JP2006163084A - Photosensitive colored composition for color filter, and the color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve conventional photosensitive colored compositions so as to satisfy both the NMP resistance (chromaticity change, swelling of film, cracking resistance of the film) and superior dispersion stability, and to improve a conventional color filter, whose NMP resistance (chromaticity change, swelling of film, cracking resistance of the film) is inferior. <P>SOLUTION: There are provided a photosensitive colored composition for a color filter, containing a urethane urea resin represented by Formula (1), a monomer and a colorant, and a color filter having filter segments formed from the photosensitive colored composition. In the Formula (1), R<SP>1</SP>denotes a tri- to pentadeca-valent organic residue; R<SP>2</SP>denotes a substituted or unsubstituted hydrocarbon group; R<SP>3</SP>denotes a divalent organic residue, having a urethane bond in a backbone; m is an integer of 2-14; n is an integer of 1-13; and x is an integer of 0-100. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photosensitive coloring composition for a color filter used for producing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter formed using the same.

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 in a fixed arrangement. It is made up of arranged ones. 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.
In general, a transparent electrode for driving a liquid crystal is formed by vapor deposition or sputtering on a color filter used in a color liquid crystal display device, and further, an alignment for aligning the liquid crystal in a certain direction on the transparent electrode. A film is formed. 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 pigment dispersion method, a photosensitive coloring composition (pigment resist material) in which a pigment is dispersed in a photosensitive resin composition is applied to a transparent substrate such as glass, the solvent is removed by drying, and then a filter color pattern is obtained. After exposure, the unexposed areas are removed in the development process to form a pattern for the first color, and after processing such as heating as necessary, the same operation is sequentially repeated for all filter colors. Can be manufactured.

However, a color filter formed from a photosensitive coloring composition containing a conventional acrylic resin has a large change in chromaticity depending on N-methylpyrrolidone (hereinafter referred to as NMP) used as a solvent in a later step. The filter segment swelled. In order to improve the NMP resistance of the color filter and reduce the swelling of the filter segment, it is necessary to reduce the double bond equivalent of the photosensitive coloring composition. In order to reduce the double bond equivalent of the photosensitive coloring composition, it is necessary to increase the ratio of the monomer in the photosensitive coloring composition or to adjust the type and ratio of the monomer constituting the acrylic resin. Become. However, when the ratio of the monomer in the photosensitive coloring composition is increased, cracks are generated in the filter segment due to NMP used as a solvent in a later step. In addition, when the type and ratio of the monomers constituting the acrylic resin are adjusted so that the double bond equivalent is lowered, the photosensitivity is reduced as the monomer component contributing to the dispersibility of the colorant decreases. The dispersion stability of the coloring composition is lowered.
JP 2004-101728 A

The problem to be solved by the present invention is that the conventional photosensitive coloring composition cannot achieve both NMP resistance (chromaticity change, coating film swelling, coating crack resistance) and excellent dispersion stability. is there.
Another problem to be solved by the present invention is that the conventional color filter has poor NMP resistance (chromaticity change, coating film swelling, coating film crack resistance).

（式中、Ｒ¹は３〜１５価の有機残基を示す。Ｒ²は置換もしくは未置換の炭化水素基を示す。Ｒ³は、主鎖にウレタン結合を有する２価の有機残基を示す。ｍは２〜１４の整数、ｎは１〜１３の整数、ｘは０〜１００の整数である。）
また、本発明のカラーフィルタは、本発明のカラーフィルタ用感光性着色組成物から形成されるフィルタセグメントを具備することを特徴とする。 The photosensitive coloring composition for color filters of this invention contains the urethane urea resin represented by following General formula (1), a monomer, and a coloring agent, It is characterized by the above-mentioned.

(In the formula, R ¹ represents a 3-15 valent organic residue. R ² represents a substituted or unsubstituted hydrocarbon group. R ³ represents a divalent organic residue having a urethane bond in the main chain. M is an integer of 2 to 14, n is an integer of 1 to 13, and x is an integer of 0 to 100.)
Moreover, the color filter of this invention comprises the filter segment formed from the photosensitive coloring composition for color filters of this invention, It is characterized by the above-mentioned.

The photosensitive coloring composition for a color filter according to the present invention uses a urethane urea resin having an acryloyl group introduced at both ends via urea bonds as a binder, so that it has excellent dispersion stability and a coating film to be formed. Demonstrates NMP resistance.
By using the photosensitive coloring composition for color filters of the present invention, it is possible to stably produce high-quality transmissive / reflective color liquid crystal display devices and color filters for color separation of solid-state imaging devices.

First, the photosensitive coloring composition for color filters of this invention is demonstrated.
The photosensitive coloring composition for color filters of this invention contains the urethane urea resin represented by the said General formula (1), a monomer, and a coloring agent, It is characterized by the above-mentioned.
The urethane urea resin represented by the general formula (1) may be produced through any method and process, but the urethane prepolymer (C) having an isocyanato group at the terminal is represented by the following general formula (2 It is most preferable to produce by the method of reacting the compound (M) having a secondary amino group represented by

（式中、Ｒ¹は３〜１５価の有機残基を示す。Ｒ²は置換もしくは未置換の炭化水素基を示す。ｐは２〜１４の整数、ｓはＲ¹の価数からｐを引いた整数である。）
前記化合物（Ｍ）は、例えば、一級アミノ基を一つ有する化合物（ａ）を、アクリロイル基を三つ以上有する化合物（ｘ）にマイケル付加させて得ることができる。この場合、Ｒ¹は、アクリロイル基を三つ以上有する化合物（ｘ）由来の３〜１５価の有機残基となり、Ｒ²は、一級アミノ基を一つ有する化合物（ａ）由来の置換もしくは未置換の炭化水素基となり、Ｒ³は、ウレタンプレポリマー（Ｃ）由来の２価の有機残基となる。Ｒ¹〜Ｒ³の具体例は、それぞれ化合物（ｘ）、化合物（ａ）、プレポリマー（Ｃ）を例示することで示す。

(In the formula, R ¹ represents a 3 to 15 valent organic residue. R ² represents a substituted or unsubstituted hydrocarbon group. P is an integer of 2 to 14, and s is p from the valence of R ^1. Subtracted integer.)
The compound (M) can be obtained, for example, by Michael addition of the compound (a) having one primary amino group to the compound (x) having three or more acryloyl groups. In this case, R ¹ is a 3- to 15-valent organic residue derived from the compound (x) having three or more acryloyl groups, and R ² is a substituted or non-substituted group derived from the compound (a) having one primary amino group. It becomes a substituted hydrocarbon group, and R ³ becomes a divalent organic residue derived from the urethane prepolymer (C). Specific examples of R ^{1 to} R ³ are shown by illustrating the compound (x), the compound (a), and the prepolymer (C), respectively.

<About urethane prepolymer (C)>
The urethane prepolymer (C) having an isocyanato group at the terminal is produced by reacting a polyol and a polyisocyanate.
The polyol used for the production of the urethane prepolymer (C) is a compound having 2 or 3 or more hydroxyl groups in one molecule, and is roughly classified into a low molecular weight polyol and a high molecular weight polyol.
Examples of the low molecular weight polyol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3 , 3′-dimethylol heptane, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, Octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanedimethanol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl, 2,2,8,10-tetraoxo Spiro [5.5] undecane, etc. Diols, trimethylol ethane, trimethylol propane, glycerin, pentaerythritol and the like.

