JP5928253B2 - Coloring composition and color filter using the same - Google Patents

Description

  The present invention relates to a colored composition, and more particularly to a colored composition for a color filter used for a liquid crystal display device or a solid-state imaging device. Moreover, this invention relates to the color filter formed using this coloring composition.

A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.
Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher.

For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.
In the case of the pigment dispersion method, a colored composition (pigment resist) in which a pigment is dispersed in a photosensitive resin solution is applied to a transparent substrate such as glass, the solvent is removed by drying, and then pattern exposure of one filter color is performed. Then, the unexposed area is removed in the development process to form the first color pattern, and after processing such as heating as necessary, the same operation is sequentially repeated for all filter colors to produce a color filter. Can do.

  In recent years, color liquid crystal display devices have become widespread as liquid crystal color televisions, monitors for car navigation and desktop personal computers, notebook personal computers with integrated liquid crystal display devices, portable electronic devices with liquid crystal display devices, etc., and have formed a large market. Yes. In a color filter in which filter segments of each color are arranged, demands for high brightness, high contrast, and high color reproducibility are increasing. In particular, in portable applications and the like, it may be assumed to be used outdoors, and reliability including light resistance is required.

  In order to increase the brightness and contrast of the color filter, a finer pigment tends to be used as a colorant. In order to improve the color reproducibility of the color filter, it is necessary to increase the pigment content in the coloring composition or to increase the film thickness, but in the method of increasing the pigment content, In the method of increasing the film thickness, the exposure light does not reach the bottom of the film and the pattern shape becomes defective. Likely to happen. Then, in order to improve the sclerosis | hardenability in pattern formation, the coloring composition is a tendency of high sensitivity.

  Among them, in a color filter for a color composition for displaying green and blue, it is common to use a pigment containing a phthalocyanine skeleton, and the pigment containing a phthalocyanine skeleton is irradiated with light in the absence of oxygen. It is known to change color when done. Therefore, in the case of a liquid crystal display device used in a state where it is shielded from air, when a phthalocyanine dye is used as a color material for a color filter, suppression of discoloration as in Patent Document 1 has been studied. In recent years, with the increase in brightness and contrast of color filters, discoloration due to light irradiation in the absence of oxygen has become a problem even when pigments containing a phthalocyanine skeleton are used, and improvements are required. Yes.

  When a pigment containing a phthalocyanine skeleton is used, a method of adding a specific compound as in Patent Document 2 has been studied in order to suppress discoloration due to light irradiation. However, since these compounds have a property of deactivating radicals generated by light irradiation, problems such as deterioration in curability in pattern formation and reduction in sensitivity occur.

Japanese Patent No. 2661135 JP 2000-214580 A

  An object of the present invention is to provide a highly reliable coloring composition that does not cause discoloration due to light irradiation in the absence of oxygen, such as a color filter, and a color filter using the same.

The present invention is a color filter coloring composition comprising at least a β-hydroxyalkylamide (A), a polymer (B) containing a carboxyl group, and a pigment (C) represented by the following general formula (1). The pigment (C) contains a phthalocyanine pigment represented by the following general formula (1).
General formula (1)
[Wherein, X _{1 to} X ₄ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. A heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or a substituent. Represents an optionally substituted arylthio group.
Y _{1 to} Y ₄ each independently represents a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group.
M represents Zn or Al-Z.
Z represents a hydroxyl group, a chlorine atom, —OP (═O) R ₈₅ R ₈₆ , or —O—SiR ₈₇ R ₈₈ R ₈₉ , wherein R _{85 to} R ₈₉ are each independently a hydrogen atom, a hydroxyl group, or a substituent. Represents an alkyl group that may have a group, an aryl group that may have a substituent, an alkoxyl group that may have a substituent, or an aryloxy group that may have a substituent, R ₈₅ to R ₈₉ each other may be sintered combined together to form a ring.
m ₁ , m ₂ , m ₃ , m ₄ , n ₁ , n ₂ , n ₃ , and n ₄ each independently represent an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + N ₃ and m ₄ + n ₄ are each 0 to 4, and may be the same or different. ]

  Further, the present invention relates to the colored composition, wherein at least one of β-hydroxyalkylamide (A) or a polymer (B) containing a carboxyl group contains a photopolymerizable functional group.

  Moreover, this invention relates to the said coloring composition which contains a photopolymerizable monomer (D) and / or a photoinitiator (E) further.

The present invention also relates to the colored composition, wherein the β-hydroxyalkylamide (A) is a compound represented by the following general formula (101).
Formula (101)
[Wherein X is an n-valent group consisting of carbon, hydrogen, oxygen, nitrogen, sulfur, or halogen, n is an integer of 2 to 6, and R ¹ and R ² are each independently a hydrogen atom Represents an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by the general formula (102), or a group represented by the general formula (103), and one or more nitrogen atoms At least one of R ¹ and R ² bonded to is a group represented by the general formula (102). ]
General formula (102)
General formula (103)
[Wherein R ^{3 to} R ⁶ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxyl group, and R ⁷ is a residue of a compound having a functional group capable of reacting with a hydroxyl group. Represents. ]

  In the present invention, in the compound having a functional group capable of reacting with the hydroxyl group, the functional group capable of reacting with the hydroxyl group is a carboxyl group, an isocyanate group, a carboxylic acid anhydride group, an acid halide group, or a carboxylic acid. The present invention relates to the coloring composition, which is at least one selected from the group consisting of a tertiary alkyl ester group, a hydroxymethylamino group, an alkoxysilyl group and an epoxy group.

  In addition, the present invention relates to the colored composition, wherein the compound having a functional group capable of reacting with the hydroxyl group is a monofunctional isocyanate or a monofunctional carboxylic acid.

In the present invention, the compound having a functional group capable of reacting with the hydroxyl group is represented by at least one selected from the group consisting of the following general formula (104), general formula (105) and general formula (106). It is related with the said coloring composition characterized by the above-mentioned.
General formula (104)
[Wherein, R ⁸ represents a linear, cyclic or branched saturated or unsaturated hydrocarbon group having 2 to 18 carbon atoms. ]
General formula (105)
[Wherein R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ is a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic group. A hydrocarbon group, and R ¹¹ is a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group. ]
Formula (106)

[Wherein, R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents a group represented by the general formula (107) or a group represented by the general formula (108). ]
General formula (107)
Wherein, n ¹ is an integer of 1-2. ]
Formula (108)
[Wherein R ¹⁴ represents a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group, and R ¹⁵ represents the number of carbon atoms. 6-13 linear or branched alkylene groups, divalent alicyclic hydrocarbon groups, or divalent aromatic hydrocarbon groups. ]

  In addition, the present invention relates to the colored composition, wherein the compound having a functional group capable of reacting with the hydroxyl group has a photopolymerizable functional group.

  The present invention also relates to the colored composition, wherein an atom directly bonded to a carbonyl group in X in the general formula (101) is a carbon atom not contained in an aromatic ring.

  In the coloring composition according to the invention, X in the general formula (101) is an n-valent aliphatic hydrocarbon group or an n-valent alicyclic hydrocarbon group having 6 or more carbon atoms. Related to things.

  The present invention also provides that the β-hydroxyalkylamide (A) is (a-1) a divalent or higher carboxylic acid or derivative thereof, and (a-2) a primary or at least one hydroxyl group at the β-position. A part of the hydroxyl group of (a-3) β-hydroxyalkylamide obtained by amidation with a secondary amine is reacted with (a-4) a compound having one or more functional groups capable of reacting with the hydroxyl group. It is related with the said coloring composition characterized by the above-mentioned.

  The present invention also relates to the colored composition, wherein the β-hydroxyalkylamide (A) is soluble in an organic solvent.

  Moreover, this invention relates to the said coloring composition for color filters.

Furthermore, this invention relates to the color filter characterized by providing the filter segment formed from the said coloring composition on a transparent substrate.

  The coloring composition of the present invention contains a β-hydroxyalkylamide and a polymer containing a carboxyl group, so that it does not change color even when irradiated with light in the absence of oxygen as in a color filter. Moreover, since this compound does not deactivate radicals, it does not adversely affect pattern formation. Therefore, a high-quality color filter can be obtained by using the coloring composition of the present invention.

  The present invention is described in detail below.

<Β-Hydroxyalkylamide (A)>
The structure of the β-hydroxyalkylamide (A) used in the present invention is not particularly limited as long as it is soluble in an organic solvent. For example, polymer derivatives obtained by polymerizing β-hydroxyethylacrylamide, tris (2-hydroxyethyl) isocyanurate derivatives, and the like can be mentioned. Preferably, it is a compound represented by General formula (101).

Formula (101)
In the formula, X is an n-valent group consisting of carbon, hydrogen, oxygen, nitrogen, sulfur, or halogen, and n is an integer of 2-6. Specific examples of X include an n-valent aliphatic hydrocarbon group having 2 or more carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group having a hetero atom.

  Examples of the halogen include fluorine, chlorine, bromine and iodine, and fluorine is preferable from the viewpoint of transparency. From the viewpoint of imparting flame retardancy, chlorine and bromine are preferred.

An n-valent group is a group obtained by removing n hydrogen atoms from a compound. Hereinafter, this is referred to as an n-valent group derived from the compound.

  Examples of the n-valent aliphatic hydrocarbon group include n-valent groups derived from alkanes, alkenes, and alkynes.

  Examples of alkanes include ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentaden, heptadecane, hexadecane, octadecane, nonadecane, icosane, heicosan, docosan, isobutane, isopentane, Neopentane, methylpentane, dimethylpentane, ethylmethylpentane, diethylpentane, methylhexane, tetramethylheptane, and the like. As the n-valent group derived from alkane, for example, 1,6-hexyl group, 1,7-heptyl group, 1,8-octyl group, 1,9-nonyl group, 1,10-decyl group, 1,11 -Undecyl group, 1,12-dodecyl group, 1,13-tridecyl group, 1,14-tetradecyl group, 1,15-pentadecyl group, 1,16-hexadecyl group, 1,17-heptadecyl group, 1,18- Octadecyl group, 1,19-nonadecyl group, 1,3,6-hexyl group, 1,4,7-heptyl group, 1,2,8-octyl group, 1,3,9-nonyl group, 1,3, Examples include 4,6-hexyl group, 1,4,6,7-heptyl group, 1,4,5,6,7-heptyl group and 1,2,3,4,5,6-hexyl group.

  Alkenes include ethylene, propylene, butylene, pentene, hexene, heptene, octene, nonene, decene, undecene, docene, tridecene, tetracene, pentadecene, heptadecene, hexadecene, octadecene, nonadecene, icosene, heicocene, dococene, methylpentene, etc. Is mentioned. Examples of the n-valent group derived from an alkene include a 1,6- (2-hexenyl) group, a 1,7- (2-heptenyl) group, a 1,8- (2-octenyl) group, and a 1,9- (2-nonenyl) group, 1,10- (2-decenyl) group, 1,11- (2-undecenyl) group, 1,12- (2-dodecenyl) group, 1,13- (2-tridecenyl) group 1,14- (2-tetradecenyl) group, 1,15- (2-pentadecenyl) group, 1,16- (2-hexadecenyl) group, 1,17- (2-heptadecenyl) group, 1,18- ( 2-octadecenyl) group, 1,19- (2-nonadecenyl) group, 1,3,6- (2-hexenyl) group, 1,4,7- (3-heptenyl) group, 1,2,8- ( 4-octenyl) group, 1,3,9- (5-nonenyl) group, 1,3,4,6- (2-hex) ) Group, 1,4,6,7- (3-Hepuseniru) group, 1,4,5,6,7- (3- Hepuseniru) group.

Alkynes include ethyne, propyne, butyne, pentyne, hexyne, peptin, octyne, nonin, decyne, undecine, dodecin, tridecine, icosin, henicosin,
Docosin, etc. Examples of the n-valent group derived from alkyne include 1,6- (
2-hexynyl) group, 1,7- (2-hepsinyl) group, 1,8- (2-octynyl) group,
1,9- (2-nonyl) group, 1,10- (2-decynyl) group, 1,11- (2-undecynyl) group, 1,12- (2-dodecynyl) group, 1,13- (2 -Tridecynyl) group, 1,
14- (2-tetradecynyl) group, 1,15- (2-pentadecynyl) group, 1,16- (
2-hexadecynyl) group, 1,17- (2-heptadecynyl) group, 1,18- (2-octadecynyl) group, 1,19- (2-nonadecynyl) group, 1,3,6- (2-hexynyl)
Group, 1,4,7- (3-hepsinyl) group, 1,2,8- (4-oxynyl) group, 1,3,
9- (5-nonyl) group, 1,3,4,6- (2-hexynyl) group, 1,4,6,7- (3
-Hepsinyl) group and 1,4,5,6,7- (3-Hepsinyl) group.

  Examples of the n-valent alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, methylcyclopentane, dimethylcyclopentane, trimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cyclohexene, methylcyclohexene, norbornane, norbornene, and bicyclo And n-valent groups derived from octene, decahydronaphthalene, adamantane, dimethyladamantane, and the like. For example, 1,1-cyclohexyl group, 1,2-cyclohexyl group, 1,3-cyclohexyl group, 1,4-cyclohexyl group, 1,2,4-cyclohexyl group, 1,3,5-cyclohexyl group, 1, Examples include 2,4,5-cyclohexyl group, 1,2,3,4,5,6-cyclohexyl group, 2,6-decahydronaphthyl group, 1,3-adamantyl group, 1,3,5-adamantyl group. .

  Examples of n-valent aromatic hydrocarbon groups include n-valent aromatic hydrocarbon groups derived from benzene, naphthalene, biphenyl, anthracene, toluene, xylene, ethylbenzene, tert-butylbenzene, diphenylethane, diphenylacetylene, 9,9-diphenylfluorene, and the like. Groups. For example, examples of the group in which an aromatic ring contains a carbon atom bonded to a carbonyl group include a phenylene group and a tolylene group. Examples of the group in which the carbon atom bonded to the carbonyl group is not contained in the aromatic ring include toluene-α, α-diyl group, ethylbenzene-α, β-diyl group, ethylbenzene-β, β-diyl group, 1,2-diphenyl. And ethane-1,2-diyl group.

