JP5433973B2 - Coloring composition for color filter and color filter - Google Patents

Description

  The present invention relates to a colored 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.

  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 general, it is difficult to obtain a stable dispersion by dispersing fine pigment particles in a colorant carrier such as a varnish, and the dispersion often has a high viscosity due to aggregation of the pigment particles over time. There was a problem of getting worse.

  In order to solve this problem, an organic pigment is used as a base skeleton, a pigment derivative having an acidic or basic substituent in the side chain is mixed as a dispersant, and the pigment is formed by the interaction between the pigment derivative and the resin component in the varnish. Methods for stabilizing the dispersion are known (for example, see Patent Documents 1 to 5), and certain effects are obtained.

  On the other hand, with the recent increase in screen size of color liquid crystal display devices, the prospective angle has increased, and high-level oblique visibility has been required. The factors affecting the visibility in the oblique direction are mainly the birefringence of the liquid crystal molecules and the viewing angle dependency of the polarizing plate, but the influence on the color filter based on the pigment dispersion method can no longer be ignored.

  The reason why the color filter deteriorates the visibility in the oblique direction is that the pigment and the resin which are constituent components have birefringence. On the other hand, it has been proposed that pigment particles having different specific surface areas are used together to make the distribution state of the pigment particles uniform and cancel the anisotropy of the pigment particles (Patent Document 6). However, this method is not versatile because the types of pigments are limited.

As a more general method, it has been proposed to cancel the anisotropy of the pigment with a resin containing a planar structure group (Patent Document 7). According to this method, the visibility in an oblique direction can be easily improved regardless of the type of pigment of the color filter coloring composition and without any change in the process of manufacturing the color filter. However, the color filter obtained by the method of Patent Document 7 has a problem that the adhesion between the coating film and a transparent substrate such as glass is not sufficient.
Japanese Patent Publication No.41-2466 U.S. Pat. No. 2,855,403 JP-A-63-305173 JP-A-1-247468 JP-A-3-26767 JP 2007-47760 A JP 2000-136253 A

  The present invention provides a coloring composition for a color filter and a color filter, which are excellent in pigment dispersion stability and oblique visibility, and have strong adhesion between a coating film and a transparent substrate such as glass. With the goal.

  As a result of intensive studies to solve the above problems, the present inventors have made fine pigment particles at least one kind selected from a triazine ring-containing epoxy resin [A] and a triazine ring-containing phenol resin [B]. By dispersing the resin and a pigment derivative having a specific basic group, an anthraquinone derivative, an acridone derivative, or a triazine derivative in a pigment carrier containing a monomer, the pigment has excellent dispersion stability and oblique visibility, and The present inventors have found that a color filter coloring composition and a color filter having strong adhesion between a coating film and a transparent substrate such as glass can be obtained, and the present invention has been achieved.

That is, the first invention includes at least one resin selected from a triazine ring-containing epoxy resin [A] and a triazine ring-containing phenol resin [B];
Pigments,
At least one basic group-containing derivative selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group; ,
The present invention relates to a coloring composition for a color filter comprising a pigment carrier containing a monomer.

  In the second invention, the triazine ring-containing epoxy resin [A] has an epoxy compound (a1) having two or more epoxy groups in the molecule and two or more functional groups capable of reacting with the epoxy group in the molecule. The color composition for color filters according to the first aspect of the present invention is a hydroxyl group-containing resin [A1] obtained by reacting a triazine compound (a2).

In the third invention, the triazine ring-containing epoxy resin [A] has an epoxy compound (a1) having two or more epoxy groups in the molecule and two or more functional groups capable of reacting with the epoxy group in the molecule. Reacting the triazine compound (a2) to produce a hydroxyl group-containing resin [A1],
A carboxyl group-containing resin [A2] obtained by reacting a hydroxyl group in the obtained hydroxyl group-containing resin [A1] with an acid anhydride group in the acid anhydride (a3). The present invention relates to a coloring composition for a color filter of the invention.

Furthermore, in the fourth invention, the triazine ring-containing epoxy resin [A] has an epoxy compound (a1) having two or more epoxy groups in the molecule and two or more functional groups capable of reacting with the epoxy group in the molecule. Reacting the triazine compound (a2) to produce a hydroxyl group-containing resin [A1],
Reacting the hydroxyl group in the obtained hydroxyl group-containing resin [A1] with the acid anhydride group in the acid anhydride (a3) to produce a carboxyl group-containing resin [A2],
Ethylenically unsaturated bond-containing resin obtained by reacting the carboxyl group in the obtained carboxyl group-containing resin [A2] with the epoxy group in the epoxy compound (a4) having an ethylenically unsaturated bond in the molecule [ A3], the coloring composition for a color filter according to the first invention.

  Further, the fifth invention relates to the coloring composition for a color filter according to any one of the second to fourth inventions, wherein the triazine compound (a2) is a compound represented by the general formula (1).

  General formula (1)

(In the formula, T is SH or NR ¹ R ² , and R ¹ and R ² each independently represents a hydrogen atom, an optionally substituted alkyl group, an alkenyl group, or a phenyl group.)
The sixth invention relates to the coloring composition for a color filter according to any one of the second to fifth inventions, wherein the epoxy compound (a1) is a glycidyl ether of a polyalcohol.

