularly limited, but is preferably 50 parts by mass or less based on 100 parts by mass of the polymerizable compound (B) having an ethylenically unsaturated bond.

In the coloring composition of the present invention, the properties of the cured product of the coloring composition of the present invention may be improved by using another organic polymer together with the polymerizable compound (B) having an ethylenically unsaturated bond. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymers, (meth) Acrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, Amide, saturated polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, and epoxy resin. Of these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer and epoxy resin are preferable Do.

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

The coloring composition of the present invention may further contain a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound and the like.

As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. Examples of the acid generator include thioglycolic acid, thioferric acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, N- (2-mercaptopropionyl) glycine, (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercapto But are not limited to, ethane sulfonic acid, 3-mercaptopropane sulfonic acid, 4-mercaptobutane sulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, Propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzoimidazole, 2-mercapto-3- (2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), and pentaerythritol tetrakis (3-mercaptopropionate) A disulfide compound obtained by oxidizing the mercapto compound, an iodinated alkyl compound such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid or 3-iodopropanesulfonic acid, a trimethylolpropane tris (3 -Mercaptoisobutyrate), butanediol bis (3-mercaptoisobutylate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bis-thiouropionate, butanediol bis- Propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether glycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiourethionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, Pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopro &lt; RTI ID = 0.0 &gt; Aliphatic polyfunctional thiol compounds such as phthalate, phonate, the following compound No. C1 and trimercapto propionic acid tris (2-hydroxyethyl) isocyanurate, carboxes MT BD1, PE1, NR1 manufactured by Showa Denko Co., have.

[Chemical Formula 15]

Examples of the surfactant include fluorine surfactants such as perfluoroalkylphosphoric acid esters and perfluoroalkylcarboxylic acid salts, anionic surfactants such as higher fatty acid alkali salts, alkylsulfonates and alkylsulfates, higher amine halides, A surfactant such as a nonionic surfactant such as a polyethylene glycol alkyl ether, a polyethylene glycol fatty acid ester, a sorbitan fatty acid ester, a fatty acid monoglyceride, a positive surfactant, or a silicone surfactant can be used as the cationic surfactant They may be used in combination.

Examples of the silane coupling agent include silane coupling agents such as KBE-9007, KBM-502 and KBE-403, among which silane coupling agents having an isocyanate group, a methacryloyl group or an epoxy group, The ring agent is used appropriately.

Examples of the melamine compound include compounds having an active methylol group (CH ₂ OH group) in a nitrogen compound such as (poly) methylol melamine, (poly) methylol glycoluryl, (poly) methylolbenzoguanamine, All or a part (at least two) of which are alkyl-etherified. Examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group and a butyl group, and they may be the same or different. The methylol group which is not alkyl-etherified may be self-condensed in one molecule or may be condensed between two molecules to form an oligomer component. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used. Of these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferred.

The coloring composition of the present invention can be applied to a supporting substrate such as a soda glass, a quartz glass, a semiconductor substrate, a metal, a paper, a plastic or the like by a known means such as a spin coater, a roll coater, a bar coater, a die coater, . &Lt; / RTI &gt; Furthermore, once applied to a supporting substrate such as a film, it may be transferred onto another supporting substrate, and the application method thereof is not limited.

As the light source of active light used for curing the coloring composition of the present invention, those emitting light having a wavelength of 300 to 450 nm can be used. For example, ultra high pressure mercury, mercury vapor arc, carbon arc, .

Further, by using the laser light for the exposure light source, the laser direct imaging method for forming an image directly from digital information of a computer or the like without using a mask can improve not only productivity but also resolution and positional accuracy As the laser light, light having a wavelength of 340 to 430 nm is suitably used. However, it is also possible to emit light in an infrared region from the viewpoint of an argon ion laser, a helium neon laser, a YAG laser, or a semiconductor laser do. When these lasers are used, a sensitizing dye for absorbing light in the infrared region is added from visible.

