JP6062732B2 - Novel compound and colored photosensitive composition - Google Patents

Description

  The present invention relates to a novel compound suitable for a dye designed to have a desired hue and having improved solvent resistance and heat resistance. Furthermore, the present invention relates to a colored photosensitive composition that can be polymerized by energy rays using the dye, and a color filter that uses the colored photosensitive composition.

  Compounds having high intensity absorption for specific light include recording layers of optical recording media such as CD-R, DVD-R, DVD + R, BD-R, liquid crystal display devices (LCD), plasma display panels (PDP). ), An electroluminescence display (ELD), a cathode ray tube display (CRT), a fluorescent display tube, and an optical display element such as a field emission display.

In an optical filter for an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode ray tube display device (CRT), a fluorescent display tube, a field emission display, etc., 300 Various compounds that absorb light having a wavelength of ˜1100 nm are used as light absorbers.
These light absorbers are required to have particularly steep light absorption, that is, having a small half-value width of λmax and not to lose its function due to light, heat, or the like.

An optical filter mainly used for a liquid crystal display (LCD) includes a color filter. In general, three primary colors of RGB have been used for a color filter, but it is difficult to have a pure RGB hue with a single color material, and a pure RGB hue using a plurality of color materials. Efforts have been made to get closer to. Therefore, color materials such as yellow, orange and purple are required instead of RGB.
Organic and / or inorganic pigments have been used as light absorbers for color filters due to their high heat resistance. However, since they are pigments, there is a problem in that the luminance of a display device is lowered. This problem has been solved by increasing the brightness of the. However, with the trend toward lower power consumption, development of color filters using dyes has become active.

In recent years, in color filters used in solid-state imaging devices, it is required to reduce the color pattern from the viewpoint of improving the image quality, and in order to reduce the thickness, it is necessary to increase the dye concentration in terms of color density. . In addition, a large amount of dye must be added even when the molar absorption coefficient of the dye is low.
However, when the dye concentration is increased, elution and precipitation of pigment from the formed pixels are observed after film formation, and when heat treatment (post bake) is performed after film formation, between adjacent pixels and in the laminated structure The problem is that color mixing tends to occur between the upper and lower layers.

Patent Document 1 discloses a dye monomer and a polymer thereof, Patent Document 2 discloses a hologram recording material containing a dye having a polymerizable group, and Patent Document 3 discloses A two-photon absorption optical recording material containing a dye having a polymerizable group is disclosed, and Patent Document 4 discloses a photosensitive coloring composition containing a triarylmethane dye monomer having a polymerizable group in an anion. Is disclosed.
However, the compounds having a polymerizable group described in these documents are not satisfactory in terms of solvent resistance and heat resistance.

JP 11-246627 A JP 2005-275158 A JP 2009-086299 A Japanese Patent No. 4266627

  Accordingly, an object of the present invention is to provide a novel compound suitable for a dye having excellent solvent resistance and heat resistance. Another object of the present invention is to provide a colored photosensitive composition (colored alkali-developable photosensitive composition) using the above dye. Another object of the present invention is an optical filter using the colored photosensitive composition (colored alkali-developable photosensitive composition), particularly suitable for an image display device such as a liquid crystal display panel without reducing luminance. It is to provide a color filter.

  As a result of intensive studies, the present inventors have found that a compound having a specific structure is excellent in heat resistance and excellent in solvent resistance in a colored photosensitive composition (colored alkali-developable photosensitive composition). The above-described colored photosensitive composition (colored alkali-developable photosensitive composition) is suitable for color filters for image display devices such as liquid crystal display panels, without reducing the brightness of optical filters (particularly color filters). It was discovered that the present invention was reached.

  This invention is made | formed based on the said knowledge, and provides the compound represented by following General formula (1).

（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁及びＲ₁₂は、それぞれ独立に、水素原子若しくはハロゲン原子、シアノ基、ニトロ基、水酸基、ハロゲン原子で置換されている若しくは無置換の炭素原子数１〜８のアルキル基又はハロゲン原子で置換されている若しくは無置換の炭素原子数１〜８のアルコキシ基を表し、
Ｒ₁₃、Ｒ₁₄、Ｒ₁₅、Ｒ₁₆、Ｒ₁₇及びＲ₁₈は、それぞれ独立に、炭素原子数１〜８のアルキル基又は下記一般式(II)で表される置換基を表し、Ｒ₂とＲ₁₃、Ｒ₃とＲ₁₄、Ｒ₆とＲ₁₅、Ｒ₇とＲ₁₆、Ｒ₁₀とＲ₁₇及びＲ₁₁とＲ₁₈は、連結して６員環を形成していてもよく、Ｒ₁₃とＲ₁₄、Ｒ₁₅とＲ₁₆、及びＲ₁₇とＲ₁₈は、連結して３〜６員環の複素環を形成していてもよく、
Ｒ₁₃、Ｒ₁₄、Ｒ₁₅、Ｒ₁₆、Ｒ₁₇及びＲ₁₈のうち少なくとも一つは、下記一般式（II）で表される置換基であり、
Ａｎ^q-はｑ価のアニオンを表し、ｑは１又は２を表し、ｐは電荷を中性に保つ係数を表す。）