  In the seventh invention, the triazine ring-containing phenol resin [B] reacts the phenols (b1), the triazine compound (b2) and the aldehydes (b3) in the presence of an acid catalyst and / or a base catalyst. It is related with the coloring composition for color filters of any one of the 1st-6th invention characterized by being phenolic hydroxyl group containing resin [B1] which becomes.

In an eighth invention, the triazine ring-containing phenol resin [B] reacts the phenols (b1), the triazine compound (b2) and the aldehydes (b3) in the presence of an acid catalyst and / or a base catalyst. Producing a phenolic hydroxyl group-containing resin [B1],
Hydroxyl group-containing resin [B2] obtained by reacting the phenolic hydroxyl group in the obtained phenolic hydroxyl group-containing resin [B1] with the epoxy group in the epoxy compound (b4) having an ethylenically unsaturated bond in the molecule It is related with the coloring composition for color filters of any one of the 1st-6th invention characterized by being.

In the ninth invention, the triazine ring-containing phenol resin [B] reacts the phenols (b1), the triazine compound (b2) and the aldehydes (b3) in the presence of an acid catalyst and / or a base catalyst. Producing a phenolic hydroxyl group-containing resin [B1],
By reacting the phenolic hydroxyl group in the obtained phenolic hydroxyl group-containing resin [B1] with the epoxy group in the epoxy compound (b4) having an ethylenically unsaturated bond in the molecule, the hydroxyl group-containing resin [B2] is reacted. Generate and
It is a carboxyl group-containing resin [B3] obtained by reacting a hydroxyl group in the obtained hydroxyl group-containing resin [B2] with an acid anhydride group in the acid anhydride (b5). 6 relates to a color composition for a color filter according to any one of the inventions.

  Further, the tenth invention relates to the coloring composition for a color filter according to any one of the seventh to ninth inventions, wherein the triazine compound (b2) is melamine and / or a melamine resin.

  Furthermore, an eleventh invention relates to the coloring composition for a color filter according to any one of the first to tenth inventions, wherein the pigment carrier containing a monomer further contains a resin.

  Furthermore, a twelfth invention relates to a color filter comprising a filter segment formed from the color filter coloring composition of any one of the first to eleventh inventions.

  According to the present invention, there are provided a coloring composition for a color filter and a color filter which are excellent in dispersion stability of a pigment and visibility in an oblique direction and have strong adhesion between a coating film and a transparent substrate such as glass. I was able to.

  The color filter using the coloring composition for a color filter of the present invention is excellent in pigment dispersibility, and at least one resin selected from a triazine ring-containing epoxy resin [A] and a triazine ring-containing phenol resin [B]. Thus, the birefringence of the pigment is canceled out, so that the birefringence measured from an oblique direction falls within a specific range. Therefore, the color filter which comprises the coating film produced using the coloring composition for color filters of this invention as a color filter segment is excellent in the visibility of a diagonal direction. Moreover, the color filter using the coloring composition for color filters of this invention has strong adhesiveness between a coating film and transparent substrates, such as glass, by having a triazine ring in resin.

  First, the triazine ring containing epoxy resin [A] contained in the coloring composition for color filters of this invention is demonstrated. The triazine ring-containing epoxy resin [A] is an epoxy resin having a triazine ring in the molecule (herein, “epoxy resin” refers to a resin obtained by reacting a compound having an epoxy group as one of raw materials. , Including those in which the epoxy group has disappeared due to the reaction.) Is not particularly limited, but it is preferably any of the three forms described below.

  That is, in the first embodiment, the triazine ring-containing epoxy resin [A] has an epoxy compound (a1) having two or more epoxy groups in the molecule and two or more functional groups capable of reacting with the epoxy group in the molecule. It is a hydroxyl group-containing resin [A1] that can be obtained by reacting with the triazine compound (a2).

  In the second form, the triazine ring-containing epoxy resin [A] reacts with a hydroxyl group in the hydroxyl group-containing resin [A1] and an acid anhydride group in the acid anhydride (a3). It is group-containing resin [A2].

  Furthermore, the third form is an epoxy in the epoxy compound (a4) in which the triazine ring-containing epoxy resin [A] has a carboxyl group in the carboxyl group-containing resin [A2] and an ethylenically unsaturated bond in the molecule. This is an ethylenically unsaturated bond-containing resin [A3] obtained by reacting with a group.

  Epoxy compound (a1) having two or more epoxy groups in the molecule, which is a raw material for the hydroxyl group-containing resin [A1] [hereinafter sometimes referred to as epoxy compound (a1). ] Will be described. The epoxy compound (a1) is not particularly limited as long as it is an epoxy compound having two or more epoxy groups in the molecule. Polyglycol glycidyl ether, glycidyl amine, polybasic acid glycidyl ester, alicyclic Epoxy and the like can be mentioned, but glycidyl ether of polyalcohol is preferable in consideration of adhesion and the like.