The coloring composition (or a cured product thereof) of the present invention can be used as a color filter in a color display liquid crystal display panel such as a photo-curable paint or varnish, a photo-curable adhesive, a printed substrate or a color TV, a PC monitor, a portable information terminal, , A color filter of a CCD image sensor, an electrode material for a plasma display panel, a powder coating, a printing ink, a printing plate, an adhesive, a dental composition, In order to manufacture color filters for both liquid and dry films, solder resists, and various display applications, or to form structures in plasma display panels, electroluminescence display devices, and LCD manufacturing processes, A solder resist, a magnetic recording material, a micromachined part, a waveguide, an optical switch, a plating mask, an etching mask , Color test system, glass fiber cable coating, stencil for screen printing, materials for producing three-dimensional objects by stereolithography, holographic recording materials, image recording materials, fine electronic circuits, decolorizing materials, decolorizing materials for image recording materials, A photoresist material for a printed wiring board, a photoresist material for a UV and visible laser direct-image system, a photoresist material or a protective film used for forming a dielectric layer in a sequential lamination of a printed circuit board And the like, and the use thereof is not particularly limited.

The coloring composition of the present invention, particularly the colored alkali developing photosensitive composition, is used for the purpose of forming a pixel of a color filter, and in particular, a photosensitive composition for forming a color filter for a display device for an image display device such as a liquid crystal display panel, .

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

The color filter for a display device includes the steps of: (1) forming a coating film of a coloring composition (in particular, a colored alkali developing photosensitive composition) of the present invention on a substrate; (2) (3) a step of developing the coating film after exposure with a developing solution (particularly, an alkali developing solution), and (4) a step of heating the coating film after development. Further, the coloring composition of the present invention is also useful as a coloring composition of an inkjet method or a transfer method without a development process.

The production of a color filter for use in a liquid crystal display panel or the like can be carried out by repeating the steps (1) to (4) above using a coloring composition of the present invention or other coloring composition, .

Example

Hereinafter, the present invention will be described in detail with reference to 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 stirred at 140 占 폚 for 8 hours. The reaction solution was added dropwise to an aqueous solution of sodium hydroxide, and the organic material was extracted from toluene, washed three times, and then the solvent was distilled off from the organic layer. The residue was purified by silica gel column chromatography (developing solvent: chloroform) to obtain 0.005 mol (yield 52%) of leuco.

[Chemical Formula 16]

<Step 2>

2.55 g (0.005 mol) of the leuco obtained in Step 1, 19.75 g of water and 3.95 g of hydrochloric acid were added and stirred. Then, 9.27 g of a 35 mass% aqueous solution of iron chloride was added and the mixture was stirred at 80 ° C for 8 hours. After cooling to room temperature, chloroform was added, the aqueous layer was taken out, washed with water and neutralized with aqueous sodium chloride solution. After the salt exchange with 4.79 g (0.01 mol) of bis (trifluoromethanesulfonyl) imidotaur, 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 obtain 1.5 g (yield: 38%) of the target compound.

Compounds No. 25, No. 26 and No. 35 were synthesized using the same method as above. Each compound was analyzed, and it was confirmed that each compound was the target compound. The analysis results are shown in [Table 1], [Table 2], [Figure 1], [Figure 2], [Figure 3] and [Figure 4].

[Table 1]

[Table 2]

Example 2 and Comparative Example 2. Preparation of colored alkali developable photosensitive composition

&Lt; Step 1 > Preparation of alkali developable photosensitive composition

30.33 g of ACA Z251 (manufactured by Daicel-Cotech Co., Ltd.) as component (B), 11.04 g of Aronix M-450 (manufactured by Doagosei Co., Ltd.), 1.93 g of Irgacure 907 (manufactured by BASF Corporation) 20.08 g of PGMEA as 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 insolubles disappeared to obtain an alkali developable photosensitive composition.

<Step 2> Preparation of dye liquid

0.10 g of each of the compounds described in [Table 3] as the component (A) and 1.90 g of PGMEA were added and dissolved by stirring to obtain dye solutions No. 1 to No. 2 and Comparative dye solutions No. 1 to No. 2.

<Step 3> Preparation of colored alkali developable photosensitive composition

1.0 g of the dye liquid obtained in Step 2 and 1.0 g of the comparative dye liquid were mixed into 5.0 g of the alkali developable photosensitive composition obtained in Step 1 and stirred until uniform, and the color developing alkali photosensitive photosensitive composition No. 1-1 to No. 2 and Comparative colored alkali-developable photosensitive composition No. 1 to No. 2 were obtained.