The high molecular weight polyol is a polyol having a number average molecular weight of about 300 to 5,000, preferably 350 to 2,100. For example, polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, epoxy polyol and the like are used.
Examples of the polyether polyol include polyethylene glycol, polyoxypropylene glycol, poly (ethylene / propylene) glycol, and polytetramethylene glycol.
The polyester polyol includes a polyester polyol obtained by polycondensation of a dibasic acid and a polyol, and a polyester polyol obtained by ring-opening polymerization of a lactone. Examples of the dibasic acid component used as the former raw material include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, and isophthalic acid. Examples of the polyol component include compounds listed as the low molecular weight polyol. Is mentioned. Examples of the lactones used as the latter raw material include polycaprolactone, poly (β-methyl-γ-valerolactone), and polyvalerolactone.

As the polycarbonate polyol, for example, a product obtained by reacting polyols or bisphenols with a carbonate ester by a known method is used. Examples of the carbonate ester used as a raw material for polycarbonate polycarbonate include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate and the like. Can be mentioned. Examples of the polyols include the compounds listed as the low molecular weight polyol. Examples of bisphenols include bisphenol A, bisphenol F, and compounds obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to the bisphenol.
As the acrylic polyol, for example, a copolymer obtained by polymerizing a hydroxyl group-containing (meth) acrylic monomer and another ethylenically unsaturated monomer by a known method is used. Hydroxyl-containing monomers include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dihydroxy (meth) acrylate, glycerol (meth) acrylate. And so on.

When producing a color filter by a photolithographic method using the photosensitive coloring composition for a color filter of the present invention, there is usually a development step with a solvent or an alkaline solution, but particularly when development is performed with an alkaline solution. It is preferable to use an anionic functional group-containing polyol as one component of the polyol.
As the anionic functional group-containing polyol, for example, a polyol having an anionic functional group such as a carboxyl group or a sulfone group can be used, and it is particularly preferable to use a carboxyl group-containing polyol.

  Examples of the carboxyl group-containing polyol include dimethylolpropionic acid, 2,2-dimethylolacetic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, dimethylolalkanoic acid such as dihydroxypropionic acid, dihydroxysuccinic acid, And dihydroxybenzoic acid. In particular, dimethylolpropionic acid and 2,2-dimethylolbutyric acid are preferably used in terms of reactivity and solubility.

In addition, if you want to increase the ethylenically unsaturated double bond density of the resin and suppress the change in chromaticity of the filter segment with the N-methylpyrrolidone solvent used in the process after the color filter is created, one component of polyol It is preferable to use a compound (E) having at least two hydroxyl groups and at least one ethylenically unsaturated double bond in one molecule. The compound (E) is preferably used in the range of 30 to 100% by weight based on the total weight of the polyol. When the amount of the compound (E) used is less than 30% by weight, the curability for ultraviolet rays is not sufficiently improved, and the chromaticity of the filter segment varies depending on the N-methylpyrrolidone solvent used in the process after the color filter is formed. There are things to do.
The compound (E) includes a compound (E1) having two hydroxyl groups and one ethylenically unsaturated double bond in one molecule, and at least two hydroxyl groups and at least two ethylene in one molecule. A compound (E2) having a polymerizable unsaturated double bond is used.
Examples of the compound (E1) having two hydroxyl groups and one ethylenically unsaturated double bond in one molecule include glycerol mono (meth) acrylate and glycerol arylate. In addition, 2- (meta) is added to the primary or secondary amino group of a compound having one primary or secondary amino group and two hydroxyl groups in one molecule such as diethylamine or 2-hydroxymethylaminoethanol. ) Isocyanato of a compound having both an isocyanato group and a radically polymerizable unsaturated group in a molecule such as an isocyanato group of acryloyloxyisocyanate or a 1: 1 molar addition compound of diisocyanate and 2-hydroxyalkyl (meth) acrylate. The thing obtained by making group react is also mentioned.

（式中、Ｒ⁴は、ＨまたはＣＨ₃基、Ｒ⁵は、ｒ価の有機残基を示す。ｒは２〜４の整数である。） In addition, as the compound (E2) having at least two hydroxyl groups and at least two ethylenically unsaturated double bonds in one molecule, for example, an epoxy group of a compound having two or more epoxy groups may be ethylenic. Examples thereof include compounds obtained by adding a compound having an unsaturated double bond and a carboxyl group so that the epoxy group and the carboxyl group are equivalent, and among these compounds, the compound represented by the following general formula (3) is particularly preferable. preferable.

(Wherein R ⁴ represents an H or CH ₃ group, R ⁵ represents an r-valent organic residue, r is an integer of 2 to 4)

The compound represented by the general formula (3) is obtained by adding (meth) acrylic acid to an epoxy group of a compound having two or more epoxy groups, preferably a compound having two epoxy groups.
Examples of the compound having two epoxy groups include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene. Glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, dibromoneopentyl Glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, 1,6 hexanediol diglycidyl ether, poly 1,6 hexanediol diglyci Ether, bisphenol A diglycidyl ether, ethylene glycol-added bisphenol A diglycidyl ether, propylene glycol-added bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, glycero Examples thereof include diglycidyl ether, trimethylolpropane diglycidyl ether, pentaerythritol diglycidyl ether, hydroquinone diglycidyl ether, orthophthalic acid diglycidyl ester, and terephthalic acid diglycidyl ester.

Examples of the compound having three or more epoxy groups include glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, and pentaerythritol tetra. Examples thereof include glycidyl ether.
Among the compounds (E1) and (E2), those having a molecular weight of 1000 or less are preferable because the number of ethylenically unsaturated double bonds that can be introduced into the urethane prepolymer (C) is relatively increased. More preferably, the molecular weight is 750 or less, and further preferably 500 or less.

Examples of the polyisocyanate used for producing the urethane prepolymer (C) include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, and the like.
Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, and 4,4′-diphenylmethane diester. Isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1 , 3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate and the like.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, and 1,2-propylene diisocyanate. 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like. .
Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate. -1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of the alicyclic polyisocyanate include isophorone diisocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, and methyl-2. , 4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane, 2, , 5- (isocyanatomethyl) bicyclo [2.2.1] heptane, 2,6- (isocyanatomethyl) bicyclo [2.2.1] heptane, and the like.

Further, as the polyisocyanate, a trimethylolpropane adduct of the above polyisocyanate, a burette reacted with water, a trimer having an isocyanurate ring, or the like can also be used.
As the polyisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane, 2, for thermal decomposition resistance and discoloration of the color filter. 5- (Isocyanatomethyl) bicyclo [2.2.1] heptane and 2,6- (isocyanatomethyl) bicyclo [2.2.1] heptane are preferred.

In the production of the urethane prepolymer (C), a known catalyst used for the reaction of an isocyanato group and a hydroxyl group, for example, a tertiary amine compound, an organometallic compound, in order to accelerate the shortening of the production time and the production temperature. A compound etc. can also be added separately.
Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-cene.