  N-valent groups having heteroatoms (oxygen, sulfur, nitrogen, halogen atoms) include ethanol, ethylene glycol, ethylene diacetate, ethylene dipivalate, ethylene dibenzoate, ethylene bis (methyl benzoate), ethylene bis (methoxy Benzoate), propanol, isopropanol, ethyl acetate, erythritol, ethylene oxide, acetaldehyde, acetone, dipropyl ketone, γ-pentadecanolactone, 1,2-cyclohexane, γ-butyrolactone, ethylamine, ethylmethylamine, propylamine, N- Propylacetamide, ethanethiol, ethanedithiol, tetrafluoroethane, dibromoethane, hexafluoropropane, octofluorobutane, dodecafluorohexane, hexadecaf Fluorooctane, 1,2,3,4,7,7-hexachloronorbornene, anisole, fluorobenzene, tetrafluorobenzene, trifluoromethylbenzene, chlorobenzene, dichlorobenzene, tetrafluorobenzene, bromobenzene, tetrabromobenzene, nitrobenzene, phenol Aniline, benzenesulfonic acid, anthraquinone, butanephosphonic acid, triethyltriazine, tripropyltriazine, triethylisocyanurate, tripropylisocyanurate, benzophenone, thiophene, diethylsulfide, diphenylsulfone, 2,2-diphenyl-1,1,1 , 3,3,3-hexafluoropropane, diphenyl ether, and the like.

  Among these, as X, from the viewpoint of reactivity, it is preferable that the atom in X that is directly bonded to the carbonyl group is a carbon atom that is not included in the aromatic ring. Further, a linear aliphatic hydrocarbon group having 6 to 18 carbon atoms or an alicyclic hydrocarbon group is preferable, and more preferably a linear aliphatic hydrocarbon group having 6 to 12 carbon atoms, or It is an alicyclic hydrocarbon group, More preferably, it is a C6-C12 linear aliphatic hydrocarbon group.

In the formula, each of R ¹ and R ² independently represents a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrogen group, an aromatic hydrocarbon group, a group represented by the general formula (102), or a general formula Of the one or more R ¹ and R ² bonded to one or more nitrogen atoms, at least one is a group represented by the general formula (102).

General formula (102)

General formula (103)

  Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.

As the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, decyl group , Dodecyl group, pentadecyl group, and octadecyl group.

  Examples of the alkenyl group include vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-octenyl group, 1-decenyl group and 1-octadecenyl group. Groups.

  Examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-octynyl group, 1-decynyl group and 1-octadecynyl group. .

  The alicyclic hydrocarbon group includes cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, 2-indeno group, decahydronaphthyl group, adamantyl group, dicyclopenta And a cycloalkyl group such as a nyl group.

Examples of the aromatic hydrocarbon group include a single ring, a condensed ring, and a ring assembly aromatic hydrocarbon group. The monocyclic aromatic hydrocarbon group includes monocyclic aromatic groups such as phenyl group, benzyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, p-cumenyl group and mesityl group. Group hydrocarbon group.
As the condensed ring aromatic hydrocarbon group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 5-anthryl group, 1-phenanthryl group, 9-phenanthryl group, 1-acenaphthyl group, Examples thereof include condensed ring aromatic hydrocarbon groups such as 2-azurenyl group, 1-pyrenyl group and 2-triphenylyl group.
Examples of the ring-assembled aromatic hydrocarbon group include ring-assembled aromatic hydrocarbon groups such as o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group.

Among them, R ¹ and R ² other than those represented by formula (102) and formula (103) are preferably an aliphatic hydrocarbon group, an alicyclic hydrocarbon, or a monocyclic aromatic hydrocarbon group, more preferably An aliphatic hydrocarbon group and an alicyclic hydrocarbon, and more preferably an aliphatic hydrocarbon group having 4 or more carbon atoms.

In the groups represented by formulas (102) and (103), R ^{3 to} R ⁶ each independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group partially substituted with a hydroxyl group, and R ⁷ represents a hydroxyl group. Represents a residue of a compound having a functional group capable of reacting with.

The hydrocarbon groups are the same as those described above for R ¹ and R ² . Examples of the hydrocarbon group substituted with a hydroxyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxyphenyl group, a hydroxycyclohexyl group, and the like.

  The residue of the compound having a functional group capable of reacting with a hydroxyl group is not particularly limited, but isocyanate, carboxylic acid, carboxylic acid halide, carboxylic acid anhydride, carboxylic acid ester, silanol, alkoxysilane, silanol ester, amino Examples thereof include resins, compounds having an epoxy, and the like, and isocyanates, carboxylic acids, carboxylic acid halides, and carboxylic anhydrides are preferable, and monofunctional isocyanates or monofunctional carboxylic acids are more preferable.

Among these, from the viewpoint of easy production, it is more preferable to obtain β-hydroxyalkylamide (A) in which R ⁷ in the general formula (103) is represented by the following general formula (201).
General formula (201)
here,
R ¹⁶ comprises a single bond, a (m ¹ +1) valent hydrocarbon group, or at least one of a urethane bond, a urea bond, an allophanate bond, a biuret bond, and an isocyanurate ring, and a carbon atom or a hydrogen atom (m ¹ +1) represents a valent group,
A ¹ represents a single bond, a urethane bond or a urea bond,
R ¹⁷ represents a divalent hydrocarbon group,
A ² represents an ether bond or an ester bond,
R ¹⁸ represents a monovalent hydrocarbon group,
m ¹ represents an integer of ¹ to 5,
p ¹ represents an integer of 0 to 100.

From the viewpoint of easy preparation, it is more preferable to obtain β-hydroxyalkylamide (A) in which R ⁷ in the general formula (103) is represented by the following general formula (202).
General formula (202)
here,
R ¹⁹ represents a single bond, a (m ² +1) valent hydrocarbon group, or a (m ² +1) valent group consisting of a carbon atom, a hydrogen atom, and an oxygen atom,
A ³ represents a single bond, an ester bond or an amide bond,
R ²⁰ represents a divalent hydrocarbon group,
A ⁴ represents an ether bond or an ester bond,
R ²¹ represents a monovalent hydrocarbon group,
m ² represents an integer of 1 to 5,
p ² is an integer of 0 to 100.

(Method for producing β-hydroxyalkylamide (A))
Although the compound represented by the general formula (101) can be produced by various methods, the main production methods [1] to [4] are listed below.

When at least one of R ¹ and R ² is a group represented by the general formula (103):

[1] A product obtained by amidating (a-1) a divalent or higher carboxylic acid or derivative thereof and (a-2) a primary or secondary amine having one or more hydroxyl groups at the β-position (a- 3) A part of the hydroxyl group of β-hydroxyalkylamide is reacted with a compound having (a-4) one or more functional groups capable of reacting with the hydroxyl group.

[2] (a-2) (a-4) having at least one functional group capable of reacting with a hydroxyl group as part of the hydroxyl group of a primary or secondary amine having at least one hydroxyl group at the β-position After reacting the compound, (a-1) amidation with a divalent or higher carboxylic acid or derivative thereof is performed.

[3] (a-2) A compound having one or more functional groups capable of reacting with a hydroxyl group by protecting the amino group of a primary or secondary amine having one or more hydroxyl groups at the β-position React. After removing the protecting group of this compound, (a-1) amidation with a divalent or higher carboxylic acid or derivative thereof is performed.

The method [1] is preferable in view of production cost, ease of reaction, and the like.

(A-3) When β-hydroxyalkylamide is available, (a-1) a divalent or higher carboxylic acid or derivative thereof, and (a-2) 1 having one or more hydroxyl groups at the β-position (A-3) a compound having at least one functional group capable of reacting with a hydroxyl group as a part of the hydroxyl group of (a-3) β-hydroxyalkylamide without undergoing a reaction of a secondary or secondary amine; The method of making it react may be sufficient.

When R ¹ and R ² are not a group represented by the general formula (103):

[4] Amidation of (a-1) a divalent or higher carboxylic acid or derivative thereof and (a-2) a primary or secondary amine having one or more hydroxyl groups at the β-position.

  β-hydroxyalkylamide (A) may or may not contain a photopolymerizable functional group. (A-1) a divalent or higher carboxylic acid or derivative thereof, (a-2) a primary or secondary amine having one or more hydroxyl groups at the β-position, or (a-4) a functional group capable of reacting with a hydroxyl group. A photopolymerizable functional group can be introduced by using a compound containing a photopolymerizable functional group as a compound having one or more groups. In view of stability during synthesis, (a-4) it is preferable to contain a photopolymerizable functional group in the compound having one or more functional groups capable of reacting with a hydroxyl group.

  (A-1) Among divalent or higher carboxylic acids or derivatives thereof, examples of divalent or higher carboxylic acids include the following. (Hereinafter, the same compound is expressed by <<). Linear saturated aliphatic dicarboxylic acid: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacin Acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid,

Branched saturated aliphatic dicarboxylic acids: methyl malonic acid, dimethyl malonic acid, ethyl malonic acid, dipropyl malonic acid, isopropyl malonic acid, methyl succinic acid, dimethyl succinic acid, butyl succinic acid, octyl succinic acid, decyl succinic acid, dodecyl succinic acid, tetra Decyl succinic acid, hexadecyl succinic acid, octadecyl succinic acid, methyl glutaric acid, dimethyl glutaric acid, ethyl methyl glutaric acid, diethyl glutaric acid, methyl adipic acid, tetramethyl pimelic acid,

Unsaturated aliphatic dicarboxylic acids: allyl succinic acid, methallyl succinic acid, hexenyl succinic acid, octenyl succinic acid, dodecenyl succinic acid, dococenyl succinic acid, decadiene-1,2-dicarboxylic acid, fumaric acid, maleic acid, acetylenedicarboxylic acid, muconic acid, itaconic acid Citraconic acid, mesaconic acid,

Alicyclic dicarboxylic acids: cyclopropanedicarboxylic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, camphoric acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, methylcyclohexenedicarboxylic acid, norbornanedicarboxylic acid, norbornenedicarboxylic acid, bicyclo [2.2.2] Oct-5-ene-2,3-dicarboxylic acid, adamantanedicarboxylic acid, cyclopentylmalonic acid, cyclopentanediacetic acid, cyclohexanediacetic acid, adamantanediacetic acid,

Aliphatic dicarboxylic acid having an aromatic ring (the carbon atom bonded to the carboxyl group does not form an aromatic ring): phenylmalonic acid, benzylmalonic acid, thiophenmalonic acid, phenylsuccinic acid, diphenylsuccinic acid,

Aliphatic or cycloaliphatic carboxylic acids containing oxygen atoms in addition to carboxyl groups: tartaric acid, diacetyltartaric acid, dipivaloyltartaric acid, dibenzoyltartaric acid, ditoluoyltartaric acid, di (p-anisoyl) tartaric acid, malic acid, acetylmalic acid, citric acid, citramal Acid, hydroxymethylglutaric acid, galactaric acid, epoxysuccinic acid, oxalacetic acid, oxoglutaric acid, oxoazelaic acid, 4,5-dicarboxy-γ-pentadecanolactone, 3,6-epoxy-1,2,3 6-hexahydrophthalic acid, butyrolactone dicarboxylic acid,

Aliphatic or alicyclic dicarboxylic acids containing nitrogen atom: aspartic acid, N-methylaspartic acid, N- (tert-butoxycarbonyl) -aspartic acid, N- (benzyloxycarbonyl) aspartic acid, N-carbamoylaspartic acid, N-[(9H-fluoren-9-ylmethoxy) carbonyl] aspartic acid, glycylaspartic acid, 3-hydroxyaspartic acid, glutamic acid, N-acetylglutamic acid, N- (tert-butoxycarbonyl) -glutamic acid, N- (benzyl Oxycarbonyl) glutamic acid, N-benzoylglutamic acid, N- (4-aminobenzoyl) glutamic acid, N-[(9H-fluoren-9-ylmethoxy) carbonyl] glutamic acid, methylglutamic acid, glycylglutamic acid Grayed azide Nino glutaric acid, N- phthalyl glutamic acid, amino adipic acid, aminopimelic acid, diaminopimelic acid, aminosuberic acid, folic acid, methotrexate,

Aliphatic or alicyclic dicarboxylic acids containing sulfur atoms: dimercaptosuccinic acid, thiomalic acid,

Aliphatic or alicyclic dicarboxylic acid containing a halogen atom: tetrafluorosuccinic acid, dibromosuccinic acid, hexafluoroglutaric acid, octafluoroadipic acid, dodecafluorosuberic acid, hexadecafluorosebacic acid, chlorendic acid «Het acid»,

Aromatic dicarboxylic acids: phthalic acid, methylphthalic acid, tert-butylphthalic acid, ethynylphthalic acid, (phenylethynyl) phthalic acid, methoxyphthalic acid, fluorophthalic acid, tetrafluorophthalic acid, trifluoromethylphthalic acid, chlorophthalic acid, dichloro Phthalic acid, tetrachlorophthalic acid, bromophthalic acid, tetrabromophthalic acid, nitrophthalic acid, hydroxyphthalic acid, aminophthalic acid, sulfophthalic acid, isophthalic acid, methylisophthalic acid bromoisophthalic acid, nitroisophthalic acid, hydroxyisophthalic acid, aminoisophthalic acid , Aminotriiodoisophthalic acid, sulfoisophthalic acid, terephthalic acid, dimethylterephthalic acid, tetrafluoroterephthalic acid, dichloroterephthalic acid, tetrachloroterephthalic acid, bromoterephthalic acid Tetrabromoterephthalic acid, nitroterephthalic acid, dihydroxyterephthalic acid, aminoterephthalic acid, sulfoterephthalic acid, naphthalene dicarboxylic acid, anthracene dicarboxylic acid, anthraquinone dicarboxylic acid, 1,3-dibenzyl-2-oxo-4,5-imidazolidine dicarboxylic acid Acid, thiophene dicarboxylic acid,

Aliphatic or alicyclic tricarboxylic acid: 1,2,3-propanetricarboxylic acid «tricarballylic acid», anicotic acid, butenetricarboxylic acid, cyclohexanetricarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 3- Butene-1,2,3-tricarboxylic acid, cyclohexanetricarboxylic acid, pentanetricarboxylic acid, tris (2-carboxyethyl) -1,3,5-triazine, tris (3-carboxypropyl) -1,3,5-triazine , Isocyanuric acid tris (2-carboxyethyl), isocyanuric acid tris (3-carboxypropyl),

Aromatic tricarboxylic acid: trimellitic acid, hemimellitic acid, benzene-1,3,5-tricarboxylic acid, benzophenone tricarboxylic acid,

Aliphatic or alicyclic tetracarboxylic acid: butanetetracarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, thiodisuccinic acid, tetrahydrofurantetracarboxylic acid, bicyclo [2.2.2] oct-7 -Ene-2,3,5,6-tetracarboxylic acid, 5- (1,2-dicarboxyethyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, 4- (1,2-dicarboxylic acid) Carboxyethyl) 1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid,

Aromatic tetracarboxylic acid: pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenylsulfonetetracarboxylic acid, oxydiphthalic acid, hexafluoroisopropylidenediphthalic acid, naphthalenetetracarboxylic acid, fluorene-9,9-bisphthalate acid,

Aliphatic or cycloaliphatic pentacarboxylic acid or hexacarboxylic acid: cyclohexane hexacarboxylic acid,

Aromatic pentacarboxylic acid or hexacarboxylic acid: benzene pentacarboxylic acid, merit acid,

In addition, as a divalent or higher carboxylic acid, polyester, polybutadiene, polyisoprene, acrylic oligomer having a carboxylic acid at the terminal and / or side chain, or polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene polyol, poly It is obtained by modifying polyols such as acrylic polyol with acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. Also included are compounds.