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a hydrogen atom or a halogen atom. , A cyano group, a nitro group, a hydroxyl group, a halogen atom-substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a halogen atom-substituted or unsubstituted alkoxy group having 1 to 8 carbon atoms Represents
_{R 13, R 14, R 15} , R 16, R 17 and R ₁₈ are independently an alkyl group or 1 to 8 carbon atoms is a substituent represented by the following general formula (II), R ₂ and R ₁₃ , R ₃ and R ₁₄ , R ₆ and R ₁₅ , R ₇ and R ₁₆ , R ₁₀ and R ₁₇ and R ₁₁ and R ₁₈ may be linked to form a 6-membered ring, R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , and R ₁₇ and R ₁₈ may be linked to form a 3- to 6-membered heterocyclic ring,
At least one of R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ is a substituent represented by the following general formula (II):
An ^q− represents a q-valent anion, q represents 1 or 2, and p represents a coefficient for keeping the charge neutral. )

（式中、Ｒ₁₉は、水素原子、メチル基又はハロゲン原子を表し、
Ｚ₁は、メチレン基が−ＯＣＯ−ＮＨ−若しくは−ＮＨ−ＯＣＯ−で置き換えられた二価の炭素原子数１〜３５のアルカンジイル基又は二価の炭素原子数２〜３５のアルケンジイル基を表し、
Ｚ ₂ は、−Ｃ（Ｈ） _3-a を表し、
Ｚ ₃ は、二価の炭素原子数１〜３５のアルカンジイル基又は二価の炭素原子数２〜３５のアルケンジイル基を表し、
ａは、１〜３の数である。）

(Wherein R ₁₉ represents a hydrogen atom, a methyl group or a halogen atom,
Z ₁ represents a divalent C1-C35 alkanediyl group or a divalent C2-C35 alkenediyl group in which a methylene group is replaced by —OCO—NH— or —NH—OCO—. ,
Z ₂ represents -C (H) _3-a,
Z ₃ represents a divalent C1-C35 alkanediyl group or a divalent C2-C35 alkenediyl group ,
a is a number from 1 to 3. )

  In addition, the present invention provides a colored photosensitive composition comprising a dye (A) comprising the compound represented by the general formula (I), a polymerizable compound (B) having an ethylenically unsaturated bond, and a photopolymerization initiator (C). The composition is provided.

  In addition, as a preferred form of the colored photosensitive composition, the present invention includes an ethylenically unsaturated group having an alkali-soluble substituent that gives alkali developability as the polymerizable compound (B) having the ethylenically unsaturated bond. The present invention provides a colored photosensitive composition (colored alkali-developable photosensitive composition) having alkali developability using a polymerizable compound (B ′) having a bond.

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

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

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

  First, the compound of the present invention will be described. The compound of the present invention is a novel compound represented by the above general formula (I) and has a substituent represented by the above general formula (II) in its structure.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R in the general formula (I) _15, as the unsubstituted alkyl group having 1 to 8 carbon atoms represented by R _16, R ₁₇ and R _18, methyl, ethyl, propyl, iso- propyl, butyl, sec- butyl, tert- butyl, iso -Butyl, amyl, iso-amyl, tert-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1- Octyl, iso-octyl, tert-octyl and the like,
_{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17 And a C 1-8 alkyl group substituted with a cyano group, a nitro group, a hydroxyl group or a halogen atom represented by R ₁₈ is one of the hydrogen atoms in the alkyl group having 1-8 carbon atoms. A group in which part or all are substituted with a cyano group, a nitro group, a hydroxyl group or a halogen atom,
Unsubstituted alkoxy having 1 to 8 carbon atoms represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ The groups include methyloxy, ethyloxy, iso-propyloxy, butyloxy, sec-butyloxy, tert-butyloxy, iso-butyloxy, amyloxy, iso-amyloxy, tert-amyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy Cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy, tert-heptyloxy, 1-octyloxy, iso-octyloxy, tert-octyloxy and the like And
₁ carbon atom substituted with a halogen atom represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ Examples of the alkoxy group having 8 to 8 include groups in which part or all of the hydrogen atoms in the alkoxy group having 1 to 8 carbon atoms are substituted with a halogen atom.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R in the general formula (I) ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ , an alkyl group having 1 to 8 carbon atoms, and a phenyl group or benzyl represented by R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ Examples of the halogen atom that substitutes the group include fluorine, chlorine, bromine, and iodine.
Examples of the alkyl group having 1 to 4 carbon atoms that substitutes the phenyl group or benzyl group represented by R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ include methyl, ethyl, propyl, and iso-propyl. , Butyl, sec-butyl, tert-butyl, iso-butyl and the like.

In the above general formula (I), R ₂ and R ₁₃ , R ₃ and R ₁₄ , R ₆ and R ₁₅ , R ₇ and R ₁₆ , R ₁₀ and R _17, and R ₁₁ and R ₁₈ may be linked. Examples of the 6-membered ring include a piperidine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, and an isoquinoline ring.
In the above general formula (I), the 3- to 6-membered heterocyclic ring that can be formed by linking R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , and R ₁₇ and R ₁₈ includes a piperidine ring, a piperazine ring, Examples include pyrrolidine ring, morpholine ring, thiomorpholine ring, pyridine ring, pyrazine ring, pyrimidine ring, quinoline ring, isoquinoline ring, imidazole ring, oxazole ring, imidazolidine ring, pyrazolidine ring, isoxazolidine ring, isothiazolidine ring, etc. These rings may be fused or substituted with other rings.