Examples of the glycidyl ether of the polyalcohol include resorcinol diglycidyl ether, dihydroxynaphthalenediglycidyl ether, bisphenol A type, bisphenol F type, bisphenol S type and the like bisphenol type diglycidyl ether, phenol novolac type, cresol novolac type, alkylphenol Aromatic polyalcohol glycidyl ethers such as glycidyl ethers of polynuclear phenols such as novolac type and trisphenol methane type;
Ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether Aliphatic polyalcohol glycidyl ethers such as trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, 2,2′-dibromo-neopentylglycol diglycidyl ether;
Examples thereof include alicyclic polyalcohol glycidyl ethers such as hydrogenated bisphenol A type diglycidyl ether and polyglycidyl ether of dicyclopentadiene-phenol polyaddition product. Two or more epoxy compounds (a1) may be used.

  Next, the triazine compound (a2) [hereinafter referred to as triazine compound (a2), which is a raw material of the hydroxyl group-containing resin [A1] and has two or more functional groups capable of reacting with an epoxy group in the molecule. ] Will be described. Examples of the functional group capable of reacting with the epoxy group in the triazine compound (a2) include a hydroxyl group, a carboxyl group, and a thiol group. A thiol group is preferred because of easy control of the reaction.

  Examples of the triazine compound (a2) having a hydroxyl group include polymethylolmelamine, tris (2-hydroxyethyl) isocyanurate, oxonic acid and the like.

  Examples of the triazine compound (a2) having a carboxyl group include trimeral acid.

  Examples of the triazine compound (a2) having a thiol group include 4,4 ′-(1,4-phenylene) bis (6-amino-1,3,5-triazine-2-thiol), 2,2′-dithiobis [ 6- (dibutylamino) -1,3,5-triazine-4-thiol], 1,3,5-triazine-2,4-dithiol, 2- (octylthio) -1,3,5-triazine-4, Examples include 6-dithiol, 6- (benzylthio) -1,3,5-triazine-2,4-dithiol, and the compound represented by the following general formula (1) is particularly preferable because of easy control of the reaction. . It may be a mixture of two or more compounds represented by the following general formula (1).

  General formula (1)

(In the formula, T is SH or NR ¹ R ² , and R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, an alkenyl group or a phenyl group which may be substituted.)

  Examples of the compound represented by the general formula (1) include 2,4,6-trimercapto-1,3,5-triazine, 2-phenylamino-4,6-dimercapto-1,3,5-triazine. 2-dibutylamino-4,6-dimercapto-1,3,5-triazine, 2-dicyclohexylamino-4,6-dimercapto-1,3,5-triazine, 2-dimethylamino-4,6-dimercapto- 1,3,5-triazine and the like can be mentioned. Among these, 2-dibutylamino-4,6-dimercapto-1,3,5-triazine is preferable because of easy control of reactivity.

  In the production of the hydroxyl group-containing resin [A1] contained in the colored composition of the present invention, a monofunctional epoxy compound reacts in addition to the essential components of the epoxy compound (a1) and the triazine compound (a2) as necessary. May be allowed. For example, aromatic epoxy compounds such as styrene oxide, phenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, glycidyl cinnamate, 2-ethylhexyl glycidyl ether, glycidyl (meth) acrylate, 4-hydroxybutyl ( Aliphatic epoxy compounds such as (meth) acrylate glycidyl ether, glycidyl allyl ether, 2,3-epoxy-2-methylpropyl (meth) acrylate, and 1,3-butadiene monoepoxide can be used in combination.

  Depending on the triazine ring concentration in the resin, the effect of improving visibility from an oblique direction and the adhesiveness change. Therefore, an epoxy compound (a1) having an appropriate epoxy equivalent is used according to the target triazine ring concentration, and epoxy is used. What is necessary is just to select the ratio of a compound (a1) and a triazine compound (a2). Moreover, the molecular weight of the resin obtained can be adjusted by changing the ratio of the epoxy compound (a1) and the triazine compound (a2). The ratio of the functional group capable of reacting with the epoxy group in the epoxy compound (a1) and the monofunctional epoxy compound and the functional group capable of reacting with the epoxy group in the triazine compound (a2) = 0. 1/1 to 1 / 0.1 (molar ratio) is preferable.

  Next, the acid anhydride (a3) that is a raw material of the carboxyl group-containing resin [A2] will be described. A carboxyl group can be introduced into the triazine ring-containing epoxy resin [A] by reacting the hydroxyl group-containing resin [A1] with the acid anhydride (a3). When the colored composition for a color filter of the present invention is prepared in the form of an alkali development type colored resist material, this can improve the solubility in a developer and can improve the development speed.

  The acid anhydride (a3) is not particularly limited as long as it is a compound having an acid anhydride group. For example, succinic anhydride, itaconic anhydride, maleic anhydride, glutaric anhydride, hexahydrophthalic anhydride, tetrahydro Aliphatic cyclic acid anhydrides such as phthalic anhydride, aromatic cyclic acid anhydrides such as phthalic anhydride, isatoic anhydride, diphenic anhydride, etc., and saturated or unsaturated aliphatic hydrocarbon groups, aryl groups, halogens And derivatives having a group or a heterocyclic group bonded thereto.