  Examples of carboxylic acid derivatives include acid anhydrides, acid chlorides, acid bromides, methyl esters, ethyl esters, phenyl esters, and tert-butyl esters of the above carboxylic acids.

  (A-2) Examples of the primary or secondary amine having one or more hydroxyl groups at the β-position include the following.

Primary amine: ethanolamine, 1-amino-2-propanol <isopropanolamine>, 2-amino-1-propanol, 2-amino-1-butanol, 2-amino-2-phenyl-ethanol, 2-amino-2 -Methyl-1-propanol, isoleucinol << 2-amino-3-methyl-1-pentanol >>, 2-isopropylamino-3-methyl-1-butanol, leucinol << 2-amino-4-methyl-1-pentanol , Tert-leucinol << 2-amino-3,3-dimethyl-1-butanol >>, phenylalaninol << 2-amino-3-phenyl-1-propanol >>, 1-amino-2-butanol, 2-amino- 1-phenylethanol, 2-amino-1-phenyl-1-propanol,

One of the substituents on the nitrogen atom is a hydrocarbon group and the other is a secondary amine represented by the general formula (2): N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N- tert-butylethanolamine, 3-tert-butylamino-1,2-propanediol, N-cyclohexylethanolamine, N-phenylethanolamine, N-benzylethanolamine,

Secondary amines in which both substituents on the nitrogen atom are represented by the general formula (2): diethanolamine, diisopropanolamine, R ^{3 to} R ⁶ containing a hydroxyl group-substituted hydrocarbon group: 2- [ (Hydroxymethyl) amino] ethanol, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, tris (hydroxymethyl) aminomethane, 3-amino-1,2- Propanediol, 3- (methylamino) -1,2-propanediol, N-methylglucamine << 6- (methylamino) -1,2,3,4,5-hexanepentaol >>, 1,3-bis [Tris (hydroxymethyl) methylamino] propane, 2-amino-1-phenyl-1,3-propanediol, phenylephrine << 1- (3-hydroxy Phenyl) -2- (methylamino) ethanol ", etilefrine" 2-ethylamino-1- (3-hydroxyphenyl) ethanol ",
Other than the above: 2- (2-aminomethylaminoethanol), 2-amino-1- (4-nitrophenyl) -1,3-propanediol, serine, serine methyl ester, N- (2,4-dinitrophenyl) Serine, methioninol << 2-amino-4-methylthio-1-butanol >>, N- (5-nitro-2-pyridyl) alaninol, pyrrolinol << 2- (hydroxymethyl) piperidine >>, 4-amino-3-hydroxybutyric acid, 3-hydroxypiperidine, isoserine, 2-aminocyclohexanol, threonine, 1-amino-2-indanol, glucosamine, 1,3-diamino-2-propanol, atenolol, adrenaline, α, α-diphenyl-2-pyrrolidinemethanol.

(A-4) Examples of compounds having at least one functional group capable of reacting with a hydroxyl group are isocyanate, carboxylic acid, carboxylic acid halide, carboxylic acid anhydride, carboxylic acid ester, silanol, alkoxysilane, silanol ester, amino Examples thereof include resins and compounds having an epoxy group. Among these, from the viewpoint of reactivity, an isocyanate group, a carboxyl group, a carboxylic acid anhydride group, and a carboxylic acid halide group are particularly preferable, and a carboxyl group and an isocyanate group are more preferable.

Examples of the isocyanate include the following.

  Monofunctional isocyanate: methyl isocyanate, butyl isocyanate, hexyl isocyanate, heptyl isocyanate, lauryl isocyanate, stearyl isocyanate, phenyl isocyanate, cyclopropyl isocyanate, phenethyl isocyanate, tosyl isocyanate, acryloyloxyethyl isocyanate, methacryloyloxyethyl isocyanate, vinyl isocyanate, allyl isocyanate 2- (2-acryloyloxyethyloxy) ethyl isocyanate, 2- (2-methacryloyloxyethyloxy) ethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, 1,1-bis (methacryloyloxymethyl) Ethyl isocyanate,

  Bifunctional isocyanates: tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, trizine diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate Isopropylidenebis (cyclohexyl isocyanate), 3- (2′-isocyanatocyclohexyl) propyl isocyanate, dianisidine isocyanate, diphenyl ether diisocyanate, dimer isocyanate, tetramethylxylylene diisocyanate,

Trifunctional isocyanate: lysine triisocyanate, tris (isocyanatophenyl) methane, tris (isocyanatophenyl) thiophosphate,

  Further, biurets, uretdiones, isocyanurates, and adducts of the above polyfunctional isocyanates are also included.

  Isocyanate selected from the above-mentioned polyfunctional isocyanate, biuret of polyfunctional isocyanate, uretdione, isocyanurate, adduct, methanol, ethanol, propanol, butanol, pentanol, phenol, benzyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, methyl Activities such as amine, ethylamine, dibutylamine, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, polycaprolactone Compounds obtained by reacting a silicon compound, also cited.

  Among the above, considering the solubility, storage stability, ease of production, etc., the above monofunctional isocyanate, or one of the polyfunctional isocyanate or biuret of polyfunctional isocyanate, uretdione, isocyanurate, adduct It is preferable to use a monofunctional isocyanate which is obtained by leaving a group and reacting the remainder with an active hydrogen compound.

Among them, since the photosensitivity is improved, that R ⁷ is obtained represented by β- hydroxyalkylamide the general formula (104) (A) with a compound represented by the following general formula (106) preferable.

Formula (106)
[Wherein, R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents a group represented by the general formula (107) or a group represented by the general formula (108). ]
General formula (107)
Wherein, n ¹ is an integer of 1-2. ]
Formula (108)
[Wherein R ¹⁴ represents a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group, and R ¹⁵ represents the number of carbon atoms. 6-13 linear or branched alkylene groups, divalent alicyclic hydrocarbon groups, or divalent aromatic hydrocarbon groups. ]

Examples of the carboxylic acid, that is, the compound having a carboxyl group include the following.
Aliphatic saturated monofunctional carboxylic acids: formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid <pentanoic acid>, 2-methylbutyric acid, isovaleric acid <3-methylbutyric acid>, pivalic acid <2,2-dimethyl Propionic acid, caproic acid <hexanoic acid>, methylvaleric acid, dimethylbutyric acid, ethylbutyric acid, enanthic acid <heptanoic acid>, caprylic acid <octanoic acid>, 2-ethylhexanoic acid, pelargonic acid <nonanoic acid>, capric acid << decanoic acid >>, undecanoic acid, lauric acid << dodecanoic acid >>, tridecanoic acid, myristic acid << tetradecanoic acid >>, pentadecanoic acid, palmitic acid << hexadecanoic acid >>, margaric acid << heptadecanoic acid >>, stearic acid << octadecanoic acid >>, isostearic acid Acid "2-heptylundecanoic acid", nonadecanoic acid, arachidic acid "icosanoic acid", henicosa Acid, behenic acid "docosanoate", tricosanoic acid, lignoceric acid "tetracosanoic acid", pentacosanoic acid, cerotic acid "hexacosanoic acid", heptacosanoic acid, montanic acid "octacosanoic", nonacosanoic acid, melissic acid "triacontanoic"

  Aliphatic unsaturated monofunctional carboxylic acids: acrylic acid, methacrylic acid, crotonic acid, undecenoic acid, palmitoleic acid <9-hexadecenoic acid>, petrothelic acid <6-octadecenoic acid>, oleic acid <9-octadecenoic acid>, elaidic acid << 9-octadecenoic acid >>, vaccenic acid, linoleic acid << 9,12-octadecadienoic acid >>, linolenic acid << 9,12,15-octadecatrienoic acid >>, gamma-linolenic acid << 6,9,12-octa Decatrienoic acid, eleostearic acid, araguidonic acid << 5,8,11,14-eicosatetraenoic acid >>, 5,8,11,14,17-eicosapentaenoic acid, erucic acid << 13-docosenoic acid >> Docosahexaenoic acid, 22-tricosenoic acid, 15-tetracosenoic acid, nervonic acid,

  Alicyclic monofunctional carboxylic acids: cyclopropanecarboxylic acid, dimethylcyclopropanecarboxylic acid, tetramethylcyclopropanecarboxylic acid, mercaptomethylcyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclopentylacetic acid, aminocyclopentanecarboxylic acid , Cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, cyclohexylpropionic acid, cyclohexylbutyric acid, methylcyclohexanecarboxylic acid, propylcyclohexanecarboxylic acid, isopropylcyclohexanecarboxylic acid, butylcyclohexanecarboxylic acid, tert-butylcyclohexanecarboxylic acid, hydroxycyclohexanecarboxylic acid , (Hydroxymethyl) cyclohexanecarboxylic acid, cyclohexenecarbo Acid, norbornene carboxylic acid, norbornane carboxylic acid, noradamantane carboxylic acid, adamantane carboxylic acid,

  Monofunctional carboxylic acid having an oxygen atom in addition to the carboxyl group: glycolic acid, lactic acid, hydroxypalmitic acid, ricinoleic acid, hydroxystearic acid, alloyed acid <trihydroxyhexadecanoic acid>, jasmonic acid <3-oxo-2- (2- Pentenyl) cyclopentaneacetic acid, cucurbic acid << 3-hydroxy-2- (2-pentenyl) cyclopentaneacetic acid >>, 3-oxobutanoic acid and the like, and (a-1) a divalent or higher valent acid And compounds listed as carboxylic acids.

  Examples of the carboxylic acid, that is, a compound having a carboxyl group, include compounds obtained by esterifying or amidating a part of a compound mentioned as a divalent or higher carboxylic acid or a derivative thereof with an alcohol or an amine. For example, methanol, ethanol, propanol, butanol, pentanol, phenol, benzyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( Such as (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, methylamine, ethylamine, dibutylamine, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, polycaprolactone, etc. Alcohol, amine, and (a-1) a compound enumerated with a divalent or higher carboxylic acid are partially esterified to leave a single carboxyl group in the molecule. Ability carboxylic acid, and the like. In particular, it is preferable to use a cyclic carboxylic acid anhydride of a divalent carboxylic acid because one carboxyl group is generated after reacting with a hydroxyl group or an amino group in a 1: 1 ratio.

  Further, acid anhydrides, acid halides, methyl esters, ethyl esters, phenyl esters, and tert-butyl esters of the above compounds having a carboxyl group are also included.

  Among the above, in consideration of solubility, storage stability, ease of production, etc., some of the monofunctional carboxylic acid, acid halide, acid anhydride, or polyfunctional carboxylic acid or derivative thereof Monofunctional carboxylic acid or derivative thereof in which carboxylic acid is reacted with alcohol or amine to leave one carboxyl group, or monofunctional carboxylic acid produced by reacting monofunctional alcohol or amine with a cyclic acid anhydride of divalent carboxylic acid Is preferably used.

  Especially, since it is easy to provide the solubility to an organic solvent, it is preferable to use the compound represented by following General formula (104), and since photocurability becomes favorable, in following General formula (105) It is preferable to use the compound represented.

General formula (104)

[Wherein, R ⁸ represents a linear, cyclic or branched saturated or unsaturated hydrocarbon group having 2 to 18 carbon atoms. ]

General formula (105)

[Wherein R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ is a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic group. A hydrocarbon group, and R ¹¹ is a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group. ]
These compounds may be used alone or in combination.

Silanol is a compound having a Si—OH structure in the molecule, and O in the silanol.
H and hydroxyl group react. Further, alkoxysilane, sulfuric acid of silanol, sulfonic acid ester, and halogenated silane (hereinafter collectively referred to as “silanol derivatives”) generate silanol by hydrolysis and can be used in the same manner as silanol. A silanol derivative is commercially available from the viewpoint of storage stability.

The following are mentioned as a silanol derivative.

Monofunctional silanol derivatives: trimethylsilyl triflate, triethylsilyl triflate, tert-butyldimethylsilyl triflate, diethylisopropylsilyl triflate, tripropylsilyl triflate, bis (trimethylsilyl) sulfate, chlorotrimethylsilane, chlorotriethylsilane, trimethylmethoxysilane,

Multifunctional silanol derivatives: dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, vinyltriethoxysilane , Vinyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycosoxypropyltriethoxy Silane, p-styryltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxy Propylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropyltrimethoxysilane, N- (2-aminomethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminomethyl) -3-aminopropyltrimethoxysilane, N- (2-aminomethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, 3-chloro B pills trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl methyl dimethoxy silane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane,

Among these, considering the solubility, storage stability, ease of production, etc., it is preferable to use the monofunctional silanol derivative.

  An amino resin is a compound having a hydroxymethylamino group in which an electron-withdrawing group is bonded to a nitrogen atom, and reacts with a hydroxyl group to form an ether bond. Examples of the electron withdrawing group include a carbonyl group, a thiocarbonyl group, and a triazine ring. A compound having an alkoxymethylamino group in which the hydroxyl group is capped with an alcohol can also be used because it generates a hydroxyl group by hydrolysis.

The following are mentioned as an amino resin.

Monofunctional amino resin: N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide, N-hydroxymethylacetamide, N-hydroxymethylurea, 1- (hydroxymethyl) -5,5-dimethylhydantoin, N- (hydroxymethyl) nicotinamide,

Multifunctional amino resin: N, N′-dimethylolurea, 1,3-bis (hydroxymethyl) -5- [1,3-bis (hydroxymethyl) ureido] hydantoin, 1,3,4,6-tetrakis (methoxy) Methyl) glycoluril, hexamethylolmelamine, hexamethoxymethylmelamine, hexabutoxymethylmelamine, etc., nitrogen, hydroxyl, methoxymethyl, butoxymethyl groups are substituted, urea, melamine, benzoguanamine, glycoluril, etc. Is mentioned.