Organometallic compounds are roughly classified into tin compounds and non-tin compounds.
Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, Examples include tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like. Of these, dibutyltin dilaurate and tin 2-ethylhexanoate are preferable because they are effective in a small amount.

Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, and lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate. Iron, such as iron 2-ethylhexanoate and iron acetylacetonate, cobalt-based such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc-based such as zinc naphthenate and zinc 2-ethylhexanoate, naphthene Examples thereof include zirconium acid.
A catalyst can be used individually by 1 type or in combination of 2 or more types.

The urethane prepolymer (C) can be produced using only the above raw materials (polyol and polyisocyanate), but it is preferable to use a known solvent because the viscosity becomes high and the reaction becomes non-uniform. Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, methoxypropyl acetate, toluene, xylene and the like.
The urethanization reaction for producing the urethane prepolymer (C) includes 1) a method in which the whole amount is charged and 2) one of polyol or polyisocyanate is charged in a reaction can and the other is dropped from a dropping can. There are no particular restrictions on the method. In the case of the method 2), when two or more raw materials are dropped from the dropping can, they may be mixed and dropped simultaneously, or they may be dropped in stages by changing the concentration gradually. You may do it.

The urethanization reaction for producing the urethane prepolymer (C) is preferably performed while introducing nitrogen, dry air, or a mixed gas thereof. In particular, when using the compound (E), it is preferable to introduce dry air in order to suppress thermal polymerization of the ethylenically unsaturated double bond derived from the compound (E). Moreover, the temperature of the urethanization reaction which manufactures a urethane prepolymer (C) is 120 degrees C or less, Especially 60-100 degreeC is preferable. When the reaction temperature exceeds 120 ° C., the ethylenically unsaturated double bond derived from the compound (E) may undergo thermal polymerization and part or all of the reaction system may gel.
The blending ratio of the polyol and polyisocyanate is such that the number of moles of isocyanate groups of the polyisocyanate is greater than 1 times the total number of moles of hydroxyl groups of the polyol so that the isocyanate groups remain at the ends. is required. The appropriate blending ratio depends on the reactivity of the compound, the abundance ratio of the trivalent or higher compound, and the like.

（式中、Ｒ¹は３〜１５価の有機残基を示す。Ｒ²は置換もしくは未置換の炭化水素基を示す。ｐは２〜１４の整数、ｓはＲ¹の価数からｐを引いた整数である。） <About the compound (M) having a secondary amino group>
In the compound (M) having a secondary amino group represented by the following general formula (2), the compound (a) having one primary amino group is Michael-added to the compound (x) having three or more acryloyl groups. Can be manufactured. In this case, in general formula (2), R ¹ is an organic residue derived from compound (x), R ² is an organic residue derived from compound (a), and (p + s) is acryloyl in one molecule of compound (x). The number of groups.

(In the formula, R ¹ represents a 3 to 15 valent organic residue. R ² represents a substituted or unsubstituted hydrocarbon group. P is an integer of 2 to 14, and s is p from the valence of R ^1. Subtracted integer.)

As a compound (a) which has one primary amino group used for manufacture of a compound (M), the compound represented by following General formula (4) is mentioned.
R ⁶ —NH ₂ General formula (4)
(In the formula, R ⁶ represents a monovalent substituted or unsubstituted hydrocarbon group having no active hydrogen group.)
Specific examples of the compound represented by the general formula (4) include benzylamine, phenethylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, n-pentylamine, isopentylamine, n- Hexylamine, cyclohexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, n-nonylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine And primary amines. Of these, amines having a substituted or unsubstituted hydrocarbon group having 5 to 10 carbon atoms are preferable from the viewpoint of reaction control, and cyclohexylamine is more preferable. These can be used alone or in combination of two or more.

As the compound (x) having three or more acryloyl groups used for the production of the compound (M), the number of acryloyl groups that can be introduced into the urethane urea resin is increased, and the curability is sufficient. Functional, particularly penta- to 15-functional acrylates are preferred.
Examples of pentafunctional or higher acrylates include dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate and the like.
Examples of tetrafunctional acrylates include pentaerythritol tetraacrylate, tetramethylol methane tetraacrylate, oligoester tetraacrylate and the like.

Examples of the trifunctional acrylates include glycerin triacrylate, glycerin ethylene oxide modified triacrylate, glycerin propylene oxide modified triacrylate, trimethylolpropane triacrylate, trimethylolpropane ethylene oxide modified triacrylate. , Trimethylolpropane propylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified triacrylate, isocyanuric acid propylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified ε-caprolactone modified triacrylate, 1,3,5-triacryloyl Hexahydro-s-triazine, pentaerythritol triacrylate, dipentaerythritol triacrylate tripropionate, tris ( Acryloyloxy) Hosufe - door, and the like.
The compound (x) having three or more acryloyl groups is not limited to the above compound, and a compound obtained by adding ethylene oxide, propylene oxide, ε-caprolactone or the like to the above compound in an arbitrary ratio may be used. it can.
These can be used alone or in combination of two or more.

  When the compound (a) having one primary amino group is Michael-added to the compound (x) having three or more acryloyl groups, it must be gelled during this reaction or the subsequent reaction with the urethane prepolymer (C). For example, the reaction may be performed in any ratio, but the reaction is performed such that the number of moles x of the compound (x) is a / x = 0.2 to 2 with respect to the number of moles a of the compound (a). It is preferable. More preferably, a / x = 0.25 to 1.9. When a / x <0.2, a large amount of unreacted compound (x) remains, and the developability may be deteriorated when the photosensitive coloring composition for a color filter of the present invention is used. If a / x> 2, a large number of compounds having three or more secondary amino groups can be formed, and therefore, the reaction with the urethane prepolymer (C) may cause three-dimensional network crosslinking and gelation.

When the compound (a) is Michael-added to the compound (x) so that a / x = 0.2 to 2, the product after the Michael addition reaction includes two or more substituents, that is, secondary compounds. A compound having two or more amino groups, a mono-substituted compound, that is, a compound having one secondary amino group, and a zero-substituted compound, that is, an unreacted compound (x) are included. In the reaction with the urethane prepolymer (C), the two or more substituents function as a chain extender that increases the molecular weight, and the one substituent functions as an end-capping agent that stops the polyaddition reaction. The ratio of two or more substitution products and one substitution product is such that when a / x is close to 0.2, there are many 1-substitution products, and as a / x approaches 2, 1-substitution product decreases, and two or more substitution products. Will increase.
The urethane urea resin may include a structure derived from the compound (M) composed of three or more substituents.

When the compound (a) having one primary amino group is Michael-added to the compound (x) having three or more acryloyl groups, to the reaction vessel in which the compound (x) is stirred in order to suppress a local reaction. A method of sequentially dropping the compound (a) is preferred. The dropping time and the reaction time are not limited because they depend on the reactivity of the compound (a) and the compound (x). Further, in order to prevent the secondary amino group of the produced compound (M) from Michael addition to another acryloyl group, the reaction between the compound (a) and the compound (x) is 60 ° C. or less, preferably 50 ° C. Do the following:
The compound (M) can be produced using only the above raw materials (compound (a) and compound (x)), but it is preferable to use a known solvent because local reactions can be suppressed. . Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, methoxypropyl acetate, toluene, xylene and the like.