In the general formula (II), the halogen atom represented by R ₁₉ , R ₂₀ and R ₂₁ , and the alkyl group having 1 to 8 carbon atoms represented by R ₂₂ are exemplified in the general formula (I). Group.
Examples of the aryl group having 6 to 30 carbon atoms represented by R ₂₀ and R ₂₁ include phenyl and naphthyl.
Examples of the arylalkyl group having 7 to 30 carbon atoms represented by R ₂₀ and R ₂₁ include benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl and the like.
Examples of the divalent C1-C35 alkanediyl group represented by Z ₁ and Z ₃ include methane, ethane, propane, isopropane, cyclopropane, butane, second butane, tertiary butane, and isobutane. , Pentane, isopentane, tertiary pentane, cyclopentane, hexane, 2-hexane, 3-hexane, cyclohexane, bicyclohexane, 1-methylcyclohexane, heptane, 2-heptane, 3-heptane, isoheptane, tertiary heptane, n- And alkane diyl groups such as octane, isooctane, tertiary octane, 2-ethylhexane, nonane, isononane, and desane.
Examples of the divalent alkenediyl group having 2 to 35 carbon atoms represented by Z ₁ and Z ₃ include vinylene, 1-methylethene, 2-methylethene, 2-propene, 1-methyl-3-propene, 3-butene, Alkene diyl groups such as 1-methyl-3-butene, isobutene, 3-pentene, 4-hexene, cyclohexene, bicyclohexene, heptene, octene, decene, pentadecene, eicosene, tricosene, etc.
Methylene groups in the alkanediyl group or an alkenediyl group, -O -, - S -, - SO 2 -, - CO -, - COO -, - OCO -, - NH-, an aromatic hydrocarbon group or those It may be replaced with a combined linking group.
Examples of the arylalkanediyl group having 6 to 35 carbon atoms represented by Z ₁ and Z ₃ include diyl groups of arylalkanes such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, and the like.
Examples of the aryldiyl group having 6 to 35 carbon atoms represented by Z ₁ and Z ₃ include diyl groups of aryl groups such as phenyl and naphthyl,
The methylene group in the arylalkanediyl group is —O—, —S—, —SO ₂ —, —CO—, —COO—, —OCO—, —NH—, an aromatic hydrocarbon group or a combination thereof. It may be replaced with a linking group.
Among the substituents represented by Z ₁ , an alkanediyl group having 1 to 35 carbon atoms or an alkenediyl group having 2 to 35 carbon atoms in which a methylene group is replaced by —OCO—NH— or —NH—COO—, In particular, an alkanediyl group having 1 to 3 carbon atoms or an alkenediyl group having 2 to 6 carbon atoms in which a methylene group is replaced by —OCO—NH— is preferable because of high solubility.

Examples of the anion represented by An ^q- in the above general formula (I) include monovalent ions such as chloride ions, bromide ions, iodide ions, fluoride ions, and the like; perchlorine Inorganic anions such as acid ion, chlorate ion, thiocyanate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tetrafluoroborate ion; methanesulfonate ion, dodecylsulfonate ion, benzenesulfonate ion, Toluenesulfonic acid ion, trifluoromethanesulfonic acid ion, naphthalenesulfonic acid ion, diphenylamine-4-sulfonic acid ion, 2-amino-4-methyl-5-chlorobenzenesulfonic acid ion, 2-amino-5-nitrobenzenesulfonic acid ion, JP 10-235999 A, JP 0-337959, JP-A-11-102888, JP-A-2000-108510, JP-A-2000-168223, JP-A-2001-209969, JP-A-2001-322180, JP-A-2006-248180, JP-A-2006-297907, JP-A-8- Organic sulfonate anions such as sulfonate ions described in JP-A-253705, JP-T-2004-503379, JP-A-2005-336150, International Publication 2006/28006, etc .; Octyl phosphate ion, dodecyl phosphorus Organic phosphate anions such as acid ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphonate ion, bistri Fluoromethylsulfonylimide ion Bisperfluorobutanesulfonylimide ion, perfluoro-4-ethylcyclohexanesulfonate ion, tetrakis (pentafluorophenyl) borate ion, tris (fluoroalkylsulfonyl) carboanion, etc. are mentioned. Benzene disulfonate ion, naphthalenedisulfonate ion and the like. In addition, quencher anions that have the function of deexciting (quenching) active molecules in the excited state, and ferrocenes having an anionic group such as a carboxyl group, phosphonic acid group, or sulfonic acid group on the cyclopentadienyl ring. Metallocene compound anions such as luteocene can also be used as necessary. Also, p is selected so that the charge is neutral throughout the molecule.

  Examples of the quencher anion include, for example, JP-A-60-234892, JP-A-5-43814, JP-A-5-305770, JP-A-6-239028, JP-A-9-309886. JP-A-9-323478, JP-A-10-45767, JP-A-11-208118, JP-A-2000-168237, JP-A-2002-201373, JP-A-2002-206061, Examples include anions as described in JP-A-2005-297407, JP-B-7-96334, WO98 / 29257, and the like.

Examples of the anion represented by An ^q- in the general formula (I) include a monovalent organic sulfonic acid anion, bistrifluoromethylsulfonylimide ion, bisperfluorobutanesulfonylimide ion, and perfluoro-4- Ethylcyclohexanesulfonate ion, benzenedisulfonate ion, and naphthalenedisulfonate ion are preferable from the viewpoint of heat resistance, and bistrifluoromethylsulfonylimide ion is more preferable.

  Specific examples of the cation moiety of the compound represented by the general formula (I) of the present invention include the following compound No. 1-No. 18 is mentioned.