Among the above, in consideration of solubility, storage stability, ease of production, etc., it is preferable to use the monofunctional amino resin.

Examples of the compound having an epoxy group include the following.
Monofunctional epoxy: allyl glycidyl ether, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, phenyl glycidyl ether, phenylphenol glycidyl ether, sec-butylphenol monoglycidyl ether, polyethylene glycol monophenyl ether monoglycidyl ether, N-glycidyl phthalimide, styrene oxide 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexane-1-carboxylic acid ester, 3,4-epoxycyclohexane-1-methanol, 3,4-epoxycyclohexane-1-carbaldehyde, 4, 5-epoxy-1,2-dicarboxylic acid ester,

Multifunctional epoxy: sorbitol polyglycidyl ether, polyglycerin polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerin polyglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether Propyl) propane diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tert-butylphenol glycidyl ether, polybutadiene diglycidyl ether, diglycidyl phthalate, diglycidyl cyclohexanedicarboxylate, glycidyl terephthalate, hydroquinone diglycidyl ether, dibromopheno Rudiglycidyl ether, dibromoneopentyl glycol diglycidyl ether, condensate of bisphenol A and epichlorohydrin, condensate of bisphenol F and epichlorohydrin, phenol novolac polyglycidyl ether, cresol novolac polyglycidyl ether, brominated bisphenol A And epichlorohydrin condensate, N, N, N ′, N′-tetraglycidyl bis (aminophenyl) methane, diglycidyl dimer, hydrogenated bisphenol A and epichlorohydrin condensate, di-tert-butyl Hydroquinone diglycidyl ether, tetramethylbisphenol F diglycidyl ether, bis (N, N-diglycidylaminomethyl) benzene, bis (N, N-diglycidylaminomethyl) cyclohexane, etc. It is below.

  Among the above, in consideration of solubility, storage stability, ease of production, etc., it is preferable to use the above monofunctional epoxy.

(Amidation)
There are various methods for amidating (a-1) a divalent or higher carboxylic acid or derivative thereof and (a-2) a primary or secondary amine having one or more hydroxyl groups at the β-position. -1) The reaction can proceed by removing water when the divalent or higher carboxylic acid or derivative thereof is a carboxylic acid, removing alcohol in the case of a carboxylic acid ester, and removing acid in the case of a carboxylic acid anhydride or halide. . In the case of water or alcohol, it is prepared to be removed from the reaction system by heating. In the case of acid, triethylamine, tributylamine, dimethylbenzylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. The basic compound can be removed.

A catalyst can be used in the amidation. For example, acid catalysts such as sulfuric acid, hydrochloric acid, methanesulfonic acid and p-toluenesulfonic acid, base catalysts such as sodium hydroxide, sodium carbonate and sodium methoxide (hereinafter referred to as “base catalyst”), triethylamine, tributylamine, Amine catalysts such as octylamine, tetramethylethylenediamine, N, N-dimethylethanolamine, N, N-dimethylbenzylamine, pyridine, 4- (dimethylamino) pyridine, imidazole, N-methylimidazole (hereinafter referred to as “amine catalyst”) Summarize), salts and complexes containing metal ions such as iron (III), zirconium (IV), scandium (III), titanium (IV), tin (IV), hafnium (IV), diphenylammonium triflate, pentafluorophenylammonium Ammonium salts such as Rifurato, and the like.

A solvent can be used in the amidation reaction. The solvent to be used can be used as long as it is other than a solvent that reacts with a reaction substrate such as alcohol, amine, or carboxylic acid. For example, hexane, heptane, octane, cyclohexane, benzene, toluene, ethylbenzene, xylene, ethyl acetate, butyl acetate, isobutyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dichloromethane, chloroform, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, etc. It is done.

In particular, the amidation with carboxylic acid can be performed using a condensing agent. A condensing agent activates a carboxylic acid or an amine, and the esterification reaction can be carried out under mild conditions. At the same time, the by-product water is combined with the condensing agent to form another compound. And a compound having a water removing action. Such condensing agents include, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, p-toluenesulfonyl chloride, 1-ethyl-3- (N, N-dimethylaminopropyl) carbodiimide hydrochloride, carbonyldiimidazole, ethyl chloroformate, chloroformate Acid isobutyl, 2,4,6-trichlorobenzoic acid chloride, 2-methyl-6-nitrobenzoic anhydride, O- (7-azabenzotriazol-1-yl) -N, N, N ′, N′— Examples thereof include tetramethyluronium hexafluorophosphate.

(Denaturation)
(A-3) When reacting a part of the hydroxyl group of β-hydroxyalkylamide with a compound having one or more functional groups capable of reacting with (a-4) hydroxyl group, What is necessary is just to make it react on suitable conditions.

(A-4) When the compound having one or more functional groups capable of reacting with a hydroxyl group is an isocyanate, the reaction proceeds by adding a non-catalyst or an appropriate catalyst and heating. Suitable catalysts include, for example, amines such as triethylamine, tributylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, and salts thereof, tetrabutyl titanate, dibutyltin dilaurate, tin octylate. And metal salts and complexes.

(A-4) When the compound having one or more functional groups capable of reacting with a hydroxyl group is a carboxylic acid, the dehydration condensation reaction proceeds by heating to 100 ° C. or higher, preferably 140 ° C. or higher without a catalyst. Alternatively, the reaction can be allowed to proceed at a lower temperature by adding an appropriate catalyst. The catalysts, condensing agents, etc. described for the amidation reaction can be used for this reaction.

(A-4) When the compound having at least one functional group capable of reacting with a hydroxyl group is a carboxylic acid anhydride or a carboxylic acid halide, a base catalyst or an amine catalyst is added and reacted at 0 to 100 ° C. preferable. At this time, it is preferable to use 1 mol or more of the base catalyst or amine catalyst with respect to 1 mol of carboxylic acid anhydride or carboxylic acid halide.

(A-4) When the compound having one or more functional groups capable of reacting with a hydroxyl group is silanol, it is preferable to add a base catalyst or an amine catalyst and react at 0 to 100 ° C. At this time, it is preferable to use 1 mol or more of the base catalyst or amine catalyst with respect to 1 mol of carboxylic acid anhydride or carboxylic acid halide.

(A-4) When the compound having one or more functional groups capable of reacting with a hydroxyl group is an amino resin, methanesulfonic acid, p-toluenesulfonic acid, ammonium salt or amine salt thereof is used as a catalyst, and 0 It is preferable to make it react at -200 degreeC.

(A-4) When the compound having at least one functional group capable of reacting with a hydroxyl group is an epoxy group, potassium hydroxide, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium hydride, etc. It is preferable to use a strong base catalyst or a metal catalyst such as tetrafluoroboric acid or tin (IV) chloride and react at 0 to 200 ° C.

  When the compound represented by the general formula (101) contains a photopolymerizable functional group, a gas having a polymerization inhibitory effect is introduced into the reaction system or a polymerization inhibitor is added during the reaction. May be. By introducing a gas having a polymerization inhibition effect into the reaction system or adding a polymerization inhibitor, gelation during the addition reaction can be prevented.

  Examples of the gas having an effect of inhibiting radical polymerization include a gas containing oxygen that does not enter the explosion range of the substance in the system, for example, air.

As the radical polymerization inhibitor, known ones can be used and are not particularly limited. For example, hydroquinone, methoquinone, 2,6-di-t-butylphenol, 2,2′-methylenebis (4-methyl- 6-t-butylphenol), phenothiazine and the like. These polymerization inhibitors may be used alone or in combination of two or more. The amount of the polymerization inhibitor to be used is preferably 0.005 to 5 parts by weight, more preferably 0.03 to 3 parts by weight, more preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the total solids in the reaction system. Most preferred is 1.5 parts by weight. If the polymerization inhibitor is less than 0.005 parts by weight, the polymerization inhibition effect may not be sufficient. On the other hand, if it exceeds 5 parts by weight, the exposure sensitivity may decrease. Moreover, it is more preferable to use a gas having a polymerization inhibiting effect in combination with the polymerization inhibitor because the amount of the polymerization inhibitor to be used can be reduced or the polymerization inhibiting effect can be enhanced.
<Polymer containing carboxyl group (B)>
The carboxyl group-containing polymer (B) of the present invention is used for the purpose of imparting alkali developability to the photosensitive composition and thermosetting reaction with β-hydroxyalkylamide (A). It is a polymer having a carboxyl group at the terminal and / or side chain. It may or may not contain a photopolymerizable functional group. The polymer may be linear, branched or star-shaped, and may be thermoplastic or thermosetting.
Examples of the polymer (B) containing a carboxyl group that does not contain a photopolymerizable functional group include, for example, carboxy-terminated polyester, polyamide, polyesteramide, polyetherester, acrylic, polybutadiene, polyisoprene, and carboxyl group side chain polyurethane, Examples thereof include carboxylic acid-added cellulose, (meth) acrylate copolymer containing a carboxyl group, and a carboxylic acid anhydride adduct of a phenol resin.

In the case of the polymer (B) containing a carboxyl group containing a photopolymerizable functional group, radically polymerizable, cationically polymerizable, and anionic polymerizable photopolymerizable functional groups can be introduced. It is preferable to contain a polymerizable photopolymerizable functional group. For example, for example,
(B-1) A method of introducing a photopolymerizable functional group into a polymer containing a carboxyl group (B-2) A method of introducing a photopolymerizable functional group into a polymer not containing a carboxyl group, and introducing a carboxyl group. Can be mentioned. Moreover, it is not limited about the polymer which has these functional groups, It is possible to use each polymer, such as an acrylic type, a urethane type, a polyester type, a polyolefin type, a polyether type, a natural rubber, a block copolymer rubber, and a silicone type. it can.

  As a method for introducing the photopolymerizable functional group used in (B-1) and (B-2), (B-11) a polymer containing a carboxyl group, a hydroxyl group, a mercapto group, an amino group, an active methylene group and the like An epoxy group, an isocyanate group, an aldehyde group, etc. in a compound containing an epoxy group, an isocyanate group, an aldehyde group, etc. and a photopolymerizable functional group on the carboxyl group, hydroxyl group, mercapto group, amino group, active methylene group, etc. Method of reaction, (B-12) Epoxy group, isocyanate group, aldehyde group, etc. in a polymer containing an epoxy group, isocyanate group, aldehyde group, etc., carboxyl group, hydroxyl group, mercapto group, amino group, active methylene group, etc. And a carboxyl group, a hydroxyl group, a mercapto group, an amino group in a compound containing a photopolymerizable functional group, The method and the like to react sexual methylene group.

As a method of introducing the carboxyl group used in (B-2),
(B-13) A method in which an acid anhydride group in a polybasic acid anhydride is reacted with a hydroxyl group, an amino group, or the like in a polymer containing a hydroxyl group, an amino group, or the like.

As a method of simultaneously introducing a photopolymerizable functional group and a carboxyl group used in (B-2),
(B-14) a method of reacting a hydroxyl group or the like in a compound containing a photopolymerizable functional group with an acid anhydride group in a polymer containing a carboxylic anhydride group,
(B-15) A method of reacting an acid anhydride group in a compound containing a photopolymerizable functional group with a hydroxyl group, an amino group, or the like in a polymer containing a hydroxyl group, an amino group, or the like. It is done.

  The polymer (B) containing a carboxyl group can be used alone or in combination of two or more. The ratio of the carboxyl group in the polymer (B) containing a carboxyl group and the hydroxyl group in the β-hydroxylamide group is preferably 10/1 to 1/10 in terms of molar ratio, and more preferably 3/1 to 1/3. Further, 1.5 / 1 to 1 / 1.5 is preferable. When it is out of the range of 10/1 to 1/10, the hydroxyl group in the carboxyl group or β-hydroxyalkylamide group is excessive in the cured film or fine pattern, and the chemical resistance and heat resistance are insufficient. There is a risk.

  The concentration of the carboxyl group in the polymer (B) containing a carboxyl group is preferably an acid value of 10 to 250 mgKOH / g, more preferably 20 to 200 mgKOH / g, and further preferably 40 to 100 mgKOH / g. If it is less than 10 mgKOH / g, the functional group (carboxyl group) that can react with the hydroxyl group in β-hydroxyalkylamide (A) decreases, and chemical resistance and heat resistance may not be obtained satisfactorily. If it exceeds 250 mgKOH / g, the viscosity of the coating agent is high, and the storage stability may deteriorate.

  In addition to the carboxyl group, an active methylene group such as a phenolic hydroxyl group, an aromatic mercapto group, or a β-diketone can be used as the functional group capable of reacting with the β-hydroxyalkylamide (A). The functional group can be introduced into the polymer (B) containing a carboxyl group. You may contain in (beta) -hydroxyalkylamide (A) and a photopolymerizable monomer (D).

  As a method of obtaining a (meth) acrylic copolymer containing a carboxyl group, a method of copolymerizing (meth) acrylic acid or a (meth) acrylate containing a carboxyl group with another monomer, or a hydroxyl group (meta ) A method of reacting a hydroxyl group in a polymer obtained by copolymerizing an acrylate with another monomer with an acid anhydride group in a polybasic acid anhydride.

Moreover, as a method for obtaining a (meth) acrylate copolymer containing a photopolymerizable functional group and a carboxyl group, there are the methods (B-1) and (B-2) described above. ) To (B-15). In particular,
A method in which a part of a carboxyl group in a (meth) acrylic copolymer containing a carboxyl group is reacted with an epoxy group in a (meth) acrylate containing an epoxy group,
The epoxy group in the (meth) acrylic copolymer containing an epoxy group is reacted with the carboxyl group in the (meth) acrylate containing (meth) acrylic acid or a carboxyl group, and the resulting hydroxyl group is polybasic. A method of reacting an acid anhydride group of an acid anhydride,
Examples include a method of reacting a hydroxyl group in a (meth) acrylic copolymer containing a carboxyl group and a hydroxyl group with an isocyanate group or an acid anhydride group in an isocyanate group-containing (meth) acrylate or unsaturated acid anhydride. .

Examples of the (meth) acrylate containing a carboxyl group include acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethylhexa. Examples include hydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, and ω-carboxypolycaprolactone (meth) acrylate.
Itaconic acid, maleic acid, fumaric acid, crotonic acid, α- (hydroxymethyl) acrylic acid, α- (hydroxymethyl) methacrylic acid, p-vinylbenzoic acid and the like can also be used.
(Meth) acrylic acid is preferred from the viewpoints of copolymerizability and availability.