  The higher the acid value of the carboxyl group-containing resin [A2], the greater the effect of improving the development speed. In such a case, an acid anhydride (a3) having a small acid anhydride equivalent may be selected to increase the reaction ratio of the acid anhydride (a3) to the hydroxyl group-containing resin [A1]. However, if the acid value of the resin is too high, problems such as an increase in viscosity and a decrease in storage stability may occur. Furthermore, when the amount of the acid anhydride (a3) incorporated in the resin is increased, the triazine ring concentration in the resin is lowered, and there may be a problem that the effect of improving the visibility from an oblique direction and the adhesiveness are lowered. is there. Therefore, the ratio of the hydroxyl group in the hydroxyl group-containing resin [A1] to the acid anhydride group in the acid anhydride (a3) is hydroxyl group / acid anhydride group = 1 / 0.001-1 / 1 (molar ratio). Is preferred.

  Epoxy compound (a4) having an ethylenically unsaturated bond in the molecule, which is a raw material for the ethylenically unsaturated bond-containing resin [A3] [hereinafter sometimes referred to as an epoxy compound (a4). ] Will be described. An ethylenically unsaturated bond can be introduced into the triazine ring-containing epoxy resin [A] by reacting the carboxyl group-containing resin [A2] with the epoxy compound (a4). Thus, photosensitivity can be imparted to the triazine ring-containing epoxy resin [A], and the color filter coloring composition of the present invention can be efficiently cured with a small amount of ultraviolet light exposure. The epoxy compound (a4) is not particularly limited as long as it has an ethylenically unsaturated bond and one epoxy group in the molecule. For example, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Glycidyl ether, glycidyl allyl ether, 2,3-epoxy-2-methylpropyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-vinyl-1-cyclohexene-1,2-epoxide, Examples thereof include glycidyl cinnamate, 1,3-butadiene monoepoxide, and Celoxide 2000 (manufactured by Daicel Chemical Industries, Ltd.).

  The lower the double bond equivalent of the ethylenically unsaturated bond-containing resin [A3], the higher the curing efficiency. In such a case, an epoxy compound (a4) having a small double bond equivalent may be selected and the reaction ratio of the epoxy compound (a4) to the carboxyl group-containing resin [A2] may be increased. However, if the double bond equivalent is too low, there may be a problem in polymerization stability and storage stability. Furthermore, when the amount of the epoxy compound (a4) incorporated in the resin increases, the triazine ring concentration in the resin decreases, and the problem that the effect of improving the visibility from an oblique direction and the adhesiveness decrease occurs. There is. Therefore, the ratio of the carboxyl group in the carboxyl group-containing resin [A2] and the epoxy group in the epoxy compound (a4) is preferably carboxyl group / epoxy group = 1 / 0.001-1 / 1 (molar ratio). .

  The form of these triazine ring-containing epoxy resins [A] can be appropriately selected depending on the purpose of use, and in some cases, several types of resins may be used in combination.

  In producing the triazine ring-containing epoxy resin [A], a known catalyst can be used. Specifically, in the reaction of thiol and epoxy group, quaternary ammonium salt such as tetrabutylammonium bromide or quaternary phosphonium salt, tertiary amines such as pyridine and N, N-dimethylbenzylamine, tributylphosphine, Examples include tertiary phosphines such as triphenylphosphine, organometallic compounds, and the like. In other reactions, a catalyst may be added as appropriate.

  The triazine ring-containing epoxy resin [A] contained in the coloring composition for a color filter of the present invention can be produced using only the above-mentioned raw materials, but there are problems such as high viscosity and non-uniform reaction. It is preferable to use a solvent. As the solvent to be used, known solvents can be used. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, methyl propylene glycol acetate, tetrahydrofuran, N, N-dimethylformamide, acetonitrile and the like can be mentioned. The reaction temperature for obtaining the triazine ring-containing epoxy resin [A] contained in the colored composition of the present invention is preferably 40 to 120 ° C.

  The weight average molecular weight of the triazine ring-containing epoxy resin [A] is preferably 1000 to 50000, and particularly preferably 2000 to 30000. When the weight average molecular weight is less than 1000, the heat resistance may be insufficient, and when the weight average molecular weight exceeds 50,000, the viscosity of the color filter coloring composition may increase, resulting in poor coating properties. is there. In addition, the higher the triazine ring concentration in the triazine ring-containing epoxy resin [A], the better the effect of improving the visibility from the oblique direction and the adhesion. The triazine ring concentration in the triazine ring-containing epoxy resin [A] is preferably 5 to 30% by weight, particularly preferably 10 to 25% by weight. A triazine ring concentration exceeding 30% by weight may limit synthesis.

  Next, the triazine ring containing phenol resin [B] contained in the coloring composition for color filters of this invention is demonstrated. The triazine ring-containing phenol resin [B] is not particularly limited as long as it is a resin having a triazine ring and a phenolic hydroxyl group in the molecule, but is preferably any one of the three forms described below.

  That is, in the first form, the triazine ring-containing phenol resin [B] reacts the phenols (b1), the triazine compound (b2), and the aldehydes (b3) in the presence of an acid catalyst and / or a base catalyst. This is a phenolic hydroxyl group-containing resin [B1].

  In the second embodiment, the triazine ring-containing phenol resin [B] is in an epoxy compound (b4) having a phenolic hydroxyl group in the phenolic hydroxyl group-containing resin [B1] and an ethylenically unsaturated bond in the molecule. It is a hydroxyl group-containing resin [B2] obtained by reacting with an epoxy group.