In the case where the produced compound (M) is reacted with the urethane polymer (C) within 24 hours after production in order to prevent further Michael addition of secondary amino groups during storage or exceeds 24 hours after production. Is preferably stored in a cool place at 10 ° C. or lower until use.
Michael addition is a nucleophilic ionic reaction in which a primary or secondary amino group is added to an ethylenically unsaturated double bond of an acryloyl group in the absence of a catalyst or, if necessary, a catalyst. When compound (a) having one primary amino group is Michael-added to compound (x) having three or more acryloyl groups to produce compound (M), compound (a) is converted to compound (x). The type, reaction ratio, reaction concentration, and temperature of the compound (a) and the compound (x) can be controlled so that the amino group that has become secondary by Michael addition does not become a tertiary amine by further Michael addition. preferable.

<Reaction of Urethane Prepolymer (C) with Compound (M) Having Secondary Amino Group>
The reaction between the urethane prepolymer (C) and the compound (M) having a secondary amino group is carried out in order to suppress a local reaction, so that the reaction mixture containing the urethane prepolymer (C) is stirred into the reaction vessel. Preferably, (M) is added dropwise successively. Further, in order to prevent the secondary amino group of the obtained compound (M) from being Michael-added to the acryloyl group, the reaction is preferably performed at 80 ° C. or lower, and further at 70 ° C. or lower.
The reaction ratio between the urethane prepolymer (C) and the compound (M) having a secondary amino group may be any ratio as long as it does not gel, but the number of moles of isocyanato groups present in the urethane prepolymer (C). Is <N>, and the number of moles of the secondary amino group of the compound (M) is <H>, it is most preferable to react at a ratio of <H> / <N> = 1.

The urethane prepolymer (C) and the compound having a secondary amino group (M) are reacted at a ratio of 0.7 <<H> / <N><1, and the remaining isocyanate group is subsequently reduced to a low molecular weight. It is also possible to consume with a secondary amine compound or a low molecular weight alcohol. If <H> / <N> is less than 0.7, the amount of ethylenically unsaturated double bonds in the resulting urethane urea resin is undesirably reduced.
Examples of the low molecular weight secondary amine compound include dimethylamine, diethylamine, N-methylethylamine, dipropylamine, di-n-butylamine, diisobutylamine, N-methylhexylamine, di-n-octylamine and di-2. -Ethylhexylamine, diallylamine, diethanolamine and the like. Examples of the low molecular weight alcohol include methanol, ethanol, n-propanol, i-propanol, n-butanol, and 2-butanol.

The urethane urea resin produced by the above method may have any weight average molecular weight as long as there is no problem in use. In particular, the weight average molecular weight in terms of standard polystyrene conversion by GPC is preferably 5,000 to 200,000. More preferably, it is 8000-150000. When the weight average molecular weight is less than 5,000, the chromaticity of the filter segment may change greatly depending on the N-methylpyrrolidone solvent used in the process after the color filter is formed. When the weight average molecular weight exceeds 200,000, the viscosity becomes very high. The coatability may be deteriorated in the manufacturing process of the filter.
The amount of the ethylenically unsaturated double bond contained in the urethane urea resin produced by the above method may be any value as long as there is no problem in use, but in particular 1.5 mmol per 1 g of urethane urea resin. It is preferably 5.0 mmol or less, more preferably 2.0 mmol or more and 4.7 mmol or less, and most preferably 2.5 mmol or more and 4.5 mmol or less. When the amount is less than 1.5 mmol / urethane urea resin g, the ultraviolet curing reactivity deteriorates, and the chromaticity of the filter segment may greatly change depending on the N-methylpyrrolidone solvent used in the process after the color filter is formed.

  The monomer contained in the photosensitive coloring composition for a color filter of the present invention is a compound having at least one ethylenically unsaturated double bond. As the monomer, from the viewpoint of increasing the sensitivity of the photosensitive coloring composition, a polyfunctional monomer having two or more ethylenically unsaturated double bonds, particularly a polyfunctional monomer having 3 to 12 ethylenically unsaturated double bonds. Are preferably used.

 Monomers and oligomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate , Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neo Pentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester (meth) acrylate, (meth) acrylate of methylolated melamine, epoxy (meth) acrylate, Various acrylic esters and methacrylic esters such as urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) Examples include acrylamide, N-vinylformamide, acrylonitrile and the like. A monomer can be used individually or in mixture of 2 or more types.

  In the photosensitive coloring composition of the present invention, in addition to the urethane urea resin and the monomer, other photosensitive transparent resins, non-photosensitive transparent resins, or mixtures thereof are used to control solubility and resistance to a developer. Can be contained. The other photosensitive transparent resin and non-photosensitive transparent resin are resins having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

  The photosensitive transparent resin is a resin having an ethylenically unsaturated double bond, for example, a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, an aldehyde group, an epoxy group, A functional group having an ethylenically unsaturated double bond such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a reactive substituent such as a carboxyl group or cinnamic acid. Resin. Specifically, a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated double bond are added to a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group and another ethylenically unsaturated monomer. Some of them are obtained by reacting the compounds they have. Examples of the functional group capable of reacting with a hydroxyl group include an isocyanate group and a carboxyl group, and an isocyanate group is particularly preferred from the viewpoint of reactivity. Specific examples of the compound having an isocyanate group and an ethylenically unsaturated double bond include 2-acryloylethyl isocyanate and 2-methacryloylethyl isocyanate. In addition, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  The non-photosensitive transparent resin is a resin that does not have an ethylenically unsaturated double bond, and includes a thermoplastic resin and a thermosetting resin. Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, styrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a phenol resin, a melamine resin, and a urea resin.

In the photosensitive coloring composition for color filters of the present invention, the content of the urethane urea resin is based on the weight of nonvolatile components (components other than the solvent contained in the photosensitive coloring composition) excluding the colorant of the photosensitive coloring composition. 10 to 80% by weight is preferable. The content of the more preferable urethane urea resin varies depending on the hue of the colorant, and is 30 to 80 for the photosensitive red colored composition containing the red colorant on the basis of the non-volatile content weight excluding the colorant of the photosensitive colored composition. The photosensitive green coloring composition containing 20% by weight of the green colorant is 20 to 75% by weight, and the photosensitive blue coloring composition containing the blue colorant is 20 to 70% by weight.
When the content of the urethane urea resin in the photosensitive coloring composition is less than 10% by weight, the photosensitivity is lowered, the NMP resistance is improved, and sufficient curability is obtained to reduce the swelling of the coating film. I can't. Further, when the content of the urethane urea resin in the photosensitive coloring composition is more than 80% by weight, NMP resistance may be reduced due to yellowing of the urethane urea resin.