  As for the weight average molecular weight (Mw) of the polymer (B) containing a carboxyl group, 2000-25000 are preferable, More preferably, it is 4000-15000. When the weight average molecular weight (Mw) is less than 2,000, the heat resistance may be deteriorated, and when the weight average molecular weight (Mw) exceeds 25,000, the viscosity becomes high and coating may be difficult.

  When the polymer (B) containing a carboxyl group of the present invention is used as a coloring composition for a color filter, high transparency is required. Therefore, the transmittance in the entire wavelength region of 400 to 700 nm in the visible light region. Is preferably 80% or more, more preferably 95% or more. From the viewpoint of transparency, a (meth) acrylic copolymer containing a carboxyl group is preferably used.

  The total amount of the β-hydroxyalkylamide (A) and the polymer (B) containing a carboxyl group is 1 to 400 parts by weight, preferably 1 to 250 parts per 100 parts by weight of the pigment in the color filter photosensitive composition. It can be used in parts by weight.

<Pigment (C)>
Examples of the pigment (C) used in the present invention include phthalocyanine pigments represented by the following general formula (1).
General formula (1)

[Wherein, X _{1 to} X ₄ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. A heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or a substituent. Represents an optionally substituted arylthio group.
Y _{1 to} Y ₄ each independently represents a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group.
M represents Zn or Al-Z.
Z represents a hydroxyl group, a chlorine atom, —OP (═O) R ₈₅ R ₈₆ , or —O—SiR ₈₇ R ₈₈ R ₈₉ , wherein R _{85 to} R ₈₉ are each independently a hydrogen atom, a hydroxyl group, or a substituent. It represents an alkyl group which may have a group, an optionally substituted aryl group, optionally alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, R ₈₅ to R ₈₉ are bonded to each other to each other may form a ring.
m ₁ , m ₂ , m ₃ , m ₄ , n ₁ , n ₂ , n ₃ , and n ₄ each independently represent an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + N ₃ and m ₄ + n ₄ are each 0 to 4, and may be the same or different. ]

  Examples of the “alkyl group” of the alkyl group which may have a substituent in the present invention include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, and n-to. Examples include a linear or branched alkyl group such as a xyl group, n-octyl group, stearyl group, 2-ethylhexyl group, etc. The “alkyl group having a substituent” includes a trichloromethyl group, a trifluoromethyl group, 2 , 2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl Group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl Etc. The.

  Examples of the “aryl group” of the aryl group which may have a substituent in the present invention include a phenyl group, a naphthyl group, and an anthryl group, and the “aryl group having a substituent” includes a p-methylphenyl group. P-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy- Examples include 1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group and the like.

  Examples of the “cycloalkyl group” of the cycloalkyl group that may have a substituent in the present invention include a cyclopentyl group, a cyclohexyl group, an adamantyl group, and the like, and the “cycloalkyl group having a substituent” Examples include a 2,5-dimethylcyclopentyl group and a 4-tert-butylcyclohexyl group.

  Examples of the “heterocyclic group” of the heterocyclic group that may have a substituent in the present invention include a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, an acridinyl group, and the like. Examples of the “heterocyclic group” include a 3-methylpyridyl group, an N-methylpiperidyl group, and an N-methylpyrrolyl group.

  As the “alkoxyl group” of the alkoxyl group which may have a substituent in the present invention, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy Group, 2,3-dimethyl-3-pentyloxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group and the like, and straight-chain or branched alkoxyl groups such as “substituents” As the “alkoxyl group having”, a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditrifluoromethylpropoxy group 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, ben Aryloxy group, and the like.

  Examples of the “aryloxy group” of the aryloxy group which may have a substituent in the present invention include a phenoxy group, a naphthoxy group, an anthryloxy group, and the like, and the “aryloxy group having a substituent” Examples include p-methylphenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group.

  Examples of the “alkylthio group” of the alkylthio group which may have a substituent in the present invention include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group. Examples of the “alkylthio group having a substituent” include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group, and the like. .

  Preferred examples of the pigment (C) used in the present invention include C.I. I. Pigment Green 58 green pigment. In order to improve the light resistance in the present invention, it is particularly preferable to use a pigment exhibiting green, and in order to exhibit green, it is preferable that 1 to 16 halogen atoms are contained in one pigment molecule. In order to obtain better color developability, it is desirable that there are 4 to 16 halogen atoms in one pigment molecule.

(Aluminum phthalocyanine pigment)
Moreover, an aluminum phthalocyanine pigment can also be used as a pigment (C). The aluminum phthalocyanine pigment is not particularly limited as long as it has a structure in which trivalent aluminum is coordinated at the center of the phthalocyanine ring. In an aluminum phthalocyanine pigment, aluminum is known to have a structure such as a dimer and a trimer in addition to a monomer, because it is trivalent and has a bond in addition to a bond with phthalocyanine. It is also known that the phthalocyanine ring can be chemically modified and can take various structures. The aluminum phthalocyanine pigment in the present invention may take any form such as not only a monomer but also a structure such as a dimer or a trimer, or a chemically modified phthalocyanine ring.

Among these, as the aluminum phthalocyanine pigment of the present invention, those represented by the structure of the general formula (1A) are preferable in terms of color characteristics and dispersibility.
General formula (1A)

[In General Formula (1A), X _{1 to} X ₄ are each independently an alkyl group that may have a substituent, an aryl group that may have a substituent, or a cyclo that may have a substituent. An alkyl group, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or The arylthio group which may have a substituent is represented.
Y _{1 to} Y ₄ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group.
Z represents a hydroxyl group, a chlorine atom, —OP (═O) R ₅₅ R ₅₆ , or —O—SiR ₅₇ R ₅₈ R ₅₉ . Here, R _{55 to} R ₅₉ are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxyl group which may have a substituent. Or an aryloxy group which may have a substituent, and R _{55 to} R ₅₉ may be bonded to each other to form a ring. m _{1 to} m ₄ and n _{1 to} n ₄ each independently represents an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ , m ₄ + n ₄ are each 0 to 4 may be the same or different. ]

In the general formula (1A), X _{1 to} X ₄ may be the same or different. Specific examples thereof include an alkyl group that may have a substituent, an aryl group that may have a substituent, and a substituent. A cycloalkyl group that may have a group, a heterocyclic group that may have a substituent, an alkoxyl group that may have a substituent, an aryloxy group that may have a substituent, and a substituent. An alkylthio group that may be substituted, and an arylthio group that may have a substituent. When X _{1 to} X ₄ have a substituent, the substituents may be the same or different. Specific examples thereof include properties such as halogen groups such as fluorine, chlorine and bromine, amino groups, hydroxyl groups and nitro groups. In addition to the group, an alkyl group, an aryl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, and the like can be given. Moreover, there may be a plurality of these substituents.

  Examples of the “arylthio group” of the arylthio group which may have a substituent in the present invention include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and the like, and “an arylthio group having a substituent” As examples of the "", a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, a 2-hydroxyphenylthio group, and the like can be given.

(Other colorants)
The coloring composition for a color filter of the present invention has a C.I. I. In addition to Pigment Green 58 and aluminum phthalocyanine pigment, other green pigments and yellow pigments may be contained. As yellow pigments, both dyes and pigments can be used.

  Examples of green pigments that can be used in combination include C.I. I. Pigment Green 7, 10, 36, 37 and the like, but are not limited thereto. Preferred green pigments to be used in combination are C.I. I. Pigment Green 36.

  Yellow dyes include azo dyes, azo metal complex dyes, quinophthalone dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes Quinoline dyes, naphthoquinone dyes, and oxazine dyes.

  Therefore, specific examples of yellow dyes include C.I. I. Acid Yellow 2,3, 4, 5, 6, 7, 8, 9, 9: 1, 10, 11, 11: 1, 12, 13, 14, 15, 16, 17, 17: 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199 Etc.

  In addition, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 etc. are also mentioned.

  In addition, C.I. I. Basic Yellow 1, 2, 5, 11, 13, 14, 15, 19, 21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, 105, 106 and the like.

  In addition, C.I. I. Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64, 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186, 187, 188, 190, 191, 192, 194, 195 and the like are also included.

  In addition, C.I. I. Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184: 1, 202, 211, 229, 231, 232 233, 241, 245, 246, 247, 248, 249, 250, 251 and the like.

  As the yellow pigment, organic or inorganic pigments can be used alone or in admixture of two or more, and pigments having high color development properties and high heat resistance, particularly pigments having high heat decomposition resistance are preferred. Organic pigments are used. As the organic pigment, commercially available ones can be used, and natural pigments and inorganic pigments can be used in combination according to the desired hue of the filter segment.

Below, the specific example of the yellow organic pigment which can be used for the said coloring composition is shown. Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, Yellow pigments such as 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214 can be used. In particular, from the viewpoint of heat resistance, light resistance, and brightness of the filter segment, C.I. I. Pigment Yellow 138, 139, 150, and 185 are preferable.
These yellow pigments can be used alone or in combination of two or more depending on the desired color characteristics.

When the yellow dye is used in combination, the weight ratio of yellow dye / pigment (C) is preferably 80/20 to 10/90.
When the weight ratio of the yellow dye / pigment (C) satisfies this range, it is possible to form a green filter segment having excellent brightness and a wide chromaticity range.

  From the viewpoint of obtaining sufficient color reproducibility, the preferable concentration of the pigment component is 10% by weight or more, more preferably 15% by weight or more, based on the total nonvolatile components of the colored composition of the present invention (100% by weight). Yes, and most preferably 20% by weight or more. Further, since the stability of the coloring composition is improved, the concentration of the preferred pigment component is 90% by weight or less, more preferably 80% by weight or less, and most preferably 70% by weight or less.

<Pigment dispersant>
In the coloring composition of the present invention, it is preferable to use a pigment dispersant such as a resin-type dispersant, a dye derivative, and a surfactant.
<Resin type dispersant>
Since the resin-type dispersant is excellent in pigment dispersion and has a large effect of preventing reaggregation of the pigment after dispersion, a color filter having high spectral transmittance can be obtained.

  The basic structure of the resin-type dispersant is not particularly limited, and examples thereof include general resins such as acrylic resins, polyester resins, polyether resins, urethane resins, silicone resins, epoxy resins, and vinyl acetate resins.

  The resin-type dispersant has a colorant-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 139 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, 21324, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, manufactured by Ciba Japan 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  When the resin type dispersant is an acidic resin type dispersant, examples of the acidic substituent include a phosphoric acid group, a sulfonic acid group, and a carboxyl group. Further, trimellitic acid and / or pyromellitic acid partially esterified are preferably used. In some cases, an aromatic ring having two or more acidic substituents may be a unit having one acidic substituent by a plurality of direct bonds and / or linking groups. Especially, it is preferable to have two or more carboxyl groups in one molecule. A dispersant having two or more carboxyl groups in one molecule has more adsorbing groups to the colorant than a resin-type dispersant having zero or one carboxyl group in one molecule. This is preferable because it has a strong function of stabilizing the dispersion on the carrier, the polarity of the dispersant is increased, and higher dispersion stability can be secured.

  As the acidic resin type dispersant, those having an acidic substituent, an aromatic group, or the like in the main chain or terminal of the linear resin, or in the main chain or side chain of the comb resin in a block or random manner are preferable. Specifically, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, poly ( An amide formed by a reaction between a lower alkyleneimine) and a polyester having a free carboxyl group, a salt thereof, or the like is used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble High molecular compounds, polyesters, modified poly (meth) acrylates, ethylene oxide / propylene oxide adducts, phosphate esters, and the like are used. These may be used alone or in admixture of two or more, but are not necessarily limited thereto.

  As a site | part with high affinity to a dispersion medium of the acidic resin type dispersing agent of this invention, the at least 1 sort (s) of polymer unit chosen from polyester, polyether, and poly (meth) acrylate is preferable.

  For example, as polyester, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol 1,4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, One or more alcohols such as glycerin or hexanetriol, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid ,Guru Conic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehycarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexa And polyester polyols obtained by cocondensation with one or more carboxylic acids such as tricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid.

  For example, as the polyether, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexane Diol, 1,4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol , Alcohols such as glycerin or hexanetriol, ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether Others include modified polyether polyols and the like obtained by ring-opening polymerization of various (cyclic) ether bond-containing compounds such as allyl glycidyl ether.

  For example, as poly (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, oxetane (meth) acrylate, etc. Alkoxypolyalkylene glycol (meth) acrylates such as xypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate, (meth) acrylamide, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meta) ) N-substituted (meth) acrylamides such as acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl ( Examples include homopolymers and copolymers such as amino group-containing (meth) acrylates such as (meth) acrylate and nitriles such as (meth) acrylonitrile. These may be used alone or in combination, or may be in the form of a block polymer, graft polymer or random polymer.

  As the acidic resin type dispersant, an acidic resin type dispersant having an aromatic carboxyl group is particularly preferable, a polymer having a hydroxyl group at one end, an aromatic tricarboxylic acid anhydride and / or an aromatic tetracarboxylic acid dianhydride. Most preferably, the dispersant is obtained by reacting a product. Examples of such resin-type dispersants include Japanese Patent No. 40201050, Japanese Patent Application Laid-Open No. 2007-140487, International Publication No. 2008/007776, Japanese Patent Application Laid-Open No. 2010-163500, and Japanese Patent Application Laid-Open No. 2010-223888. And exhibits excellent effects such as compatibility between fluidity and dispersibility.

  Among these, preferable acidic resin type dispersants are radical polymerization of ethylenically unsaturated monomers in the presence of a compound having two hydroxyl groups and one thiol group in the molecule described in WO2008 / 007776 pamphlet or the like. A polyester dispersant produced by reacting a hydroxyl group in a vinyl copolymer having two hydroxyl groups in one end region with an acid anhydride group in tetracarboxylic dianhydride is preferable. More preferably, the polyester dispersant is characterized in that the tetracarboxylic dianhydride contains an aromatic tetracarboxylic dianhydride. Color filter coloring compositions using these polyester dispersants are preferable because they are excellent in pigment dispersion stability, and are synthesized using the method described in WO2008 / 007776 pamphlet or the like. be able to.

  When the resin type dispersant is added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the pigment. When the blending amount of the resin-type dispersant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion may be affected by an excessive dispersant. is there.