  Further, in the third embodiment, a triazine ring-containing phenol resin [B] reacts with a hydroxyl group in the hydroxyl group-containing resin [B2] and an acid anhydride group in the acid anhydride (b5). This is a group-containing resin [B3].

  The phenols (b1) used as the raw material for the phenolic hydroxyl group-containing resin [B1] are not particularly limited as long as they can be added with aldehydes (b3) and further undergo a condensation reaction. Phenols, or alkylphenols such as orthocresol, paracresol, metacresol, xylenol, paranonylphenol, polyhydric phenols such as catechol, resorcinol, hydroquinone, phenylphenol, bisphenol A, bisphenol F, bisphenol B, bisphenol E, bisphenol H, Examples thereof include polycyclic phenols such as bisphenol S, and phenol resins such as phenol novolac, cresol novolac, and alkylphenol novolac obtained by addition condensation of these with aldehydes. . Two or more phenols (b1) may be used.

  The triazine compound (b2), which is a raw material for the phenolic hydroxyl group-containing resin [B1], is not particularly limited as long as it can be added with an aldehyde (b3) and further undergo a condensation reaction. For example, melamine, Examples thereof include guanamines, cyanuric acids, and resins such as melamine resins and guanamine resins obtained by addition condensation of these with aldehydes. From the viewpoint of the effect of improving oblique visibility, melamine and melamine resin are particularly preferable. As the triazine compound (b2), the above-mentioned triazine compound (a2) can also be used, but it may cause a problem in the stability of polymerization, so that the use of the triazine compound (a2) is minimized. Is good. Two or more triazine compounds (b2) may be used.

  The aldehyde (b3) that is a raw material of the phenolic hydroxyl group-containing resin [B1] is not particularly limited as long as it has an aldehyde group, and examples thereof include formaldehyde and acetaldehyde. Examples of the formaldehyde supply source include formalin, formit NB (formaldehyde n-butanol solution, manufactured by DIC Corporation), paraformaldehyde, trioxane, and the like.

  When a methylol group derived from the addition of aldehydes (b3) is present in the phenolic hydroxyl group-containing resin [B1] contained in the coloring composition for a color filter of the present invention, the methylol group has a high reactivity, and thus has room temperature. The self-condensation proceeds and the storage stability of the resin may deteriorate. In that case, the methylol group can be usefully handled by reacting with an alkyl alcohol to form an alkoxymethyl group. Therefore, when producing the phenolic hydroxyl group-containing resin [B1], an alkyl alcohol may be reacted in addition to the phenols (b1), the triazine compound (b2) and the aldehydes (b3). Examples of the alkyl alcohol include methanol, ethanol, propanol, butanol, hexanol, octanol, nonanol, decanol, and allyl alcohol.

  The effect of improving the visibility from an oblique direction and the adhesiveness change depending on the triazine ring concentration in the resin. Therefore, the ratio of the phenols (b1) to the triazine compound (b2) according to the target triazine ring concentration You can adjust. The higher the triazine ring concentration, the greater the effect of improving the visibility from the oblique direction. However, since the triazine compound (b2) has a higher polymerization rate than the phenols (b1), the triazine compound ( If the ratio of b2) is increased, there may be a problem in the stability of polymerization. The ratio of the phenols (b1) to the triazine compound (b2) is preferably phenols (b1) / triazine compound (b2) = 0.1 / 1 to 1 / 0.1 (molar ratio).

  The aldehydes (b3) are preferably reacted in an amount of 0.6 to 2 equivalents per 1 equivalent of the total theoretical functional hydrogen of the phenols (b1) and the triazine compound (b2). The phenolic hydroxyl group-containing resin [B1] produced when the amount of aldehydes is less than 0.6 equivalents relative to 1 equivalent of the total theoretical functional hydrogen is increased in molecular weight, and is used for a general-purpose solvent used in the color filter coloring composition. Solubility deteriorates, and the color filter coating film is liable to be blistered. On the other hand, the amount of aldehydes that cannot actually react even when used in an excessive amount increases and is contained in the waste water when it is removed after completion of the reaction, so usually 2 equivalents per 1 equivalent of the total theoretical functional hydrogen. It is appropriate that:

  Here, the theoretical functional hydrogen in the phenols and triazine compounds of the present invention refers to hydrogen at the reaction site of phenols and triazine compounds that can react with aldehydes. That is, in the phenols, the ortho position and the para position are reaction sites with respect to the phenolic hydroxyl group. Accordingly, ortho-cresol, para-cresol and the like are phenols having 2 reaction sites in one molecule and having 2 equivalents. Phenol, metacresol, resorcinol and the like are phenols having 3 reaction sites in one molecule and having an equivalent number of 3. Further, bisphenols such as bisphenol A and bisphenol F, catechol, hydroquinone, and the like are phenols having an equivalent number of 4 having 4 reactive sites in one molecule. Furthermore, melamine is a triazine compound having 6 reaction sites in one molecule and having 6 equivalents.

  As the catalyst for producing the phenolic hydroxyl group-containing resin [B1], an acid catalyst or a base catalyst can be used. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, formic acid, and acetic acid. And organic acids such as oxalic acid, succinic acid, maleic acid, fumaric acid, and toluenesulfonic acid. Examples of the base catalyst include alkali metal hydroxides or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide, ammonia or amines. Two or more kinds of catalysts can be used.