As a colorant contained in the photosensitive coloring composition for a color filter of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. As the pigment, a pigment having high color developability and high heat resistance, particularly a pigment having high heat decomposition resistance is preferable, and an organic pigment is usually used.
The colorant is generally contained in a proportion of 10 to 60% by weight, preferably 20 to 50% by weight, based on the non-volatile content of the photosensitive coloring composition.
Below, the specific example of the organic pigment which can be used for the photosensitive coloring composition for color filters of this invention is shown by a color index number.

  When forming a red filter segment using the photosensitive coloring composition for a color filter of the present invention, for example, C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 184, Red pigments such as 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, and 279 are used. Red pigments include C.I. I. An orange pigment such as Pigment Orange 43, 71, 73 can be used in combination.

  When forming a green filter segment using the photosensitive coloring composition for color filters of the present invention, for example, C.I. I. Green pigments such as Pigment Green 7, 10, 36, and 37 are used. Green 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, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214 and the like can be used in combination.

When forming a blue filter segment using the photosensitive coloring composition for a color filter of the present invention, for example, C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. Blue pigments include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.
When forming a magenta color filter segment using the photosensitive coloring composition for a color filter of the present invention, for example, C.I. I. Pigment Violet 1, 19, C.I. I. Purple pigments such as Pigment Red 144, 146, 177, 169, 81, and red pigments are used.

When forming a yellow color filter segment using the photosensitive coloring composition for color filters of the present invention, yellow pigments exemplified as yellow pigments that can be used in combination with green pigments are used.
When forming a cyan filter segment using the photosensitive coloring composition for a color filter of the present invention, for example, C.I. I. Blue pigments such as Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, and 81 are used.
The photosensitive coloring composition for a color filter of the present invention can contain a dye within a range that does not reduce heat resistance for color matching.

The photosensitive coloring composition for a color filter of the present invention comprises a urethane roll resin, a monomer, and a composition containing other photosensitive transparent resin and non-photosensitive transparent resin as necessary. It can be produced by finely dispersing using various dispersing means such as a roll mill, a sand mill, a kneader, an attritor, and a paint conditioner.
When a pigment is used as the colorant, a dispersion aid such as a resin-type pigment dispersant, a dye derivative, or a surfactant can be appropriately used. The dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, the dispersion aid is used to disperse a pigment in a composition containing a urethane urea resin and a monomer. When the coloring composition is used, a color filter excellent in transparency can be obtained.

  The resin-type pigment dispersant has a pigment-affinity part that has the property of adsorbing to the pigment, and a part that is compatible with urethane urea resin, other photosensitive transparent resin, and non-photosensitive transparent resin, and is adsorbed to the pigment. Thus, it functions to stabilize the dispersion of the pigment into the urethane urea resin or the like. Resin-type pigment dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polycarboxylic acid esters Siloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof 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 Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and the like are also used. These can be used alone or in admixture of two or more.

  Commercially available resin-type pigment dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, manufactured by Big Chemie. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen SOLSPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 320 manufactured by Abyssia 0, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402 manufactured by Efka Chemicals , 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503, and the like.

  A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Organic dyes include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used singly or in combination of two or more.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer; polyoxyethylene oleyl ether, polyoxyethylene Lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol Nonionic surfactants such as monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaines; amphoteric surfactants such as alkylimidazolines These may be used alone or in combination of two or more.

When the composition is cured by irradiation with light such as ultraviolet rays, a photopolymerization initiator or the like is added to the photosensitive coloring composition for a color filter of the present invention.
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Acetophenone photopolymerization initiators such as -1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4 Benzophenone photopolymerization initiators such as phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone photopolymerization initiators such as 2,4-diisopropylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 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 (trick (Romethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, etc. A polymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, or the like is used.
A photoinitiator can be used in 5-25 weight% of a range based on the non volatile matter weight of a photosensitive coloring composition.

The above photopolymerization initiators are used alone or in admixture of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrene. Compounds such as quinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone Can also be used together.
The sensitizer can be used in an amount of 0.1 to 30% by weight based on the weight of the photopolymerization initiator.

  The photosensitive coloring composition for color filters of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite.

  Moreover, in the photosensitive coloring composition for color filters of this invention, a coloring agent is fully disperse | distributed to urethane urea resin etc., and a dry film thickness will be 0.2-5 micrometers on transparent substrates, such as a glass substrate. A solvent can be included to facilitate application and formation of the filter segment. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether toluene, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination. The solvent is generally used in a range of 1.2 to 20 times by weight, preferably 3 to 10 times by weight, based on the nonvolatile content weight of the photosensitive coloring composition.

The photosensitive coloring composition for a color filter of the present invention includes a three-roll mill, a two-roll mill, a sand mill, a photosensitive resin composition containing a urethane urea resin, a monomer, and the like, with one or more colorants. It can be produced by finely dispersing using various dispersing means such as a kneader, an attritor, and a paint conditioner.
The photosensitive coloring composition for color filter of the present invention is 5 μm or more coarse particles, preferably 1 μm or more coarse particles, more preferably 0.5 μm or more by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove coarse particles and mixed dust.

Next, the color filter of the present invention will be described.
The color filter of this invention is a color filter which comprises the filter segment formed from the photosensitive coloring composition for color filters of this invention. The color filter is one in which filter segments of one color or a plurality of colors are formed on a transparent substrate, and generally, at least one red filter segment, at least one green filter segment, and at least one blue filter segment And a subtractive color type having at least one magenta color filter segment, at least one cyan color filter segment, and at least one yellow color color filter segment.

The color filter of this invention can be manufactured by forming the filter segment of each color on a transparent substrate by the photolithographic method using the photosensitive coloring composition for color filters of this invention.
As the transparent substrate, a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.

  The formation of each color filter segment by photolithography is performed by the following method. That is, the photosensitive coloring composition prepared in a solvent development type or an alkali development type is dried on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, etc., with a dry film thickness of 0.2 to 5 μm. The pigment dispersion coating film is formed by drying as necessary. Next, ultraviolet exposure is performed through a mask having a predetermined pattern in contact with or non-contact with the film. Then, after immersing in a solvent or an alkaline developer, or spraying the developer with a spray 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 the photosensitive coloring composition, it can also heat as needed. According to the photolithography method, a color filter with higher accuracy than the 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 applying and drying the photosensitive coloring composition, a water-soluble or alkali-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.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto. In the following examples, “parts” means “parts by weight” unless otherwise specified. In addition, a weight average molecular weight shows the standard polystyrene conversion molecular weight measured by GPC. Further, the viscosity of the solution is a value when a rotor of # 2 is set in a BL type viscometer and measured at 25 ° C. for 1 minute.
Prior to the examples, a synthesis example of the urethane urea resin, the photosensitive transparent resin, and the non-photosensitive transparent resin used in the examples will be described.

(Synthesis Example 1)
To a 5-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel, polytetramethylene glycol (trade name: PTG850: manufactured by Hodogaya Chemical Co., Ltd., hydroxyl value: 127.1 mgKOH / g , Number average molecular weight 880) 25.6 parts, dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) 38.6 parts, isophorone diisocyanate (manufactured by Huls Japan Co., Ltd.) 85.8 parts, methoquinone 0.15 And 150 parts of cyclohexanone were gradually heated up and reacted at 80 ° C. for 4 hours while introducing nitrogen. After confirming the remaining amount of isocyanato group by titration, it was cooled to 40 ° C. to obtain a urethane prepolymer solution (C-1). This reaction solution was yellow and transparent, had a solid content of 50% by weight, a weight average molecular weight of 5500, and the amount of residual isocyanate groups relative to 1 g of the solution was 0.5203 mmol.