Among the compounds represented by the general formula (I), the following are preferable.
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are preferably hydrogen atoms from the viewpoint of ease of synthesis.
R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are preferably an alkyl group having 1 to 8 carbon atoms or a substituent represented by the above general formula (II) from the viewpoint of solvent solubility. .
Since Z ₁ in the general formula (II) has high solubility, the alkanediyl group having 1 to 35 carbon atoms or the number of carbon atoms in which the methylene group is replaced by —OCO—NH— or —NH—COO— An alkenediyl group having 2 to 35 carbon atoms is preferable, and an alkanediyl group having 1 to 3 carbon atoms or a alkenediyl group having 2 to 6 carbon atoms in which a methylene group is replaced by —OCO—NH— is preferable.
Z ₂ is preferably —C (H) _{3 -a} from the viewpoint of solvent solubility,
Z ₃ is preferably an alkanediyl group having 1 to 35 carbon atoms or an alkenediyl group having 2 to 35 carbon atoms, particularly an alkanediyl group having 1 to 3 carbon atoms or 2 carbon atoms from the viewpoint of solvent solubility. -6 alkenediyl groups are preferred.

  Although the manufacturing method of the compound represented by the said general formula (I) is not specifically limited, For example, it can manufacture according to following Reaction Formula. The substituent represented by the general formula (II) can be introduced by a conventionally known organic reaction such as a condensation reaction such as an esterification reaction or an addition reaction.

（式中、Ｒ₁〜Ｒ₁₈は、上記一般式（Ｉ）と同じである。）

(Wherein R _{1 to} R ₁₈ are the same as those in the general formula (I)).

  The compound represented by the general formula (I) is used as a colored alkali-developable photosensitive composition described below, as well as an optical filter used for a display or an optical lens, a silver salt photographic photosensitive material, a dyed material, and a paint. Used for optical recording dyes and the like.

  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 later is appropriately described as a colored composition.

  The coloring composition of the present invention comprises a dye (A) comprising the compound of the present invention (hereinafter also referred to as dye (A)), a polymerizable compound (B) having an ethylenically unsaturated bond (alkali-soluble to impart alkali developability) And a polymerizable compound (B ′) having an ethylenically unsaturated bond), and a photopolymerization initiator (C), and if necessary, a coloring material (however, in the above general formula (I)) 1 type or more (D) except the dye which consists of a compound represented.

  Dye (A) used by this invention should just contain at least 1 type of the compound of this invention, and can be used individually or in combination of multiple types. In addition to the compound of the present invention, a known dye can be used as the dye (A). Known dyes include, for example, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes. , Phthalocyanine dyes, cyanine dyes, and the like. 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, more preferably 70 to 100% by mass. When content of the compound of this invention is smaller than 50 mass%, the solubility to a solvent may fall or heat resistance may fall.

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

<Polymerizable compound (B) having an ethylenically unsaturated bond>
The polymerizable compound (B) having an ethylenically unsaturated bond is not particularly limited, and those conventionally used in photosensitive compositions can be used. For example, ethylene, propylene, butylene, isobutylene can be used. , Vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, and other unsaturated aliphatic hydrocarbons; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, highmic acid, Crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] , A carboxy group and a hydroxyl group at both ends of ω-carboxypolycaprolactone mono (meth) acrylate, etc. Mono (meth) acrylate, hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or one carboxyl group and two or more (meth) acryloyl groups Unsaturated polybasic acids such as polyfunctional (meth) acrylates; (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, glycidyl (meth) acrylate, the following compound No. A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (t-butyl) (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meta ) Ethylhexyl acrylate, (meth) acrylic acid Phenoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-anhydrous Acid anhydrides of unsaturated polybasic acids such as rain acid adducts, dodecenyl succinic anhydride, methyl hymic anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyvalent amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinyl Unsaturated aromatic compounds such as ruphenol, vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; 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, allyl glycidyl ether; maleimide, N-phenylmaleimide, N -Unsaturated imides such as cyclohexylmaleimide; Indenes such as indene and 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene Macromolecules 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, polysiloxane, etc .; vinyl chloride, vinylidene chloride, divinyls Cuccinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomers and vinyl isocyanate compounds of polyisocyanate compounds, hydroxyl groups -Containing vinyl monomers and polyepoxy compounds such as vinyl epoxy compounds, pentaerythritol triacrylate and dipentaerythritol pentaacrylate Reaction products of polyfunctional isocyanates such as relate and tolylene diisocyanate and hexamethylene diisocyanate, hydroxyl-containing polyfunctional acrylates such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, etc. The polyfunctional acrylate which has an acid value which is a reaction product of a dibasic acid anhydride is mentioned.

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

  In the colored composition of the present invention, as the polymerizable compound (B) having an ethylenically unsaturated bond, a polymerizable compound (B) having an ethylenically unsaturated bond having an alkali-soluble substituent that imparts alkali developability. When ') (hereinafter also referred to as an alkali-developable compound (B') having an ethylenically unsaturated bond) is used, the colored photosensitive composition of the present invention becomes a colored alkaline-developable photosensitive composition. Examples of the alkali-developable compound (B ′) having an ethylenically unsaturated bond include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylates such as (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate; N-vinylpyrrolidone; styrene and derivatives thereof Styrenes such as α-methylstyrene; acrylamides such as (meth) acrylamide, methylol (meth) acrylamide, alkoxymethylol (meth) acrylamide, diacetone (meth) acrylamide; (meth) acrylonitrile, ethylene, propylene, butylene, Other vinyl compounds such as vinyl chloride and vinyl acetate, and macromonomers such as polymethyl methacrylate macromonomer and polystyrene macromonomer, monomethacrylate of tricyclodecane skeleton, N-phenylmaleimide, methacryloyloxymethyl-3-ethyloxetane, etc. And a copolymer of (meth) acrylic acid and an isocyanate compound having an unsaturated bond such as Karenz MOI and AOI manufactured by Showa Denko K.K. Copolymers of formic acid, novolac epoxy compounds such as phenol and / or cresol novolac epoxy resins, novolac epoxy resins having a biphenyl skeleton and a naphthalene skeleton, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds, A polyphenylmethane type epoxy resin having a functional epoxy group, obtained by allowing an unsaturated monobasic acid to act on an epoxy group such as an epoxy compound represented by the following general formula (I), and further reacting with a polybasic acid anhydride Resins can be used. These monomers can be used individually by 1 type or in mixture of 2 or more types. Moreover, it is preferable that the alkali developable compound (B ') which has the said ethylenically unsaturated bond contains 0.2-1.0 equivalent of unsaturated groups.