<Dye derivative>
The coloring composition of the present invention can use a pigment derivative. The dye derivative has a large effect of preventing reaggregation of the pigment.

  Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, β-naphthol compound, acridone, or triazine. For example, JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717 Gazette, JP-A-2003-128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, Described in Japanese Patent Application Laid-Open No. 2008-195916 and Japanese Patent No. 45855781 You can use what is, they may be used alone or in combination of two or more. When a pigment derivative is used, one having a quinophthalone skeleton is preferable from the viewpoint of brightness.

That is, the structure of the pigment derivative that can be used in the present invention is a compound represented by the following general formula (4).
P-Ln General formula (4)
[In general formula (4),
P: organic pigment residue, anthraquinone, β-naphthol residue, acridone residue or triazine residue L: basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group n: 1 to 1 It is an integer of 4. ]

  Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; benzoisoindole pigments; copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine Phthalocyanine pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, etc .; quinacridone pigment; dioxazine pigment; perinone pigment; perylene pigment; Examples thereof include thiaindigo pigments; isoindoline pigments; isoindolinone pigments; quinophthalone pigments; selenium pigments; metal complex pigments.

  Triazines constituting the triazine residue of P are alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, diethylamino group, dibutylamino group, etc.), nitro groups, hydroxyl groups, Alkoxy group (methoxy group, ethoxy group, butoxy group etc.), halogen (chlorine, bromine etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen etc.) And a phenylamino group (which may be substituted with an alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) 3,5-triazine.

Especially, the pigment derivative which has a basic substituent whose L in General formula (4) is a basic substituent can be used preferably.
By including a dye derivative having a basic substituent, a pigment composition having excellent dispersibility, fluidity, and storage stability can be obtained even in the case of a pigment that is difficult to disperse without a dye derivative having a basic substituent. This is preferable. The pigment can be effectively dispersed by the synergistic effect of the acidic resin type dispersant and the dye derivative having a basic substituent, and a pigment composition having excellent fluidity and storage stability can be obtained.
Among the basic substituents, L is preferably a substituent selected from the group represented by the general formulas (5), (6), and (7).

General formula (5):

General formula (6):

General formula (7):
[In the general formulas (5) to (7),
X _{is, -SO 2 -, - CO -} , - CH 2 -, - CH 2 NHCOCH 2 -, - CH 2 NHSO 2 CH 2 -, or a direct bond,
Y is —NH—, —O—, or a direct bond;
n is an integer of 1 to 10,
Y ¹ is —NH—, —NR ⁵⁸ —Z—NR ⁵⁹ —, or a direct bond;
R ⁵⁸ and R ⁵⁹ are each independently a hydrogen bond, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or A phenyl group which may have a substituent,
Z is an alkylene group which may have a substituent, or an arylene group which may have a substituent,
R ⁵⁰ and R ⁵¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted alkenyl group having 2 to 30 carbon atoms, or R ⁵⁰ and R ⁵¹ together are a heterocyclic ring which may further have a substituent containing a further nitrogen, oxygen or sulfur atom,
R ⁵² , R ⁵³ , R ⁵⁴ , and R ⁵⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or 2 to carbon atoms that may have a substituent. 20 alkenyl group, an arylene group having 6 to 20 carbon atoms which may have a substituent,
R ⁵⁶ is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms,
R ⁵⁷ is a substituent represented by the general formula (5) or a substituent represented by the general formula (6);
Q is a hydroxyl group, an alkoxyl group, a substituent represented by the above general formula (5), or a substituent represented by the above general formula (6). ]

  Examples of the amine component used for forming the substituents represented by the general formulas (5) to (7) include dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethyl. Propylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine , Dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadeci Amine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylamino Ethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N , N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopen Ruamine, N, N-methyl-laurylaminopropylamine, N, N-ethylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isonipecotate, Isonipecotic acid Ethyl, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, -Aminopropyl-4-pipecholine, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine, etc. Can be mentioned.

  The pigment derivative, β-naphthol derivative, and acridone derivative having a basic substituent of the present invention can be synthesized by various synthetic routes. For example, after introducing the substituents represented by the formulas (8) to (11) into the organic dye, β-naphthol or acridone, the substituents represented by the formulas (5) to (7) are reacted with the above substituents. The amine component to be formed, for example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine, or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5 -Triazin-2-ylamino] aniline and the like are obtained by reaction.

Equation (8): -SO ₂ Cl
Formula (9): -COCl
Equation _{(10): -CH 2 NHCOCH 2} Cl
Equation (11): -CH ₂ Cl

  When the substituents of the formulas (8) to (11) and the amine component are reacted, a part of the substituents of the formulas (8) to (11) are hydrolyzed and chlorine is substituted with a hydroxyl group. It may be. In that case, the formula (8) and the formula (9) are respectively a sulfonic acid group and a carboxylic acid group, but any of them may be a free acid, or a 1-3 valent metal or the above monoamine. Or a salt thereof.

  Further, when the organic dye is an azo dye, the substituent represented by the general formulas (5) to (7) is introduced into the diazo component or the coupling component in advance, and then the coupling reaction is performed, thereby performing the azo pigment. Derivatives can also be produced.

  The triazine derivative having a basic substituent of the present invention can be synthesized by various synthetic routes. For example, an amine component starting from cyanuric chloride and forming a substituent represented by the general formulas (5) to (7) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N- It can be obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  The matrix skeleton is preferably a dye derivative in which P in the general formula (4) is an organic pigment residue, a β-naphthol residue, or a triazine residue, and among them, thiaindigo pigments, benzoisoindole pigments, diesters, and the like. Organic pigment residues that are ketopyrrolopyrrole pigments or anthraquinone pigments, or triazine residues are preferred.

  That is, in the colored composition of the present invention, P in the general formula (4) is an organic pigment residue, β-naphthol residue, or triazine residue, and L in the general formula (4) is a basic substitution. From the viewpoint of dispersion stability, a dye derivative having a basic substituent, a β-naphthol derivative having a basic substituent, and a triazine derivative having a basic substituent are preferable. Among these, triazine derivatives having a basic substituent are excellent in the dispersion of benzimidazolone pigments and have the greatest effect of preventing reaggregation of the pigment after dispersion.

  In the present invention, the amount of the dye derivative is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and most preferably 15 parts by weight or more with respect to 100 parts by weight of the pigment (C) from the viewpoint of improving dispersibility. It is. Further, from the viewpoint of heat resistance and light resistance, it is preferably 30 parts by weight or less, and most preferably 25 parts by weight or less with respect to 100 parts by weight of the pigment (C).

<Surfactant>
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When the surfactant is added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the pigment. When the blending amount of the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion may be affected by an excessive dispersant. .

<Photopolymerizable monomer (D)>
Examples of the photopolymerizable monomer (D) used in the present invention include ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, 2-acryloyloxyethyl succinic acid, and 2-methacryloyloxyethyl succinic acid. , 2-acryloyloxypropyl succinic acid, 2-methacryloyloxypropyl succinic acid, methoxyethylene glycol acrylate, methoxyethylene glycol methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol Acrylate, methoxypropylene glycol methacrylate, methoxydi Propylene glycol acrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, and commercially available products such as 2-acryloyloxyethyl succinic acid (trade name M-5300) And monofunctional monomers.
These monofunctional monomers can be used singly or in combination of two or more in any ratio as necessary.

  Examples of the photopolymerizable monomer (D) used in the present invention include ethylene glycol di (meth) acrylate, epoxy (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, and 1,4-butanediol di (meth). ) Acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, epoxy acrylate, and the like.

  Examples of the photopolymerizable monomer (D) used in the present invention include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate. And tri- or higher functional monomers such as monohydroxy oligoacrylates or monohydroxy oligomethacrylates.

The photopolymerizable monomer (D) used in the present invention may include a polyfunctional monomer having an acidic group, for example, a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid. And esterified products of dicarboxylic acids; and esterified products of polycarboxylic acids and monohydroxyalkyl (meth) acrylates.
Specific examples include monomethyl oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. And monoesterified products containing free carboxyl groups with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids, such as benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And a free carboxyl group-containing oligoester product of monohydroxy monoacrylate or monohydroxy monomethacrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. be able to.

  The photopolymerizable monomer (D) used in the present invention is preferably 10 to 300 parts by weight with respect to 100 parts by weight of the pigment (C), and 10 to 200 parts by weight from the viewpoint of photocurability and developability. More preferably, it is a part.

<Photopolymerization initiator (E)>
As the photopolymerization initiator (E) used in the present invention, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl Propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4 -Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, etc. Acetophenone compounds: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin iso Benzoin compounds such as propyl ether or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 Benzophenone compounds such as', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4- Thioxanthone compounds such as diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-tria 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, Or a triazine compound such as 2,4-trichloromethyl- (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- ( -Benzoyloxime)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4 , 6-trimethylbenzoyl) phenylphosphine oxide or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; Compounds: carbazole compounds; imidazole compounds; or titanocene compounds.
These photopolymerization initiators (E) can be used singly or as a mixture of two or more at any ratio as required.

  It is preferable that content of a photoinitiator (E) is 5-200 weight part with respect to 100 weight part of pigments (C), and is 10-150 weight part from a viewpoint of photocurability and developability. Is more preferable.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Solvent>
The solvent sufficiently disperses the colorant in the resin, and the filter composition is formed by applying the colored composition of the present invention on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. Used to make things easier.
As the solvent, 1,2,3-trichloropropane, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl -1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N- Methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, P-chlorotoluene, P-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene Glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl Ether, ethylene glycol monohexyl ether, ethylene glycol Recall monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate , Cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl Pill ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, Propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-acetate Chill, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used singly or in combination of two or more at any ratio as required.

  Among them, since the dispersibility of the pigment (C) of the present invention is good, glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, benzyl It is preferable to use aromatic alcohols such as alcohol and ketones such as cyclohexanone.

  The solvent can be used in an amount of 800 to 4000 parts by weight with respect to 100 parts by weight of the pigment (C) because the solvent can adjust the coloring composition to an appropriate viscosity and form a filter segment with a desired uniform film thickness. preferable.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen. Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight in 100% by weight of the total weight of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by weight based on the total weight of the thermosetting resin (100 parts by weight).

<Other additive components>
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the total weight of the pigment (C).

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the total weight of the pigment (C).

<Method for producing colored composition>
The coloring composition of the present invention comprises a pigment (C) and various dispersions such as a three-roll mill, a two-roll mill, a sand mill, a kneader, a trimix, or an attritor together with a resin, a solvent, and a dye derivative as necessary. It can be produced by finely dispersing using means. In addition, the coloring composition of the present invention may be prepared by dispersing other colorants such as a yellow pigment to be used together or by separately dispersing them.

It is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less. It is preferable that the color filter red coloring composition of the present invention does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less. (Measurement of particle size by SEM)
In addition, the average dispersed particle size of the color filter red coloring composition of the present invention is preferably 0.05 to 0.2 μm to increase the brightness and contrast ratio, and is 0.06 to 0.15 μm. Since brightness and contrast ratio can be made high, it is more preferable.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition comprises the pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other dispersants, and additives. Can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

<Removal of coarse particles>
The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust. Thus, it is preferable that the coloring composition for color filters substantially does not contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
The color filter of the present invention is a color filter comprising at least one filter segment formed from the colored composition of the present invention.
The color filter includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the at least one green filter segment is a red coloring composition for a color filter of the present invention. It is preferable to use a product.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.
[Printing method]
The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

[Photolithography]
When forming a filter segment by a photolithography method, the photosensitive coloring composition prepared as the solvent development type or alkali development type coloring composition is spray coated, spin coated, slit coated, roll coated, etc. on a transparent substrate. The coating method is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays, which are active energy rays, through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate | stimulate superposition | polymerization of a coloring composition, it can also heat as needed. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored composition, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, etc. in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  The colored composition of the present invention can be used in any of the methods described above, but is most suitable for the photolithography method.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight” and “%” represents “% by weight”. In the following examples, the molecular weight of the resin is a polystyrene-equivalent weight average molecular weight measured by GPC (gel permeation chromatography).

All NMR measurements in the examples were performed in DMSO-d6 using 1H-NMR measurement using JNM-ECX400P manufactured by JEOL. The number average molecular weight (Mn) and the weight average molecular weight (Mw) are values in terms of polystyrene measured by GPC-8020 manufactured by Tosoh Corporation.

  All IR measurements in the examples were performed using Spectrum One manufactured by PerkinElmer.

(Average primary particle size measurement method)
The average primary particle diameter of the pigment was measured (calculated) by the following method.
Add propylene glycol monomethyl ether acetate to the pigment powder and add the dispersant Disper
A small amount of byk-161 (Bic Chemie's dispersant) was added and treated with ultrasound for 1 minute to prepare a measurement sample. Using a transmission (TEM) electron microscope, three photographs (for 3 fields of view) in which primary particles of 100 or more pigments could be confirmed were prepared, and the size of 100 primary particles was measured sequentially from the upper left. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment are measured in nm units, the average is the primary particle diameter of the pigment particles, and a total of 300 distributions are created in increments of 5 nm. The median value in increments of 5 nm (for example, 8 nm in the case of 6 nm or more and 10 nm or less) was approximated as the particle diameter of those particles, and the number average particle diameter was calculated by calculating based on each particle diameter and the number thereof.

<< Synthesis of β-hydroxyalkylamide (A) >>
Synthesis example 1
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. To 447 parts of this liquid product, a mixture of 141 parts of 2-acryloyloxyethyl isocyanate (Karenz AOI manufactured by Showa Denko KK) and 0.3 part of methoquinone was dropped from a dropping device over 1 hour. It stirred at 100 degreeC after dripping for 1 hour. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A1 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis example 2
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, N, N, N ′, N′-tetrakis (hydroxyethyl) adipamide (Primid XL-552 manufactured by Emschemy) ) 320 parts were added and heated to 150 ° C. with stirring to melt. A mixture of 144 parts of 2-ethylhexanoic acid, 270 parts of 2-acryloyloxyethyl hexahydrophthalate (light acrylate HOA-HH manufactured by Kyoeisha Chemical Co., Ltd.), and 0.4 part of methoquinone was added to the dropping apparatus while blowing dry air. From about 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A2 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis example 3
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. While blowing dry air, 119 parts of 3,5,5-methylhexanoic acid (Kyowa Hakko Chemical Co., Ltd. Kyowanoic-N), 2-acryloyloxyethyl succinic acid (HO-MS, Kyoeisha Chemical Co., Ltd.) A mixture of 173 parts and methoquinone 0.3 part was added dropwise from a dropping device over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A3 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis example 4
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. While blowing dry air, a mixture of 198 parts of oleic acid and 0.3 part of methoquinone was dropped into the flask over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. Thereafter, the temperature was lowered to 60 ° C., and 2022 parts of cyclohexanone was added. A β-hydroxyalkylamide solution A4 containing a uniform yellowish brown transparent photopolymerizable functional group having a solid content of 20% was obtained.