  The order of reaction of the phenols (b1), the triazine compound (b2) and the aldehydes (b3) is not particularly limited. The reaction may be performed simultaneously in the same system, or the phenols (b1) and the aldehydes (b3), the triazine compound (b2) and the aldehydes (b3) are separately reacted and then mixed. You may let them. Alternatively, the phenols (b1) and the aldehydes (b3) may be reacted, and the triazine compound (b2) may be added and reacted later. Conversely, the triazine compound (b2) and the aldehydes (b3) may be reacted. It is allowed to react, and phenols (b1) may be added later to react. In order to carry out the polymerization stably, the phenols (b1) having a low polymerization rate are reacted with the aldehydes (b3) in an acidic range, preferably in the range of pH 1 to 4, for polymerization. Thereafter, by adding a basic catalyst, the pH of the system is neutral, preferably 5-7, and the polymerization rate is lowered, and the triazine compound (b2) that has been reacted with the aldehydes (b3) in advance is added. Addition and copolymerization are preferred.

  As the phenolic hydroxyl group-containing resin [B1], commercially available resins such as aminotriazine novolak resins (Phenolite LA-1356, Phenolite LA-7054, etc., manufactured by DIC Corporation) can also be used.

  Epoxy compound (b4) having an ethylenically unsaturated bond in the molecule, which is a raw material for the hydroxyl group-containing resin [B2] [hereinafter, sometimes referred to as an epoxy compound (b4). ] Can be the same as the epoxy compound (a4). An ethylenically unsaturated bond can be introduced into the triazine ring-containing phenol resin [B] by reacting the phenolic hydroxyl group-containing resin [B1] with the epoxy compound (b4). Thereby, photosensitivity can be imparted to the triazine ring-containing phenol resin [B], and the color filter coloring composition of the present invention can be efficiently cured with a small amount of ultraviolet light exposure.

  The lower the double bond equivalent of the hydroxyl group-containing resin [B2], the higher the curing efficiency. In such a case, an epoxy compound (b4) having a small double bond equivalent may be selected to increase the reaction ratio of the epoxy compound (b4) to the phenolic hydroxyl group-containing resin [B1]. However, if the double bond equivalent is too low, there may be a problem in polymerization stability and storage stability. Furthermore, when the amount of the epoxy compound (b4) incorporated in the resin increases, the triazine ring concentration in the resin decreases, and the problem that the effect of improving the visibility from an oblique direction and the adhesiveness decrease occurs. There is. Therefore, the ratio of the phenolic hydroxyl group in the phenolic hydroxyl group-containing resin [B1] to the epoxy group in the epoxy compound (b4) is phenolic hydroxyl group / epoxy group = 1 / 0.001-1 / 1 (molar ratio). ) Is preferred.

  A known catalyst can be used in producing the hydroxyl group-containing resin [B2]. Quaternary ammonium salts or quaternary phosphonium salts such as tetrabutylammonium bromide, tertiary amines such as pyridine and N, N-dimethylbenzylamine, tertiary phosphines such as tributylphosphine and triphenylphosphine, organometallic compounds Etc. Two or more kinds of catalysts can be used.

  As the acid anhydride (b5) used as a raw material of the carboxyl group-containing resin [B3], the same acid anhydride (a3) as that described above can be used. A carboxyl group can be introduced into the triazine ring-containing phenol resin [B] by reacting the hydroxyl group-containing resin [B2] with the acid anhydride (b5). As a result, it is possible to obtain the effect that the solubility in an alkali developer is improved and the development speed is improved.

  The higher the acid value of the carboxyl group-containing resin [B3], the greater the effect of improving the development speed. In such a case, an acid anhydride (b5) having a small acid anhydride equivalent may be selected to increase the reaction ratio of the acid anhydride (b5) to the hydroxyl group-containing resin [B2]. However, if the acid value of the resin is too high, problems such as an increase in viscosity and a decrease in storage stability may occur. Furthermore, when the amount of the acid anhydride (b5) incorporated in the resin increases, the triazine ring concentration in the resin decreases, and the problem that the effect of improving the visibility from an oblique direction and the adhesiveness decrease may occur. is there. Therefore, the ratio of the hydroxyl group in the hydroxyl group-containing resin [B2] to the acid anhydride group in the acid anhydride (b5) is hydroxyl group / acid anhydride group = 1 / 0.001-1 / 1 (molar ratio). Is preferred.

  When manufacturing carboxyl group-containing resin [B3], the same well-known catalyst as the case where hydroxyl group-containing resin [B2] is manufactured can be used.

  The form of the triazine ring-containing phenol resin [B] can be appropriately selected depending on the purpose of use, and in some cases, several types of resins may be used in combination.

  The triazine ring-containing phenol resin [B] contained in the coloring composition for a color filter of the present invention can be produced using only the raw materials listed so far, but there are problems such as high viscosity and non-uniform reaction. It is preferable to use a solvent. As the solvent to be used, known solvents can be used. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, methyl propylene glycol acetate, tetrahydrofuran, N, N-dimethylformamide, acetonitrile and the like can be mentioned.