（式中、Ｘ¹は直接結合、メチレン基、炭素原子数１〜４のアルキリデン基、炭素原子数３〜２０の脂環式炭化水素基、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＳＳ−、−ＳＯ−、−ＣＯ−、−ＯＣＯ−又は下記式（イ）、（ロ）若しくは（ハ）で表される置換基を表し、該アルキリデン基はハロゲン原子で置換されていてもよく、Ｒ³¹、Ｒ³²、Ｒ³³及びＲ³⁴は、それぞれ独立に、水素原子、炭素原子数１〜５のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数２〜５のアルケニル基又はハロゲン原子を表し、上記アルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されていてもよく、ｒは０〜１０の整数である。）

(In the formula, X ¹ is a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, —O—, —S—, —SO ₂ —, -SS-, -SO-, -CO-, -OCO- or a substituent represented by the following formula (I), (B) or (C), wherein the alkylidene group may be substituted with a halogen atom R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyl having 2 to 5 carbon atoms. Represents a group or a halogen atom, and the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and r is an integer of 0 to 10.)

（式中、Ｙ²は、炭素原子数１〜１０のアルキル基若しくは炭素原子数１〜１０のアルコキシ基により置換されてもよいフェニル基、炭素原子数１〜１０のアルキル基若しくは炭素原子数１〜１０のアルコキシ基により置換されてもよい炭素原子数３〜１０のシクロアルキル基、又は、水素原子を表し、Ｙ¹は炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のアルケニル基又はハロゲン原子を表し、上記Ｙ¹におけるアルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されていてもよく、ｂは０〜５の整数である。）

(In the formula, Y ² is a phenyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or 1 carbon atom. Represents a cycloalkyl group having 3 to 10 carbon atoms which may be substituted by an alkoxy group having 10 to 10 carbon atoms, or a hydrogen atom, and Y ¹ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. Represents 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. )

（式中、Ｙ³及びＹ⁴は、それぞれ独立して、ハロゲン原子で置換されてもよい炭素原子数１〜１０のアルキル基、ハロゲン原子で置換されてもよい炭素原子数６〜２０のアリール基、ハロゲン原子で置換されてもよい炭素原子数６〜２０のアリールオキシ基、ハロゲン原子で置換されてもよい炭素原子数６〜２０のアリールチオ基、ハロゲン原子で置換されてもよい炭素原子数８〜２０のアリールアルケニル基、ハロゲン原子で置換されてもよい炭素原子数７〜２０のアリールアルキル基、ハロゲン原子で置換されてもよい炭素原子数２〜２０の複素環基、これらの基を複数組み合わせた基、又はハロゲン原子を表し、上記Ｙ³及びＹ⁴におけるアルキル基及びアリールアルキル基中のメチレン基は不飽和結合、−Ｏ−又は−Ｓ−で中断されていてもよく、Ｙ⁴は、隣接するＹ⁴同士で環を形成していてもよく、ｐは０〜４の整数を表し、ｑは０〜８の整数を表し、ｒは０〜４の整数を表し、ｓは０〜４の整数を表し、ｒとｓの数の合計は２〜４の整数である。）

Wherein Y ³ and Y ⁴ are each independently an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or an aryl having 6 to 20 carbon atoms which may be substituted with a halogen atom. Group, an aryloxy group having 6 to 20 carbon atoms that may be substituted with a halogen atom, an arylthio group having 6 to 20 carbon atoms that may be substituted with a halogen atom, and the number of carbon atoms that may be substituted with a halogen atom An arylalkenyl group having 8 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom, a heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom, and these groups; multiple combined group, or a halogen atom, a methylene group in the alkyl group and arylalkyl group in the Y ³ and Y ⁴ are interrupted by an unsaturated bond, -O- or -S- May have, Y ⁴ may form a ring with the adjacent Y ⁴ each other, p represents an integer of 0 to 4, q represents an integer of 0 to 8, r is 0 to 4 integer S represents an integer of 0 to 4, and the total number of r and s is an integer of 2 to 4.)

Examples of the unsaturated monobasic acid that acts on the epoxy group of the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, and the like. Examples thereof include hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate, and dicyclopentadiene / malate.
In addition, the polybasic acid anhydride to be acted after the unsaturated monobasic acid is allowed to act is biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride , Pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydro phthalic anhydride, methyl tetrahydro phthalic anhydride Acid, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2- Dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride Maleic anhydride adduct, dodecenyl succinic anhydride, and anhydride and methyl high Mick acid.

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows. That is, in the epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound, the hydroxyl group of the epoxy adduct is 1 It is preferable that the acid anhydride structure of the polybasic acid anhydride has a ratio of 0.1 to 1.0.
Reaction of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride can be performed in accordance with a conventional method.