  In another 5-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel, 6 mol acrylic acid adduct of ε-caprolactone 2 mol adduct of dipentaerythritol (product) Name KAYARAD DPCA-20, 6-functional acrylate with an average molecular weight of 807, manufactured by Nippon Kayaku Co., Ltd.) 249.4 parts, 80.0 parts of methoxypropyl acetate were charged, the temperature was raised to 40 ° C., and dry air was introduced. To the stirring site, a mixed solution of 30.6 parts of cyclohexylamine (manufactured by Shin Nippon Rika Co., Ltd.) and 20.0 parts of methoxypropyl acetate was added dropwise at 40 ° C. over 30 minutes with a dropping funnel. 20.0 parts of methoxypropyl acetate was added after completion | finish of dripping, and reaction was performed at 40 degreeC after that for 2 hours. After completion of the reaction, 400.0 parts of cyclohexanone was added to obtain a colorless and transparent compound solution (M-1) having a secondary amino group.

About 2 g of the solution (M-1) was placed in a conical beaker, precisely weighed, and 30 ml of methyl ethyl ketone was added and dissolved. This solution was titrated with a 0.2 mol / L ethanolic hydrochloric acid standard solution using bromophenol blue as an indicator to obtain the total of primary, secondary and tertiary amine values (total amine value). .
Next, about 2 g of the solution (M-1) was placed in an Erlenmeyer flask, precisely weighed, 20 ml of acetic anhydride and acetic acid mixed solution (weight ratio 9: 1) was added and dissolved, and left at room temperature for 3 hours. Subsequently, 30 ml of acetic acid was added, titrated with a 0.1 mol / L perchloric acid and acetic acid solution with a potentiometric titrator, and at the same time, a tertiary amine value was determined by performing a blank test.

Next, about 2 g of the solution (M-1) was placed in an Erlenmeyer flask, precisely weighed, 2 ml of a 25% ethanol solution of salicylaldehyde was added, and allowed to stand at room temperature for about 30 minutes (salicylaldehyde was a primary amino group and Reacts to neutralize). 30 ml of methyl ethyl ketone was added thereto and titrated with a 0.2 mol / L ethanolic hydrochloric acid solution with a potentiometric titrator to determine the total of secondary and tertiary amine values (partial amine value).
According to the above operation, (primary amine value) = (total amine value) − (partial amine value), (secondary amine value) = (partial amine value) − (tertiary amine value). When cyclohexylamine reacted with hexafunctional acrylate KAYARAD DPCA-20, it was confirmed that the conversion rate to produce the desired secondary amino group was 99.0% based on cyclohexylamine. As a result, the amount of secondary amine present in 1 g of the solution (M-1) was 0.3823 mmol.

While stirring the 4-necked flask in which 295 parts of the urethane prepolymer solution (C-1) is present at 60 ° C., 377.6 parts of a solution (M-1) of a compound having a secondary amino group is added. It was added dropwise over a period of minutes. After completion of the dropwise addition, stirring was continued for 60 minutes at 60 ° C., 117 parts of cyclohexanone and 10 parts of methanol were added, and the mixture was further stirred for 120 minutes. It was confirmed by infrared absorption spectrum that the peak at 2266 cm ⁻¹ , which is the characteristic absorption of the isocyanato group, disappeared, and a urethane urea resin solution (U-1) was obtained. This solution is yellow and transparent. The solid content is 35% by weight, the weight average molecular weight is 38400, the acid value per dry weight is 52 mgKOH / g, and the calculated amount of ethylenically unsaturated double bonds per dry weight is 2.60 mmol / g. there were. Cyclohexanone was added to the obtained urethane urea resin solution to prepare a solid content of 20% by weight.

(Synthesis Example 2)
To a 5-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel, a 2-mol adduct of propylene glycol diglycidyl ether (trade name: Epoxy ester 70PA: Kyoeisha Chemical Co., Ltd., molecular weight 332.3) 20.2 parts, dimethylolbutanoic acid (made by Nippon Kasei Co., Ltd.) 37.2 parts, isophorone diisocyanate (made by Huls Japan Co., Ltd.) 92.5 parts Then, 0.15 part of methoquinone and 150 parts of cyclohexanone were added, the temperature was gradually raised, and the reaction was carried out at 80 ° C. for 4 hours while introducing dry air. After confirming the remaining amount of the isocyanate group by titration, it was cooled to 40 ° C. to obtain a urethane prepolymer solution (C-2). This reaction solution was yellow and transparent, had a solid content of 50% by weight, a weight average molecular weight of 5060, and the amount of residual isocyanate groups relative to 1 g of the solution was 0.5035 mmol.

A solution of a compound having a secondary amino group obtained by the same production method as in Synthesis Example 1 while stirring a 4-necked flask containing 295 parts of the urethane prepolymer solution (C-2) at 60 ° C. (M-1) 365.4 parts was added dropwise over 60 minutes. After completion of the dropwise addition, stirring was continued for 60 minutes at 60 ° C., 117 parts of cyclohexanone and 10 parts of methanol were added, and the mixture was further stirred for 120 minutes. In the infrared absorption spectrum, it was confirmed that the peak at 2266 cm ⁻¹ , which is the characteristic absorption of the isocyanato group, disappeared, and a urethane urea resin solution (U-2) was obtained. This solution is yellow and transparent, the solid content is 35% by weight, the weight average molecular weight is 34200, the acid value per dry weight is 51 mgKOH / g, and the calculated amount of ethylenically unsaturated double bonds per dry weight is 3.00 mmol / g. there were. Cyclohexanone was added to the obtained urethane urea resin solution to prepare a solid content of 20% by weight.

(Synthesis Example 3)
To a 5-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel, a 2-mol adduct of propylene glycol diglycidyl ether (trade name: Epoxy ester 70PA: 21.5 parts by Kyoeisha Chemical Co., Ltd., molecular weight 332.3), polytetramethylene glycol (trade name PTG850: manufactured by Hodogaya Chemical Co., Ltd., hydroxyl value 127.1 mg KOH / g), 15.6 parts, dimethylolbutanoic acid (Japan) (Made by Kasei Co., Ltd.) 31.3 parts, isophorone diisocyanate (manufactured by Huls Japan Co., Ltd.) 81.6 parts, methoquinone 0.15 parts, cyclohexanone 150 parts, and gradually heated to dry air The reaction was carried out at 80 ° C. for 4 hours while introducing. After confirming the remaining amount of the isocyanate group by titration, it was cooled to 40 ° C. to obtain a urethane prepolymer solution (C-3). This reaction solution was transparent and yellow, had a solid content of 50% by weight, a weight average molecular weight of 4720, and the amount of residual isocyanate groups relative to 1 g of the solution was 0.4975 mmol.