[Chemical Formula 17]

[Table 3]

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

The colored alkali-developable photosensitive compositions No. 1 and No. 2 obtained in Example 2 and Comparative Colored Alkali-developable photosensitive compositions No. 1 and No. 2 obtained in Comparative Example 2 were applied to a glass substrate at 410 rpm for 7 seconds And dried on a hot plate (90 DEG C, 90 seconds). The obtained coating film was exposed (150 mJ / cm 2) with an ultra-high pressure mercury lamp. The coated film after the exposure was fired under the conditions of 230 캜 x 30 min. The color difference (? E _ab *) before and after firing was examined. As the heat resistance is good, the value of the color difference becomes high. The results are shown in Table 4.

[Table 4]

Example 4 and Comparative Example 4. Wave form control of light absorption spectrum

Compound № 13, the compound № 26, the compound № 35, the comparative compound № 1 and the comparative compound № 2 light absorption spectra. The measuring solvent and the equipment to be used are as follows.

Measuring solvent: chloroform

Dilution ratio: 1 mol / L

Equipment used: Hitachi Spectrophotometer U-3010

The half width of the spectral waveform obtained with each compound was measured. The half width is the absolute value of the wavelength difference between the long wavelength side and the short wavelength side where the absorbance of? Max is 1 and the absorbance is 0.5. As the half width is small, the waveform is steep and is good as a dye for an alkali developable photosensitive composition. The results are shown in Table 5.

[Table 5]

Claims (6)

A compound represented by the following general 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,
A cyano group, a nitro group, a hydroxyl group or an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms which is substituted with a halogen atom,
An unsubstituted or substituted alkoxy group having 1 to 8 carbon atoms,
An aryl group having 6 to 20 carbon atoms which is unsubstituted or substituted with a halogen atom,
An aryloxy group having 6 to 20 carbon atoms which is unsubstituted or substituted with a halogen atom,
An arylthio group substituted with a halogen atom or an unsubstituted carbon atom number of 6 to 20,
An arylalkenyl group having 8 to 20 carbon atoms which is substituted with a halogen atom or is unsubstituted or
An arylalkyl group of 7 to 20 carbon atoms which is substituted with a halogen atom or which is unsubstituted,
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,
An alkyl group having 1 to 8 carbon atoms which is substituted with a nitro group, a carboxyl group, a sulfonic acid group, a hydroxyl group or a halogen atom, or 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 with 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 substituted or unsubstituted phenyl group,
A substituted or unsubstituted 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, an ester of a carboxyl group, an ester of a sulfonic acid group, Substituted or unsubstituted benzyl group.
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 connected to form a 6-membered ring,
R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , and R ¹⁵ and R ¹⁶ may be connected to form a 3- to 6-membered heterocyclic ring,
R ³ and R ⁴ and R ⁷ and R ⁸ may form a ring through a single bond, an oxygen atom, a sulfur atom, a selenium atom, CR ¹⁷ R ¹⁸ , CO, NR ¹⁹ , PR ²⁰ or SO ₂ ,
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 are each independently an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms or an unsubstituted or substituted alkoxy group having 1 to 8 carbon atoms which is substituted with a halogen atom ,
An ^{q -} represents an anion of q, q represents 1 or 2, and p represents a coefficient for keeping the charge neutral.
Provided that at least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is a hydrogen atom). The method according to claim 1,
Wherein at least one of R ⁴ and R ⁷ is a hydroxyl group, a halogen atom, an alkyl group having 1 to 8 carbon atoms which is substituted with a halogen atom, or an alkoxy group having 1 to 8 carbon atoms which may be substituted with a halogen atom, &Lt; / RTI &gt; A colored photosensitive composition comprising a dye (A) comprising the compound according to any one of claims 1 to 3, a polymerizable compound (B) having an ethylenically unsaturated bond and a photopolymerization initiator (C). The method of claim 3,
Further, the colored photosensitive composition contains at least one coloring material (excluding the compound represented by the above-mentioned general formula (I)). A cured product of the colored photosensitive composition according to claim 3 or 4. A color filter for a display device comprising at least a part of the cured product according to claim 5.

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