  The temperature of the reaction for obtaining the triazine ring-containing phenol resin [B] contained in the colored composition of the present invention is preferably 40 to 120 ° C. After the reaction to obtain the phenolic hydroxyl group-containing resin [B1], it is preferable that the reaction system is depressurized as necessary at 100 to 200 ° C. to dehydrate and remove unreacted substances.

  The weight average molecular weight of the triazine ring-containing phenol resin [B] is preferably 300 to 20,000, and particularly preferably 500 to 10,000. When the weight average molecular weight is less than 300, the heat resistance may be insufficient, and when the weight average molecular weight exceeds 20000, the viscosity of the color filter coloring composition may increase and the coating property may deteriorate. In addition, the higher the triazine ring concentration in the triazine ring-containing phenol resin [B], the better the effect of improving the visibility from the oblique direction and the adhesion. The triazine ring concentration in the triazine ring-containing phenol resin [B] is preferably 5 to 50% by weight, and particularly preferably 10 to 25% by weight. A triazine ring concentration exceeding 50% by weight may limit synthesis.

  In the present invention, even when only one of the triazine ring-containing epoxy resin [A] and the triazine ring-containing phenol resin [B] is used, the dispersion stability of the pigment and the visibility in the oblique direction are excellent, and the coating film A colored composition for a color filter having strong adhesion between the glass and a transparent substrate such as glass can be obtained, but both may be used together as necessary.

  As a pigment contained in the 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. The pigment is preferably a pigment having high color developability and high heat resistance, particularly a pigment having high heat decomposition resistance, and an organic pigment is usually used. Below, the specific example of the organic pigment which can be used for the coloring composition of this invention is shown with a color index number.

  Examples of the red coloring composition for forming the red filter segment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, Red pigments such as 272 can be used. A yellow pigment and an orange pigment can be used in combination with the red composition.

  Examples of the yellow coloring composition for forming the yellow filter segment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 1 Yellow pigments such as 75, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199 can be used.

  Examples of the orange coloring composition for forming the orange filter segment include C.I. I. Orange pigments such as Pigment Orange 36, 43, 51, 55, 59, 61 can be used.

  Examples of the green coloring composition for forming the green filter segment include C.I. I. Green pigments such as Pigment Green 7, 10, 36, and 37 can be used. A yellow pigment can be used in combination with the green composition.

  Examples of the blue coloring composition for forming the blue filter segment include C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, and 64 can be used. Blue compositions 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.

  Examples of the cyan coloring composition for forming the cyan filter segment include C.I. I. Blue pigments such as Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, and 81 can be used.

  Examples of magenta colored compositions for forming magenta color filter segments include C.I. I. Pigment Violet 1, 19, C.I. I. Purple pigments such as Pigment Red 144, 146, 177, 169, 81, and red pigments can be used. A yellow pigment can be used in combination with the magenta composition.

  In addition, inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean [red iron oxide (III)], cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber , Titanium black, synthetic iron black, carbon black and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness. The coloring composition of the present invention can contain a dye within a range that does not decrease heat resistance for color matching.

  A pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, or a triazine derivative having a basic group included in the present invention are represented by the following general formulas (2), (3), It has at least one substituent selected from the group represented by (4) and (5).

  General formula (2)

  General formula (3)

  General formula (4)

  General formula (5)

X represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.

  m represents an integer of 1 to 10.

R ³ , R ⁴ Each independently represents an optionally substituted alkyl group, alkenyl group, phenyl group, or a heterocycle formed by combining R ³ and R ⁴ together. However, the heterocycle may contain further nitrogen, oxygen or sulfur atoms. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.

R ⁵ Represents an alkyl group, an alkenyl group or a phenyl group which may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom, an optionally substituted alkyl group, an alkenyl group or a phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.

Y represents —NR ¹⁰ —Z—NR ¹¹ — or a direct bond.

R ¹⁰ and R ¹¹ each independently represents a hydrogen atom, an optionally substituted alkyl group, an alkenyl group or a phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.

  Z represents an alkylene group, an alkenylene group, or a phenylene group, which may be substituted. As for carbon number of an alkylene group and an alkenylene group, 1-8 are preferable.

  P represents a substituent represented by the general formula (6) or a substituent represented by the general formula (7).

  Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (6) or a substituent represented by the general formula (7).

  General formula (6)

  General formula (7)

X ¹ and X ² represent —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.

  m represents an integer of 1 to 10.

R ³ , R ⁴ Each independently represents an optionally substituted alkyl group, alkenyl group, phenyl group, or a heterocycle formed by combining R ³ and R ⁴ together. However, the heterocycle may contain further nitrogen, oxygen or sulfur atoms. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.

R ⁵ Represents an alkyl group, an alkenyl group or a phenyl group which may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom, an optionally substituted alkyl group, an alkenyl group or a phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.

Examples of the alkyl group in R ^{3 to} R ¹¹ in the above general formula include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the alkenyl group include a vinyl group and a propenyl group.

  Examples of the alkylene group in Z in the general formula include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the alkenylene group include a vinylene group and a propenylene group.

  Examples of the alkoxyl group for Q in the above general formula include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  Examples of the functional group that may be substituted include a halogen group, a cyano group, an alkoxyl group, an amino group, a hydroxyl group, a nitro group, and an epoxy group.