Synthesis example 5
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. While blowing dry air, 133 parts of Ricacid DDSA (manufactured by Shin Nippon Chemical Co., Ltd.) was added dropwise from the dropping device over 1 hour. After the dropping, a mixture of 78 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko KK) and 0.3 part of methoquinone was added dropwise over 1 hour from the dropping device. After dropping, the mixture was stirred at 150 ° C. for 1 hour. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A5 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 6
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 361 parts of n-octanoic acid was dripped over 1 hour from the dripping apparatus. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. A mixture of 636 parts of this liquid product, 49 parts of maleic anhydride, 4 parts of dimethylbenzylamine and 0.4 part of methoquinone was heated again to 100 ° C. while blowing dry air and stirred for 1 hour. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A6 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis example 7
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. Thereafter, the temperature was lowered to 60 ° C., and 1786 parts of cyclohexanone was added. A β-hydroxyalkylamide solution A7 having a solid content of 20% and containing no uniform yellowish brown transparent photopolymerizable functional group was obtained.

Synthesis Example 8
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. A mixture of 320 parts of this product and 83 parts of isophthalic acid was again put in the reaction vessel and heated to 150 ° C. with stirring to melt. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. Thereafter, the temperature was lowered to 60 ° C., and 1542 parts of cyclohexanone was added. A β-hydroxyalkylamide solution A8 containing no uniform yellowish brown transparent photopolymerizable functional group having a solid content of 20% was obtained.

Synthesis Example 9
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 266 parts of diisopropanolamine, 10 parts of potassium hydroxide and 202 parts of sebacic acid were placed at 120 ° C. for 4 hours. Heated. 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water formed by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 433 parts of this product was again placed in the reaction vessel and melted by heating to 150 ° C. with stirring. In this, 72 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. Thereafter, the temperature was lowered to 60 ° C. and 1983 parts of cyclohexanone was added. A β-hydroxyalkylamide solution A9 having a solid content of 20% and containing no uniform yellowish brown transparent photopolymerizable functional group was obtained.

Synthesis Example 10
After putting 178 parts of 1-amino-2-butanol and 10 parts of potassium hydroxide into a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, and heating to 60 ° C. 100 parts of succinic anhydride was added little by little over 1 hour. After heating to 120 ° C. and heating for 4 hours, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 260 parts of this product was placed in the reaction vessel again and melted by heating to 150 ° C. with stirring. In this, 60 parts of phenyl isocyanate was dripped over 1 hour from the dripping apparatus. After dropping, the mixture was stirred at 150 ° C. for 1 hour, then the temperature was lowered to 60 ° C., and 1280 parts of cyclohexanone was added. A β-hydroxyalkylamide solution A10 having a solid content of 20% and containing no uniform yellowish brown transparent photopolymerizable functional group was obtained.

Synthesis Example 11
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed, and the integration ratio of the ester bond methylene group (near δ = 4.1) to the methyl group derived from 2-ethylhexanoic acid (near δ = 0.85) was 2: 6. From this, it was confirmed that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A11 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 12
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, N, N, N ′, N′-tetrakis (hydroxyethyl) adipamide (Primid XL-552 manufactured by Emschemy) ) 320 parts were added and heated to 150 ° C. with stirring to melt. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A12 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 13
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 216 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A13 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 14
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. 288 parts of 2-ethylhexanoic acid was dripped in this over 1 hour from the dripping apparatus. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A14 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 15
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. 158 parts of 3,5,5-methylhexanoic acid (Kyowa Hakko Chemical Co., Ltd. Kyowanoic N) was dripped in this over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. In a second reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, gas introduction tube, 222 parts of isophorone diisocyanate, 116 parts of 2-hydroxyethyl acrylate, 0.1 part of tetrabutyl titanate The reaction was carried out at 60 ° C. for 8 hours while blowing dry air. 461 parts of the above slurry product was added to the second reaction vessel and reacted at 60 ° C. for 8 hours. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A15 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 16
225 parts of dimethyl suberate, 234 parts of diethanolamine, 10 parts of potassium hydroxide, and 300 parts of toluene are placed in a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube. The tube was filled with toluene and heated to reflux while blowing nitrogen to remove methanol produced by azeotropy. After 4 hours, all the toluene was removed, and 1H-NMR measurement and IR measurement were performed to confirm that the target product was produced. After cooling to 50 ° C., cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A16 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 17
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean Stark tube, a reflux condenser, and a gas introduction tube, 256 parts of dimethyl sebacate, 234 parts of diethanolamine, 10 parts of potassium hydroxide, and 300 parts of toluene are added. The tube was filled with toluene and heated to reflux while blowing nitrogen to remove methanol produced by azeotropy. After 4 hours, all the toluene was removed, and 1H-NMR measurement and IR measurement were performed to confirm that the target product was produced. After cooling to 50 ° C., cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A17 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 18
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 287 parts of dimethyl dodecanedioate, 234 parts of diethanolamine, 10 parts of potassium hydroxide and 300 parts of toluene were added. The Stark tube was filled with toluene and heated to reflux while blowing nitrogen to remove methanol produced by azeotropy. After 4 hours, all the toluene was removed, and 1H-NMR measurement and IR measurement were performed to confirm that the target product was produced. After cooling to 50 ° C., cyclohexanone was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A18 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 19
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. To 447 parts of this liquid product, a mixture of 141 parts of 2-acryloyloxyethyl isocyanate (Karenz AOI manufactured by Showa Denko KK) and 0.3 part of methoquinone was dropped from a dropping device over 1 hour. It stirred at 100 degreeC after dripping for 1 hour. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C. and methoxypropyl acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A19 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 20
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, N, N, N ′, N′-tetrakis (hydroxyethyl) adipamide (Primid XL-552 manufactured by Emschemy) ) 320 parts were added and heated to 150 ° C. with stirring to melt. A mixture of 144 parts of 2-ethylhexanoic acid, 270 parts of 2-acryloyloxyethyl hexahydrophthalate (light acrylate HOA-HH manufactured by Kyoeisha Chemical Co., Ltd.), and 0.4 part of methoquinone was added to the dropping apparatus while blowing dry air. From about 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C. and methoxypropyl acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A20 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 21
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. While blowing dry air, 119 parts of 3,5,5-methylhexanoic acid (Kyowa Hakko Chemical Co., Ltd. Kyowanoic-N), 2-acryloyloxyethyl succinic acid (HO-MS, Kyoeisha Chemical Co., Ltd.) A mixture of 173 parts and methoquinone 0.3 part was added dropwise from a dropping device over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C. and methoxypropyl acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A21 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 22
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. While blowing dry air, a mixture of 198 parts of oleic acid and 0.3 part of methoquinone was dropped into the flask over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. Thereafter, the temperature was lowered to 60 ° C., and 2022 parts of methoxypropyl acetate was added. A β-hydroxyalkylamide solution A22 containing a uniform yellowish brown transparent photopolymerizable functional group having a solid content of 20% was obtained.

Synthesis Example 23
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. While blowing dry air, 133 parts of Ricacid DDSA (manufactured by Shin Nippon Chemical Co., Ltd.) was added dropwise from the dropping device over 1 hour. After the dropping, a mixture of 78 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko KK) and 0.3 part of methoquinone was added dropwise over 1 hour from the dropping device. After dropping, the mixture was stirred at 150 ° C. for 1 hour. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C. and methoxypropyl acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A23 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 24
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 361 parts of n-octanoic acid was dripped over 1 hour from the dripping apparatus. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. A mixture of 636 parts of this liquid product, 49 parts of maleic anhydride, 4 parts of dimethylbenzylamine and 0.4 part of methoquinone was heated again to 100 ° C. while blowing dry air and stirred for 1 hour. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C. and methoxypropyl acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A24 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 25
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. Thereafter, the temperature was lowered to 60 ° C., and 1786 parts of methoxypropyl acetate was added. A β-hydroxyalkylamide solution A25 containing a uniform yellowish brown transparent photopolymerizable functional group having a solid content of 20% was obtained.

Synthesis Example 26
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. A mixture of 320 parts of this product and 83 parts of isophthalic acid was again put in the reaction vessel and heated to 150 ° C. with stirring to melt. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. Thereafter, the temperature was lowered to 60 ° C., and 1542 parts of methoxypropyl acetate was added. A β-hydroxyalkylamide solution A26 having a solid content of 20% and containing no uniform yellowish brown transparent photopolymerizable functional group was obtained.

Synthesis Example 27
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 266 parts of diisopropanolamine, 10 parts of potassium hydroxide and 202 parts of sebacic acid were placed at 120 ° C. for 4 hours. Heated. 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water formed by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 433 parts of this product was again placed in the reaction vessel and melted by heating to 150 ° C. with stirring. In this, 72 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. Thereafter, the temperature was lowered to 60 ° C., and 1983 parts of methoxypropyl acetate was added. A β-hydroxyalkylamide solution A27 having a solid content of 20% and containing no uniform yellowish brown transparent photopolymerizable functional group was obtained.

Synthesis Example 28
After putting 178 parts of 1-amino-2-butanol and 10 parts of potassium hydroxide into a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, and heating to 60 ° C. 100 parts of succinic anhydride was added little by little over 1 hour. After heating to 120 ° C. and heating for 4 hours, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, the slurry-like product produced in the container was taken out and dried in vacuum. 260 parts of this product was placed in the reaction vessel again and melted by heating to 150 ° C. with stirring. In this, 60 parts of phenyl isocyanate was dripped over 1 hour from the dripping apparatus. After dropping, the mixture was stirred at 150 ° C. for 1 hour, the temperature was lowered to 60 ° C., and 1280 parts of methoxypropyl acetate was added. A β-hydroxyalkylamide solution A28 having a solid content of 20% and containing no uniform yellowish brown transparent photopolymerizable functional group was obtained.

Synthesis Example 29
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed, and the integration ratio of the ester bond methylene group (near δ = 4.1) to the methyl group derived from 2-ethylhexanoic acid (near δ = 0.85) was 2: 6. From this, it was confirmed that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C. and methoxypropyl acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A29 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 30
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, N, N, N ′, N′-tetrakis (hydroxyethyl) adipamide (Primid XL-552 manufactured by Emschemy) ) 320 parts were added and heated to 150 ° C. with stirring to melt. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C. and methoxypropyl acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A30 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 31
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 216 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C. and methoxypropyl acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A31 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 32
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. 288 parts of 2-ethylhexanoic acid was dripped in this over 1 hour from the dripping apparatus. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C. and methoxypropyl acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A32 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 33
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. 158 parts of 3,5,5-methylhexanoic acid (Kyowa Hakko Chemical Co., Ltd. Kyowanoic N) was dripped in this over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. In a second reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, gas introduction tube, 222 parts of isophorone diisocyanate, 116 parts of 2-hydroxyethyl acrylate, 0.1 part of tetrabutyl titanate The reaction was carried out at 60 ° C. for 8 hours while blowing dry air. 461 parts of the above slurry product was added to the second reaction vessel and reacted at 60 ° C. for 8 hours. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, methoxypropyl acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A33 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 34
225 parts of dimethyl suberate, 234 parts of diethanolamine, 10 parts of potassium hydroxide, and 300 parts of toluene are placed in a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube. The tube was filled with toluene and heated to reflux while blowing nitrogen to remove methanol produced by azeotropy. After 4 hours, all the toluene was removed, and 1H-NMR measurement and IR measurement were performed to confirm that the target product was produced. After cooling to 50 ° C., methoxypropyl acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A34 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 35
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean Stark tube, a reflux condenser, and a gas introduction tube, 256 parts of dimethyl sebacate, 234 parts of diethanolamine, 10 parts of potassium hydroxide, and 300 parts of toluene are added. The tube was filled with toluene and heated to reflux while blowing nitrogen to remove methanol produced by azeotropy. After 4 hours, all the toluene was removed, and 1H-NMR measurement and IR measurement were performed to confirm that the target product was produced. After cooling to 50 ° C., methoxypropyl acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A35 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

Synthesis Example 36
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 287 parts of dimethyl dodecanedioate, 234 parts of diethanolamine, 10 parts of potassium hydroxide and 300 parts of toluene were added. The Stark tube was filled with toluene and heated to reflux while blowing nitrogen to remove methanol produced by azeotropy. After 4 hours, all the toluene was removed, and 1H-NMR measurement and IR measurement were performed to confirm that the target product was produced. After cooling to 50 ° C., methoxypropyl acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A36 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

<< Synthesis of Polymer Solution (B) Containing Carboxyl Group >>
Synthesis Example 37
Put 100 parts of cyclohexanone into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction tube, heat to 80 ° C. while injecting nitrogen gas into the vessel, and 20 parts of methacrylic acid at the same temperature, A mixture of 10 parts of methyl methacrylate, 55 parts of n-butyl methacrylate, 15 parts of benzyl methacrylate and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. After completion of dropping, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour to obtain an acrylic resin solution. Got. After cooling to room temperature, by diluting with cyclohexanone, a polymer solution B1 containing a carboxyl group not containing a photopolymerizable functional group having a solid content of 20% was obtained. The weight average molecular weight was 40,000.

Synthesis Example 38
Put 100 parts of cyclohexanone into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction tube, heat to 80 ° C. while injecting nitrogen gas into the vessel, and 25 parts of methacrylic acid at the same temperature, A mixture of 20 parts of 2-hydroxyethyl methacrylate, 30 parts of methyl methacrylate, 25 parts of styrene and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and then the mixture was stirred at the same temperature for 3 hours. Obtained. Subsequently, the temperature of the reaction vessel was cooled to 70 ° C., and dry air was further introduced into the reaction vessel, and 24 parts of 2-methacryloyloxyethyl isocyanate, 36 parts of cyclohexanone, 0.1 part of dibutyltin dilaurate, 0.1 part of methoquinone 0.1 Then, stirring was continued at the same temperature for 10 hours. After cooling to room temperature, the solution was diluted with cyclohexanone to obtain a polymer solution B2 containing a photopolymerizable functional group having a solid content of 20% and a carboxyl group. The weight average molecular weight was 42,000.