  In order to improve the developability of the colored composition of the present invention that is colored alkali-developable photosensitive by adjusting the acid value, in addition to the alkali-developable compound having an ethylenically unsaturated bond, a monofunctional or polyfunctional epoxy compound is further added. Can be used. The alkali-developable compound having an ethylenically unsaturated bond preferably has a solid content acid value in the range of 5 to 120 mgKOH / g, and the use amount of the monofunctional or polyfunctional epoxy compound satisfies the acid value. It is preferable to select as follows.

  Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl. Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidylate , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl Ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinyl Cyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, propylene oxide, the above-mentioned compound no. A2, No. A3 etc. are mentioned.

It is preferable to use one or more selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers as the polyfunctional epoxy compound because a colored alkali-developable photosensitive composition with better characteristics can be obtained. As the bisphenol type epoxy compound, an epoxy compound represented by the above general formula (I) can be used, and for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used. Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1 , 10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-tri (g Glycidyl oxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) include methane.
Other novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxies such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl-p-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as cyclopentadiene dioxide; naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclopentadiene type epoxy compounds and the like can also be used.

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

  In the colored composition of the present invention, the content of the polymerizable compound (B) having the ethylenically unsaturated bond (including the alkali developable compound (B ′) having the ethylenically unsaturated bond) is the content of the present invention. In a coloring composition, 30-99 mass%, Especially 60-95 mass% is preferable. If 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 and cracks occur, or if it has alkali developability, development failure occurs. If it is larger than 99% by mass, curing due to exposure will be insufficient and tack will occur, or if it has alkali developability, the development time will be longer and the cured part will be filmed with alkali. There is a case.

<Photopolymerization initiator (C)>
As the photopolymerization initiator (C), conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethyl ketal, 1-benzyl- 1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholyl-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl Anthraquinone, 4-benzoyl-4′-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4′-isopropyl) benzoylpropane, 4-butyl Benzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9′-acridinyl) heptane, 9-n-butyl-3,6-bis (2′-morpholinoisobutyroyl) carbazole, 2 -Methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s -Triazine, 2,2-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1-2'-biimidazole, 4,4-azobisisobutyronitrile, triphenylphosphine, Examples include camphorquinone and benzoyl peroxide, and commercially available products include N-1414, N-1717, N-1919, PZ-4. 8, (manufactured by (Corporation) ADEKA Corporation) NCI-831, NCI-930, IRGACURE369, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02 (BASF (Co.) Co., Ltd.).

  Among the photopolymerization initiators (C), from the viewpoint of sensitivity and color tone, 2-morpholylu 2- (4′-methylmercapto) benzoylpropane, 9-n-butyl-3,6-bis (2′-morpholinoisopetite). Royl) carbazole is preferred, and 2-morpholylu 2- (4′-methylmercapto) benzoylpropane is more preferred.

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

  The coloring composition of the present invention may further contain a color material (D) other than the dye composed of the compound represented by the general formula (I). These color materials can be used alone or in admixture of two or more.

Examples of the color material (D) include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, Antanthrone compound, perinone compound, perylene compound, diketopyrrolopyrrole compound, thioindigo compound, dioxazine compound, triphenylmethane compound, quinophthalone compound, naphthalene tetracarboxylic acid; azo dye, metal complex compound of cyanine dye; lake pigment; furnace method, Carbon black obtained by channel method or thermal method, or carbon black such as acetylene black, ketjen black or lamp black; A product prepared by coating and coating with a epoxy resin, a carbon black previously dispersed with a resin in a solvent, adsorbed 20 to 200 mg / g of resin, and a carbon black treated with an acidic or alkaline surface The average particle size is 8 nm or more, the DBP oil absorption is 90 ml / 100 g or less, and the total oxygen amount calculated from CO and CO ₂ in the volatile content at 950 ° C. is 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 aerogel, fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin, chromium oxide green, miloli blue, cobalt green , Cobalt blue, manganese series, Fe Cyanide, phosphate ultramarine, bitumen, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, synthetic iron black, amber, etc. Inorganic pigments or organic pigments can be used.

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

  As the coloring material (D), a known dye can be used. Known dyes include, for example, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, Examples thereof include phthalocyanine dyes and cyanine dyes.

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

  A solvent can be further added to the coloring composition of the present invention. The solvent is usually a solvent that can dissolve or disperse each of the above components (the dye (A) comprising the compound of the present invention) as necessary, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl Ketones such as isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; acetic acid Ester solvents such as methyl, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ester Cellosolve solvents such as Tell; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl Ether ester solvents such as ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene; hexane, heptane and octane Aliphatic hydrocarbon solvents such as cyclohexane, terpene hydrocarbon oils such as turpentine oil, D-limonene, and pinene; mineral spirits, swazol # 310 (Cosmo Matsuyama Oil) Co., Ltd.), parasol solvents such as Solvesso # 100 (Exxon Chemical Co., Ltd.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; Halogenated aromatic hydrocarbon solvents; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, Water etc. are mentioned, These solvents can be used as 1 type, or 2 or more types of mixed solvents. Among these, ketones, ether ester solvents, etc., particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, and the like are preferable because the compatibility between the resist and the photopolymerization initiator (C) is good in the colored composition. .

  In the colored composition of the present invention, the amount of the solvent used is such that the concentration of the composition other than the solvent is preferably 5 to 30% by mass, and if it is less than 5% by mass, it is difficult to increase the film thickness. Yes, it is not preferable because it cannot absorb light of a desired wavelength sufficiently, and when it is larger than 30% by mass, the storage stability of the composition due to the precipitation of the composition may be reduced, or the handling may be reduced because the viscosity is improved. There is.