  In another 5-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name KAYARAD DPHA, average An average 5.5 functional acrylate having a molecular weight of 535.5: Nippon Kayaku Co., Ltd.) 126.6 parts and 60.0 parts of methoxypropyl acetate were charged, heated to 40 ° C., and stirred while introducing dry air. Then, a mixed solution of 23.4 parts of cyclohexylamine (manufactured by Shin Nippon Rika Co., Ltd.) and 45 parts of methoxypropyl acetate was added dropwise at 40 ° C. over 30 minutes with a dropping funnel. After the completion of dropping, 45 parts of methoxypropyl acetate was added. Thereafter, the reaction was performed at 40 ° C. for 2 hours. After completion of the reaction, 300.0 parts of cyclohexanone was added to obtain a colorless transparent solution (M-2) of a compound having a secondary amino group.

As a result of quantification of the primary, secondary and tertiary amines of the solution (M-2) in the same manner as in the solution (M-1) shown in Synthesis Example 1, cyclohexylamine was 5.5 functional acrylate KAYARAD DPHA. It was confirmed that the conversion rate to produce the desired secondary amino group was 98.9% based on cyclohexylamine. As a result, the amount of secondary amine present in 1 g of the solution (M-2) was 0.3895 mmol.
A solution of a compound having a secondary amino group obtained by the same production method as in Synthesis Example 1 while stirring a 4-necked flask containing 295 parts of the urethane prepolymer solution (C-3) at 60 ° C. (M-2) 354.0 parts were added dropwise over 60 minutes. After completion of the dropwise addition, stirring was continued for 60 minutes at 60 ° C., then 15 parts of cyclohexanone and 10 parts of methanol were added and further stirred for 120 minutes. From the infrared absorption spectrum, it was confirmed that the peak at 2266 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, disappeared, and a urethane urea resin solution (U-3) was obtained. This solution is transparent in yellow, has a solid content of 35% by weight, a weight average molecular weight of 29700, an acid value per dry weight of 50 mgKOH / g, and a calculated amount of ethylenically unsaturated double bonds per dry weight of 3.21 mmol / g. there were. Cyclohexanone was added to the obtained urethane urea resin solution to prepare a solid content of 20% by weight.

(Synthesis Example 4)
560 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 34.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, 23.0 parts of n-butyl methacrylate at the same temperature. 22.0 parts of paracumylphenol ethylene oxide modified acrylate (trade name Aronix M110: manufactured by Toa Gosei Co., Ltd.), 47.0 parts of glycerol monomethacrylate, 2,2′-azobisisobutyro as monomer (a) A mixture of 4.0 parts of nitrile was added dropwise over 1 hour to conduct a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 55 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained.
Next, a mixture of 32.0 parts of 2-methacryloyloxyethyl isocyanate, 0.4 parts of dibutyltin laurate and 120.0 parts of cyclohexanone was added to 338 parts of the obtained transparent resin solution at 70 ° C. over 3 hours. The solution was dropped to obtain a photosensitive transparent resin solution. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Cyclohexanone was added as follows. The obtained photosensitive transparent resin had a weight average molecular weight of 21,000, and the calculated amount of ethylenically unsaturated double bonds per dry weight was 2.13 mmol / g.

(Synthesis Example 5)
370 parts of cyclohexanone was put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate at the same temperature, A mixture of 15.0 parts of 2-hydroxyethyl methacrylate and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A photosensitive transparent resin solution was obtained.
After cooling to room temperature, about 2 g of the non-photosensitive transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The non-photosensitive transparent resin solution synthesized earlier had a non-volatile content of 20% by weight. Cyclohexanone was added so that The obtained non-photosensitive transparent resin had a weight average molecular weight of 40,000.

[Example 1]
(Method for producing pigment dispersion)
After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A pigment dispersion was prepared.
Diketopyrrolopyrrole red pigment (CI Pigment Red 254)
("Irga Four Red B-CF" manufactured by Ciba Specialty Chemicals) 9.5 parts Phosphoric ester pigment dispersant ("BYK111" manufactured by Big Chemie) 0.5 parts Photosensitive transparent resin solution obtained in Synthesis Example 4 28.0 parts Non-photosensitive transparent resin solution obtained in Synthesis Example 5 22.5 parts Cyclohexanone 39.5 parts

(Method for producing photosensitive red coloring composition)
Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a photosensitive red colored composition.
Pigment dispersion 25.0 parts Urethane urea resin solution obtained in Synthesis Example 2 29.2 parts Dipentaerythritol hexaacrylate 4.2 parts Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Geigy) 0.5 parts Increase Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.1 parts Cyclohexanone 41.0 parts

[Example 2]
In the method for producing the photosensitive red coloring composition of Example 1, the amount of the urethane urea resin solution obtained in Synthesis Example 2 was changed from 29.2 parts to 13.2 parts, and the photosensitivity obtained in Synthesis Example 4 was obtained. A photosensitive red colored composition was obtained in the same manner as in Example 1 except that the amount of the transparent transparent resin solution was changed from 0 part to 16.0 parts.
[Example 3]
In the method for producing the pigment dispersion of Example 1, the same procedure as in Example 1 was used, except that the urethane urea resin solution obtained in Synthesis Example 2 was used instead of the photosensitive transparent resin solution obtained in Synthesis Example 4. Thus, a photosensitive red coloring composition was obtained.
[Example 4]
The urethane dispersion obtained in Synthesis Example 2 in place of the photosensitive transparent resin solution obtained in Synthesis Example 4 and the non-photosensitive transparent resin solution obtained in Synthesis Example 5 in the method for producing the pigment dispersion of Example 1. A photosensitive red colored composition was obtained in the same manner as in Example 1 except that the resin solution was used.

[Example 5]
Example 1 except that the urethane urea resin solution obtained in Synthesis Example 1 was used in place of the urethane urea resin solution obtained in Synthesis Example 2 in the method for producing the photosensitive red coloring composition of Example 1. In the same manner, a photosensitive red coloring composition was obtained.
[Example 6]
Example 1 except that the urethane urea resin solution obtained in Synthesis Example 3 was used in place of the urethane urea resin solution obtained in Synthesis Example 2 in the method for producing the photosensitive red coloring composition of Example 1. In the same manner, a photosensitive red coloring composition was obtained.