Synthesis Example 39
Put 100 parts of cyclohexanone into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction tube, heat to 80 ° C. while injecting nitrogen gas into the vessel, and 40 parts of methacrylic acid at the same temperature, A mixture of 25 parts of methyl methacrylate, 12.5 parts of styrene, 17.5 parts of n-butyl methacrylate, 5 parts of 2-methoxyethyl acrylate, and 4 parts of 2,2′-azobisisobutyronitrile is added dropwise over 1 hour. The polymerization reaction was carried out. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and then the mixture was stirred at the same temperature for 3 hours. Obtained. Subsequently, dry air was introduced into the reaction vessel, and 25 parts of glycidyl methacrylate, 37 parts of cyclohexanone, 1 part of dimethylbenzylamine, and 0.1 part of methoquinone were charged, and stirring was continued at the same temperature for 10 hours. After cooling to room temperature, it was diluted with cyclohexanone to obtain a polymer solution B3 containing a photopolymerizable functional group having a solid content of 20% and a carboxyl group. The weight average molecular weight was 41000.

Synthesis Example 40
Into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction tube, 100 parts of cyclohexanone was heated to 80 ° C. while injecting nitrogen gas into the vessel, and 68 parts of glycidyl methacrylate at the same temperature, A mixture of 17 parts of methyl methacrylate, 7.5 parts of n-butyl methacrylate, 7.5 parts of benzyl methacrylate and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and then the mixture was stirred at the same temperature for 3 hours. Obtained. Subsequently, dry air was introduced into the reaction vessel, and 55 parts of acrylic acid, 83 parts of cyclohexanone, 1 part of dimethylbenzylamine and 0.1 part of methoquinone were charged, and stirring was continued for 10 hours at the same temperature. Further, 117 parts of tetrahydrophthalic anhydride was charged and stirring was continued for 10 hours at the same temperature. After cooling to room temperature, it was diluted with cyclohexanone to obtain a polymer solution B4 containing a photopolymerizable functional group having a solid content of 20% and a carboxyl group. The weight average molecular weight was 44,000.

<< Synthesis of polymer solution (b5) containing no carboxyl group >>
Comparative Synthesis Example 1
Put 100 parts of cyclohexanone into a reaction vessel equipped with a stirrer, thermometer, dripping device, reflux condenser, and gas introduction tube, heat to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature 2-hydroxyethyl methacrylate A mixture of 55.5 parts, 10 parts of methyl methacrylate, 19.5 parts of n-butyl methacrylate, 15 parts of benzyl methacrylate and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. went. After completion of dropping, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour to obtain an acrylic resin solution. Got. After cooling to room temperature, the polymer solution b5 containing a hydroxyl group with a solid content of 20% was obtained by diluting with cyclohexanone. The weight average molecular weight was 38000.

<< Method for Producing Pigment Dispersion >>
[Adjustment Example 1]
C. I. 200 parts of Pigment Green 58, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of pigment 1 were obtained. The primary particle diameter determined by TEM (transmission electron microscope) was 50 nm.

(Preparation of pigment dispersion (C-1))
After the mixture having the composition shown below was uniformly stirred and mixed, it was dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. Filtration through a filter gave a pigment dispersion (C-1).
Pigment 1: 11.0 parts Polymer solution (B1): 40 parts Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts Resin type dispersant (EFKA4300): 1.0 parts

[Adjustment Example 2]
100 parts of a hydroxyaluminum phthalocyanine pigment represented by the following formula (500), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product is poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a whole day and night. 2 was obtained. The average primary particle size was 30.4 nm.
Formula (500)

(Preparation of pigment dispersion (C-2))
After the mixture having the composition shown below was uniformly stirred and mixed, it was dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. Filtration through a filter gave a pigment dispersion (C-2).
Pigment 2: 11.0 parts Polymer solution (B1): 40 parts Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts Resin type dispersant (EFKA4300): 1.0 parts

[Adjustment Example 3]
In a reaction vessel, 100 parts of a hydroxyaluminum phthalocyanine pigment represented by the formula (500) and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and then dried to obtain 114 parts of a pigment represented by the following formula (501).
Next, pigment 3 was obtained by the same salt milling method as that of pigment 2. The average primary particle size was 31.2 nm.

Formula (501)

(Preparation of pigment dispersion (C-3))
After the mixture having the composition shown below was uniformly stirred and mixed, it was dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. Filtration through a filter gave a pigment dispersion (C-3).
Pigment 3: 11.0 parts Polymer solution (B1): 40 parts Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts Resin type dispersant (EFKA4300): 1.0 parts

[Adjustment Example 4]
In a reaction vessel, 100 parts of methanol and 100 parts of a hydroxyaluminum phthalocyanine pigment represented by the formula (500) and 43.2 parts of diphenylphosphinic acid were added and heated to 40 ° C. and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain 112 parts of a pigment represented by the following formula (502).
Next, pigment 4 was obtained by the same salt milling method as that for pigment 2. The average primary particle size was 29.5 nm.

Formula (502)

(Preparation of pigment dispersion (C-4))
After the mixture having the composition shown below was uniformly stirred and mixed, it was dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. Filtration through a filter gave a pigment dispersion (C-4).
Pigment 4: 11.0 parts Polymer solution (B1): 40 parts Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts Resin type dispersant (EFKA4300): 1.0 parts

(Preparation of pigment dispersion (C-5))
After stirring and mixing a mixture having the following composition to be uniform, using a zirconia bead having a diameter of 0.5 mm, using an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) as a media type wet disperser. After dispersing for 4 hours, the mixture was filtered through a 5 μm filter to obtain a pigment dispersion (C-5).
Pigment 4: 10.0 parts Resin-type dispersant (“BYK-LPN6919” manufactured by Big Chemie): 8.3 parts Propylene glycol monomethyl ether acetate (PGMAC): 56.7 parts Polymer solution (B1): 25.0 parts

[Preparation Example 5]
C. I. 200 parts of Pigment Green 36, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of pigment 5 were obtained.

(Preparation of pigment dispersion (C-6))
After the mixture having the composition shown below was uniformly stirred and mixed, the mixture was dispersed for 3 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. Filtration through a filter gave a green pigment dispersion (C-6).
Pigment 5: 11.0 parts Polymer solution (b5): 40 parts Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts Resin type dispersant (EFKA4300): 1.0 parts

[Preparation of photosensitive composition for color filter]
[Examples 1 to 43 and Comparative Examples 1 to 4]
Each material was mixed and stirred at a formulation ratio shown in Table 1 and Table 2, and filtered through a 1 μm filter to obtain each colored composition.

Abbreviations in Table 1 and Table 2 are described below.
Photopolymerizable monomer (D): Dipentaerythritol hexaacrylate
("Aronix M-402" manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator (E): N1919: Photoradical polymerization initiator
("Optomer" N1919 "manufactured by Adeka Corporation)
Sensitizer: 2,4-diethylthioxanthone
(“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
Amine-based additive: Triethanolamine Curing agent: Full ether type ("Nicarac MW-30" manufactured by Nippon Carbide Industries, Ltd.)
Effect accelerator: 4- (dimethylamino) -N, N-dimethylbenzylamine Leveling agent: “BYK-333” manufactured by Big Chemie

<Light resistance evaluation>
[Color difference evaluation]
The colored compositions obtained in Examples 1 to 43 and Comparative Examples 1 to 4 were placed on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater and y (SB2) = 0. The film was applied to a film thickness of 60, then dried under reduced pressure, heated at 230 ° C. for 20 minutes, allowed to cool, and then a transparent conductive film was formed on the coating film by sputtering. [L * (1), a * (1), b * (1)] was measured for the chromaticity of the obtained coating film using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.).
[Light resistance evaluation]
Further, chromaticity [L * (2), a * (2), b * (2)] after irradiation with ultraviolet rays using a 470 W / m ² xenon lamp was measured, and the color difference was calculated by the following formula (1). ΔE * ab was determined.
Formula (1) ΔE * ab = [[L * (2) −L * (1)] ² + [a * (2) −a * (1)] ² + [b * (2) −b * (1 )] ² ] ^1/2
The smaller the color difference ΔE * ab, the smaller the color change due to light irradiation, and a colored composition with good light resistance. Each sample was evaluated according to the following criteria.
○: ΔE * ab is less than 3.0 Δ: ΔE * ab is 3.0 or more and less than 5.0 ×: The result of ΔE * ab is 5.0 or more is shown in Table 3.

As shown in Table 3, as in Examples 1 to 43, at least β-hydroxyalkylamide (A), a polymer (B) containing a carboxyl group, and a pigment represented by the general formula (1) (C The color composition for color filters composed of) was excellent in light resistance, while β-hydroxyalkylamide (A), a polymer (B) containing a carboxyl group, and a general formula as in Comparative Examples 1 to 4 The sample formed from the colored composition not containing any of the pigment (C) represented by (1) was inferior in light resistance.
Moreover, the sensitivity was good also in the coloring composition of Examples 1-43.

  As described above, for a color filter comprising a colored composition comprising at least β-hydroxyalkylamide (A), a polymer (B) containing a carboxyl group, and a pigment (C) represented by the general formula (1) By combining the coloring compositions, it is possible to obtain a high-quality color filter that does not cause discoloration due to light irradiation in the absence of oxygen.

  Thereby, the coloring composition for color filters which consists of at least (beta) -hydroxyalkylamide (A), the polymer (B) containing a carboxyl group, and the pigment (C) represented by General formula (1) in a coloring composition. Obviously, the product is excellent in light resistance and sensitivity, and can provide a high-quality color filter.

Claims (11)

A color comprising at least a β-hydroxyalkylamide (A) represented by the following general formula (101), a polymer (B) containing a carboxyl group, and a pigment (C) represented by the following general formula (1) A coloring composition for a filter, wherein the pigment (C) contains a phthalocyanine pigment represented by the following general formula (1).

Formula (101)

[Wherein, X is an n-valent group consisting of carbon and hydrogen, n is an integer of 2 to 6, and R ¹ and R ² are each independently a hydrogen atom, an aliphatic hydrocarbon group, The alicyclic hydrocarbon group, the aromatic hydrocarbon group, the group represented by the general formula (102), or the group represented by the general formula (103) represents one or more R bonded to one or more nitrogen atoms. ^At least one of ¹ and R ² is a group represented by the general formula (102). ]

General formula (102)
General formula (103)

[Wherein R ^{3 to} R ⁶ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxyl group, and R ⁷ is a residue of a compound having a functional group capable of reacting with a hydroxyl group. And the functional group capable of reacting with a hydroxyl group includes a carboxyl group, an isocyanate group, a carboxylic acid anhydride group, an acid halide group, a carboxylic acid tertiary alkyl ester group, a hydroxymethylamino group, an alkoxysilyl group, and an epoxy group. Is at least one selected from the group consisting of ]]

General formula (1)
[Wherein, X _{1 to} X ₄ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. A heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or a substituent. Represents an optionally substituted arylthio group.
Y _{1 to} Y ₄ each independently represents a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group.
M represents Zn or Al-Z.
Z represents a hydroxyl group, a chlorine atom, —OP (═O) R ₈₅ R ₈₆ , or —O—SiR ₈₇ R ₈₈ R ₈₉ .
Wherein R _{85 to} R ₈₉ may each independently have a hydrogen atom, a hydroxyl group or a substituent.
Alkyl group, aryl group which may have a substituent, alkoxyl group which may have a substituent
Or an aryloxy group which may have a substituent, and R _{85 to} R ₈₉ are bonded to each other.
They may combine to form a ring.
m ₁ , m ₂ , m ₃ , m ₄ , n ₁ , n ₂ , n ₃ , and n ₄ each independently represent an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + N ₃ and m ₄ + n ₄ are each 0 to 4, and may be the same or different. ] The coloring composition according to claim 1, wherein at least one of β-hydroxyalkylamide (A) or a polymer (B) containing a carboxyl group contains a photopolymerizable functional group. Furthermore, the coloring composition of Claim 1 or 2 containing a photopolymerizable monomer (D) and / or a photoinitiator (E). The colored composition according to any one of claims 1 to 3, wherein the compound having a functional group capable of reacting with a hydroxyl group in the general formula (103) is a monofunctional isocyanate or a monofunctional carboxylic acid. The compound having a functional group capable of reacting with a hydroxyl group in the general formula (103) is represented by at least one selected from the group consisting of the following general formula (104), general formula (105), and general formula (106). The coloring composition according to any one of claims 1 to 4, wherein the coloring composition is a compound to be obtained.

General formula (104)

[Wherein, R ⁸ represents a linear, cyclic or branched saturated or unsaturated hydrocarbon group having 2 to 18 carbon atoms. ]

General formula (105)


[Wherein R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ is a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic group. A hydrocarbon group, and R ¹¹ is a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group. ]

Formula (106)

[In the formula, R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents a group represented by the general formula (107) or a group represented by the general formula (108). ]

General formula (107)

Wherein, n ¹ is an integer of 1-2. ]

Formula (108)

[Wherein R ¹⁴ represents a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group, and R ¹⁵ represents the number of carbon atoms. 6-13 linear or branched alkylene groups, divalent alicyclic hydrocarbon groups, or divalent aromatic hydrocarbon groups. ]] The colored composition according to any one of claims 1 to 5, wherein the compound having a functional group capable of reacting with a hydroxyl group in the general formula (103) has a photopolymerizable functional group. The coloring composition according to any one of claims 1 to 6, wherein an atom directly bonded to a carbonyl group in X in the general formula (101) is a carbon atom not contained in an aromatic ring. The X in the general formula (101) is an n-valent aliphatic hydrocarbon group having 6 or more carbon atoms or an n-valent alicyclic hydrocarbon group. Coloring composition. β-hydroxyalkylamide (A) is (a-1) a divalent or higher carboxylic acid or derivative thereof, and (a-2) a primary or secondary amine having one or more hydroxyl groups at the β-position, (A-3) a compound obtained by reacting a part of the hydroxyl group of (a-3) β-hydroxyalkylamide obtained by amidation with a compound having one or more functional groups capable of reacting with hydroxyl group (a-4) It is, The manufacturing method of the coloring composition in any one of Claims 1-8 characterized by the above-mentioned. β- hydroxyalkylamide (A) is, according to claim 1-8 coloring composition according to any one which is soluble in organic solvents. A color filter comprising a filter segment formed from the colored composition according to any one of claims 1 to 8 or claim 10 on a transparent substrate.