  The coloring composition of the present invention can further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; lamellar clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper Among these, titanium oxide, silica, layered clay mineral, silver and the like are preferable. In the colored composition of the present invention, the content of the inorganic compound is preferably 0.1 to 50 parts by mass, more preferably 0, relative to 100 parts by mass of the polymerizable compound (B) having the ethylenically unsaturated bond. It is 5-20 mass parts, and these inorganic compounds can use 1 type (s) or 2 or more types.

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

  In the coloring composition of the present invention, when a pigment and / or an inorganic compound is used, a dispersant can be added. As the dispersant, any pigment or inorganic compound can be used as long as it can disperse and stabilize, and commercially available dispersants such as BYK series manufactured by BYK Chemie, Inc. can be used. Polymer dispersant made of ether, polyurethane, having a nitrogen atom as a basic functional group, the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof, and an amine value of 1 to 100 mgKOH / g Are preferably used.

  In addition, the coloring composition of the present invention includes, if necessary, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; plasticizer; adhesion promoter; filler; Conventional additives such as an agent, a leveling agent, a surface conditioner, an antioxidant, an ultraviolet absorber, a dispersion aid, a coagulation inhibitor, a catalyst, an effect accelerator, a cross-linking agent, and a thickener can be added.

  In the colored composition of the present invention, optional components other than the dye (A), the polymerizable compound (B) having the ethylenically unsaturated bond, and the photopolymerization initiator (C) (however, the colorant (D) and The content of the solvent (excluding the solvent) is appropriately selected according to the purpose of use and is not particularly limited, but is preferably a total with respect to 100 parts by mass of the polymerizable compound (B) having the ethylenically unsaturated bond. And 50 parts by mass or less.

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

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

  As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- Mercapto compounds such as mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Alkyl compound, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, the following compound no. C1, aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, Showen Denko Karenz MT BD1, PE1, NR1, and the like.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

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

Examples of the melamine compound include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Mention may be made of compounds in which (at least two) are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used. Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.

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

  Moreover, as the light source of the active light used when curing the colored composition of the present invention, one that emits light having a wavelength of 300 to 450 nm can be used, for example, ultrahigh pressure mercury, mercury vapor arc, carbon arc. And xenon arc.

  Furthermore, by using laser light as the exposure light source, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used, but an argon ion laser, a helium neon laser, a YAG laser, a semiconductor laser, etc. are visible to infrared region. Those that emit light are also used. When these lasers are used, a sensitizing dye that absorbs light in the visible to infrared region is added.

  The colored composition of the present invention (or a cured product thereof) is a liquid crystal display panel for color display such as a photocurable paint or varnish, a photocurable adhesive, a printed board or a color TV, a PC monitor, a portable information terminal, a digital camera, Color filters, color filters for CCD image sensors, electrode materials for plasma display panels, powder coatings, printing inks, printing plates, adhesives, dental compositions, resin for stereolithography, gel coats, photoresists for electronics, Electroplating resist, etching resist, both liquid and dry film, solder resist, forming a structure in the manufacturing process of plasma display panel, electroluminescent display device, and LCD for manufacturing color filters for various display applications Resist, composition for encapsulating electrical and electronic components, solder Resist, magnetic recording materials, micromechanical components, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, materials for manufacturing 3D objects by stereolithography Holographic recording material, image recording material, fine electronic circuit, decoloring material, decoloring material for image recording material, decoloring material for image recording material using microcapsules, photoresist material for printed wiring board, UV and visible It can be used for various applications such as a photoresist material for a laser direct image system, a photoresist material used for forming a dielectric layer in the sequential lamination of printed circuit boards, or a protective film, and the application is not particularly limited.

The colored photosensitive composition of the present invention, which is a colored alkali-developable photosensitive composition, is used for the purpose of forming a pixel of a color filter, and is particularly a color for a display device for an image display device such as a liquid crystal display panel or an organic EL. It is useful as a photosensitive composition for forming a filter.
Moreover, the color filter for display devices of the present invention may have red, green, blue, orange, purple and black optical elements in addition to the cured product of the present invention.

The color filter for display device includes (1) a step of forming a coating film of the colored composition of the present invention (particularly a colored alkali-developable photosensitive composition) on a substrate, and (2) a predetermined pattern shape on the coating film. Preferably formed by a step of irradiating actinic light through a mask having, (3) a step of developing a film after exposure with a developer (particularly an alkali developer), and (4) a step of heating the film after development. Is done. The colored composition of the present invention is also useful as a colored composition for an ink jet system or a transfer system without a development step.
The production of a color filter for use in a liquid crystal display panel or the like is produced by repeating the above steps (1) to (4) using a coloring composition of the present invention or other combination, and combining patterns of two or more colors. Can do.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

Example 1-1 shows the synthesis example of the compound of this invention, Example 2-1 is the coloring photosensitive composition of this invention using the compound of this invention obtained in Example 1-1. Colored alkali-developable photosensitive composition No. Comparative Example 2-1 shows a comparative colored alkali-developable photosensitive composition No. 1 shows a preparation example.
In Evaluation Example 1-1, the colored alkali-developable photosensitive composition No. 1 obtained in Example 2-1. In Comparative Evaluation Example 1-1, the comparatively colored alkali-developable photosensitive composition No. 1 obtained in Comparative Example 2-1 was evaluated. The heat resistance of 1 was evaluated.