[Example 7]
(Method for producing pigment dispersion)
After the mixture having the following composition is stirred and mixed uniformly, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A pigment dispersion was prepared.
Phthalocyanine green pigment (CI Pigment Green 36)
(“Lionol Green 6YK” manufactured by Toyo Ink Co., Ltd.) 12.0 parts Phosphoric ester pigment dispersant (“BYK111” manufactured by BYK Chemie) 1.0 part Photosensitive transparent resin solution obtained in Synthesis Example 4. 5 parts Non-photosensitive transparent resin solution obtained in Synthesis Example 5 17.5 parts Cyclohexanone 66.0 parts

(Method for producing photosensitive green coloring composition)
Next, the mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a photosensitive green colored composition.
Pigment dispersion 12.5 parts Urethane urea resin solution obtained in Synthesis Example 3 37.6 parts Dipentaerythritol hexaacrylate 4.5 parts Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Geigy Co.) 1.0 part Increase Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.1 part Cyclohexanone 44.3 parts

[Example 8]
(Method for producing pigment dispersion)
After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A pigment dispersion was prepared.
Phthalocyanine blue pigment (CI Pigment Blue 15: 6)
("Heliogen Blue L-6700F" manufactured by BASF) 9.0 parts Phosphoric ester pigment dispersant ("BYK111" manufactured by Big Chemie) 1.0 part Photosensitive transparent resin solution obtained in Synthesis Example 4 20.5 Part Non-photosensitive transparent resin solution obtained in Synthesis Example 5 18.5 parts Cyclohexanone 51.0 parts

(Method for producing photosensitive blue coloring composition)
Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a blue colored composition.
Pigment dispersion 12.5 parts Urethane urea resin solution obtained in Synthesis Example 2 40.0 parts Dipentaerythritol hexaacrylate 3.6 parts Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Geigy Co.) 1.0 part Increase Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.1 part Cyclohexanone 42.8 parts

[Comparative Example 1]
Instead of the photosensitive transparent resin solution obtained in Synthesis Example 4, the non-photosensitive transparent resin solution obtained in Synthesis Example 5 was used in the method for producing the pigment dispersion of Example 1, and a photosensitive red coloring composition was used. In the same manner as in Example 1 except that the photosensitive transparent resin solution obtained in Synthesis Example 4 was used instead of the urethane urea resin solution obtained in Synthesis Example 2 in the production method of the product. I got a thing.
[Comparative Example 2]
Example 1 except that the photosensitive transparent colored resin solution obtained in Synthesis Example 4 was used in place of the urethane urea resin solution obtained in Synthesis Example 2 in the production method of the photosensitive red coloring composition of Example 1. In the same manner as in Example 1, a photosensitive red coloring composition was obtained.

[Comparative Example 3]
In the method for producing the photosensitive red coloring composition of Example 1, 5.84 parts of dipentaerythritol hexaacrylate was used instead of 29.2 parts of the urethane urea resin solution obtained in Synthesis Example 2, and the amount of cyclohexanone was adjusted. A photosensitive red coloring composition was obtained in the same manner as in Example 1 except that the amount was changed from 41.0 parts to 64.36 parts.
[Comparative Example 4]
In the production method of the photosensitive green coloring composition of Example 7, the Example was used except that the photosensitive transparent resin solution obtained in Synthesis Example 4 was used instead of the urethane urea resin solution obtained in Synthesis Example 2. In the same manner as in Example 1, a photosensitive green coloring composition was obtained.
[Comparative Example 5]
In the method for producing the photosensitive blue coloring composition of Example 8, Example 1 was used except that instead of the urethane urea resin solution obtained in Synthesis Example 2, the photosensitive transparent resin solution obtained in Synthesis Example 4 was used. In the same manner as in Example 1, a photosensitive blue coloring composition was obtained.

About the photosensitive coloring composition obtained by the Example and the comparative example, the solvent resistance and viscosity stability were evaluated by the following method. The results are shown in Table 1.
(Solvent resistance evaluation)
The photosensitive coloring composition was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater to form a coating film having a thickness of 2.0 μm. Next, after pre-baking at 70 ° C. for 20 minutes, UV exposure was performed using a super high pressure mercury lamp through a mask that exposes a stripe pattern at a saturated exposure amount of +100 mJ / cm ² . After the exposure, development was performed with an alkaline developer for 90 seconds to form each color filter segment in a stripe shape on the substrate. The developed substrate was heat-treated at 230 ° C. for 60 minutes. After immersing a part of the substrate in N-methylpyrrolidone (NMP) for 30 minutes, the chromaticity before and after immersion was measured with a microspectrophotometer (trade name OSP-SP100: Olympus Optical Co., Ltd.) using a C light source. The degree change ΔE was calculated. Moreover, the film thickness before and behind immersion was measured with the surface shape measuring apparatus (brand name DEKTAK8: ULVAC, Inc.), and the film thickness swelling amount was computed by the following formula.
[Thickness of film thickness] = [film thickness after immersion] − [film thickness before immersion]
Furthermore, the state of the pattern surface (crack resistance) was observed with an optical microscope. The pattern surface state showed no change, ◯, a slight but crack etc. was observed, and a severe crack was found. What was obtained was evaluated as x.

(Viscosity stability evaluation)
Using an E-type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.), the initial viscosity of the next day after the preparation of the photosensitive coloring composition and the time-lapse viscosity accelerated at 40 ° C. for 1 week is 25 ° C. The measurement was performed under the condition of a rotational speed of 20 rpm. The thickening rate from the initial viscosity to the viscosity with time was calculated by the following formula.
[Viscosity] = | ([Initial viscosity] − [Time viscosity]) / [Initial viscosity] × 100 |

As shown in Table 1, in the photosensitive coloring compositions for color filters of Comparative Examples 1 to 5 using an acrylic resin as the main binder, NMP resistance (chromaticity change, film thickness swelling amount or appearance) was poor.
On the other hand, as shown in Examples 1 to 8, the photosensitive coloring composition for a color filter containing a urethane urea resin can improve the NMP resistance without reducing the crack resistance and dispersion stability of the coating film. It was.

Claims (8)

A photosensitive coloring composition for a color filter comprising a urethane urea resin represented by the following general formula (1), a monomer, and a colorant.

(In the formula, R ¹ represents a 3-15 valent organic residue. R ² represents a substituted or unsubstituted hydrocarbon group. R ³ represents a divalent organic residue having a urethane bond in the main chain. M is an integer of 2 to 14, n is an integer of 1 to 13, and x is an integer of 0 to 100.) The color according to claim 1, wherein R ³ in the general formula (1) is a divalent organic residue having at least one anionic functional group in the side chain and having a urethane bond in the main chain. Photosensitive coloring composition for filters. 2. R ³ in the general formula (1) is a divalent organic residue having at least one ethylenically unsaturated double bond in the side chain and a urethane bond in the main chain. Or the photosensitive coloring composition for color filters of 2. Urethane urea resin reacts with a compound (M) having a secondary amino group represented by the following general formula (2) to a urethane prepolymer (C) having an isocyanate group at the terminal obtained by reacting a polyol and a polyisocyanate. The photosensitive coloring composition for a color filter according to any one of claims 1 to 3, wherein the photosensitive coloring composition is a resin obtained from the above.

(In the formula, R ¹ represents a 3 to 15 valent organic residue. R ² represents a substituted or unsubstituted hydrocarbon group. P is an integer of 2 to 14, and s is p from the valence of R ^1. Subtracted integer.)   The color according to claim 4, wherein the compound (M) is a compound obtained by Michael addition of the compound (a) having one primary amino group to the compound (x) having three or more acryloyl groups. Photosensitive coloring composition for filters.   6. The photosensitive coloring composition for a color filter according to claim 4, wherein the polyol is a polyol (E) having at least one ethylenically unsaturated double bond and a polyol other than the polyol (E). object.   7. The color filter photosensitive material according to claim 1, wherein the content of the urethane urea resin is 10 to 80% by weight based on the weight of the nonvolatile content excluding the colorant of the photosensitive coloring composition. Coloring composition.   A color filter comprising a filter segment formed from the photosensitive coloring composition for a color filter according to claim 1.