[Example 1-1] Compound No. 1 Synthesis of 1 bis (trifluoromethanesulfonyl) imide salt 0.13 g of the compound S-1 represented by the following [Chemical Formula 16] was dissolved in 5.00 g of dimethylacetamide, and 0.18 g of Karenz BEI (manufactured by Showa Denko KK) And 0.18 g of 3,5-dibutyl-4-hydroxytoluene, 0.06 g of ADK STAB BT-11 (dibutyltin laurate) was added dropwise at 20 ° C. while stirring under a nitrogen stream, and at 50 to 60 ° C. for 3 hours. Stir at 65 ° C. for 20 hours. The obtained reaction solution was poured into a separatory funnel charged with 40 ml of water and 40 ml of chloroform, shaken well, and the aqueous layer was discarded. Next, 0.16 g of potassium bis (trifluoromethanesulfonyl) imide dissolved in 20 g of water was added, and stirring at 30 to 35 ° C. for 1 hour was repeated three times. The organic layer was washed 3 times and the solvent was distilled off. The residue was purified by silica gel column chromatography (developing solvent: chloroform → chloroform / ethyl acetate = 1/1 → 3/7) to obtain 0.29 g (yield 90%) of a dark yellow solid.
Various analyzes were performed, and the resulting deep yellow solid was obtained as the target compound No. 1 was confirmed. The analysis results are shown in [Table 1] and [Table 2].

[Example 2-1 and Comparative Example 2-1] Colored alkali-developable photosensitive composition No. 1 and comparative colored alkali-developable photosensitive composition No. 1 Preparation of Compound No. 1 obtained in Example 1-1 as component (A) No. 1 bis (trifluoromethanesulfonyl) imide salt or comparative compound no. 1.43 g of 1 bis (trifluoromethanesulfonyl) imide salt, 18.48 g of V-259 (manufactured by Nippon Steel Chemical Co., Ltd.) as component (B) and 8.40 g of KAYARAD R-684 (manufactured by Nippon Kayaku Co., Ltd.) (C) 0.37 g of OXE-01 (manufactured by BASF), 42.09 g of PGMEA and 27.14 g of dimethylacetamide as the component (E), and FZ2122 (Toray Dow Corning Co., Ltd.) as the other components 2.10 g) was mixed and stirred until the insoluble matter disappeared, and the colored alkali-developable photosensitive composition No. 1 and comparative colored alkali-developable photosensitive composition No. 1 1 was obtained.

[Evaluation Example 1-1 and Comparative Evaluation Example 1-1] Evaluation of heat resistance by baking The colored alkali-developable photosensitive composition No. 1 obtained in Example 2-1. 1 and comparative colored alkali-developable photosensitive composition No. 1 obtained in Comparative Example 2-1. 1 was coated on a glass substrate under conditions of 410 rpm × 7 seconds and dried on a hot plate (90 ° C., 90 seconds). The obtained coating film was exposed (150 mJ / cm ² ) with an ultrahigh pressure mercury lamp. The coated film after exposure was baked under conditions of 230 ° C. × 30 min. The absorbance of the coating film before firing (after exposure) and the absorbance of the coating film after firing at the maximum absorption wavelength (λmax) of the compound (dye) used were measured, and the absorbance of the coating film before firing (after exposure) was 100. And evaluated as relative strength. In addition, it shows that heat resistance is so high that the light absorbency of the coating film after baking is close to 100. Further, the color difference (ΔE _{ab *} ) before and after firing was examined. The results are shown in [Table 3].

From the above results, it is clear that the colored alkali-developable photosensitive composition using the compound of the present invention as a dye has little change in color difference and high heat resistance.
Therefore, the colored photosensitive composition of the present invention, which is a colored alkali-developable photosensitive composition using the compound of the present invention as a dye, is useful for a color filter for a display device.

Claims (5)

The compound represented by the following general formula (I).

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a hydrogen atom or a halogen atom. , A cyano group, a nitro group, a hydroxyl group, a halogen atom-substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a halogen atom-substituted or unsubstituted alkoxy group having 1 to 8 carbon atoms Represents
_{R 13, R 14, R 15} , R 16, R 17 and R ₁₈ are independently an alkyl group or 1 to 8 carbon atoms is a substituent represented by the following general formula (II), R ₂ and R ₁₃ , R ₃ and R ₁₄ , R ₆ and R ₁₅ , R ₇ and R ₁₆ , R ₁₀ and R ₁₇ and R ₁₁ and R ₁₈ may be linked to form a 6-membered ring, R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , and R ₁₇ and R ₁₈ may be linked to form a 3- to 6-membered heterocyclic ring,
At least one of R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ is a substituent represented by the following general formula (II):
An ^q− represents a q-valent anion, q represents 1 or 2, and p represents a coefficient for keeping the charge neutral. )

(Wherein R ₁₉ represents a hydrogen atom, a methyl group or a halogen atom,
Z ₁ represents a divalent C1-C35 alkanediyl group or a divalent C2-C35 alkenediyl group in which a methylene group is replaced by —OCO—NH— or —NH—OCO—. ,
Z ₂ represents -C (H) _3-a,
Z ₃ represents a divalent C1-C35 alkanediyl group or a divalent C2-C35 alkenediyl group ,
a is a number from 1 to 3. ) A colored photosensitive composition comprising a dye (A) comprising the compound according to claim 1, a polymerizable compound (B) having an ethylenically unsaturated bond, and a photopolymerization initiator (C). Furthermore, the coloring photosensitive composition of Claim 2 containing 1 or more types (D) of coloring materials (however, except the dye which consists of a compound represented with the said general formula (I)). Hardened | cured material of the coloring photosensitive composition of Claim 2 or 3 . The color filter for display devices which comprises the hardened | cured material of Claim 4 at least in part.