  Examples of the amine component used to form the substituents represented by the general formulas (2) to (7) include dimethylamine, diethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, 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, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, Didecylamine, diallylamine, N N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylamino Amylamine, 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-diisobutylaminopentylamine, N, N-methyl-laurylamino The Pyramine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecholine, 3-pipecholine, 4 -Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isnicopetinate, Ethyl isonicopetic acid, 2-Piperidinethanol, Pyrrolidine, 3-hydroxy Pyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, N-aminopropyl-4-pipecholine, N-amino Examples thereof include propylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

  Organic dyes contained in pigment derivatives having basic groups include, for example, diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, anthanthrones Anthraquinone dyes such as indanthrone, pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, sulene dyes It is a dye such as a dye or a metal complex dye. In addition, anthraquinone derivatives having a basic group and acridone derivatives having a basic group include alkyl groups such as methyl and ethyl groups, amino groups, nitro groups, hydroxyl groups or methoxy groups, alkoxy groups such as ethoxy groups, chlorine, etc. It may have a substituent such as halogen.

  The triazine contained in the triazine derivative having a basic group includes an alkyl group such as a methyl group and an ethyl group, an amino group, or an alkylamino group such as a dimethylamino group, a diethylamino group, and a dibutylamino group, a nitro group, a hydroxyl group, Alternatively, an alkoxy group such as a methoxy group, an ethoxy group, or a butoxy group, a halogen such as chlorine, or a phenyl group that may be substituted with a methyl group, a methoxy group, an amino group, a dimethylamino group, a hydroxyl group, or the like, a methyl group, or an ethyl group Group, methoxy group, ethoxy group, amino group, dimethylamino group, diethylamino group, nitro group, optionally substituted with phenylamino group etc. Triazine.

  The pigment derivative, anthraquinone derivative, and acridone derivative having a basic group included in the present invention can be synthesized by various synthetic routes. For example, after introducing the substituents represented by the formulas (8) to (11) into an organic dye, anthraquinone or acridone, the substituents represented by the general formulas (2) to (5) are formed by reacting with the above substituents. Amine components such as N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5-triazine- It can be obtained by reacting 2-ylamino] aniline or the like.

Equation (8) -SO ₂ Cl
Formula (9) -COCl
Equation (10) -CH ₂ NHCOCH ₂ Cl
Equation (11) -CH ₂ Cl

  When the organic dye is an azo dye, the substituent represented by the general formulas (2) to (5) is previously introduced into the diazo component or the coupling component, and then a coupling reaction is performed, thereby performing the azo pigment. Derivatives can also be produced.

  The triazine derivative having a basic group included in 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 general formulas (2) to (5) 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.

  Specific examples of the derivative having a specific basic group are shown below, but are not limited thereto. These derivatives can be used alone or in admixture of two or more.

As described above, the triazine ring-containing epoxy resin [A] and the triazine ring-containing phenol resin [B] contained in the coloring composition for a color filter of the present invention may each be used alone or in combination. You can also As for the amount of use, the total of the triazine ring-containing epoxy resin [A] and the triazine ring-containing phenol resin [B] is preferably 0.01 to 40 parts by weight with respect to 100 parts by weight of the pigment. The amount of the basic group-containing derivative used is preferably 0.001 to 40 parts by weight with respect to 100 parts by weight of the pigment.
Moreover, you may mix various solvents, resin, an additive, a dispersing agent, etc. if needed.

  The pigment carrier contained in the coloring composition for a color filter of the present invention comprises a monomer and, if necessary, a resin. As monomers, 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, neopentylglyco Various acrylic esters such as rubidiglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate And methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile These may be used alone or in combination of two or more.

  The resin is a transparent resin 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 transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and these can be used alone or in combination of two or more. 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 phenol resin. , Polyester resins, acrylic resins, alkyd resins, styrene resins, polyamide resins, rubber resins, cyclized rubbers, celluloses, polybutadiene, polyimide resins, and the like. Moreover, as a thermosetting resin, an epoxy resin, a benzoguanamine resin, a rosin modified maleic acid resin, a rosin modified fumaric acid resin, a melamine resin, a urea resin etc. are mentioned, for example.

  As the photosensitive resin, a (meth) acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group, A resin obtained by reacting cinnamic acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Also, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin maleic anhydride copolymer is half-treated with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. An esterified product is also used.

  When the composition is cured by ultraviolet irradiation, a photoinitiator or the like is added to the coloring composition for a color filter of the present invention. As photoinitiators, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxy Acetophenone photoinitiators such as cyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin photoinitiators such as benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4 -Benzophenone photoinitiators such as methyldiphenyl sulfide, thioxanthone photoinitiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 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-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl)- -Triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4- Triazine photoinitiators such as trichloromethyl (4′-methoxystyryl) -6-triazine, borate photoinitiators, carbazole photoinitiators, imidazole photoinitiators and the like are used.

  These photoinitiators are used alone or in combination of two or more. As sensitizers, α-acyloxime 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 colored composition for a color filter of the present invention can be prepared in the form of a solvent developing type or alkali developing type colored resist material. The colored resist material is obtained by dispersing a pigment in a pigment carrier containing a thermoplastic resin, a thermosetting resin or a photosensitive resin and a monomer, and a pigment composition composed of a pigment or two or more pigments is necessary. Accordingly, together with the photoinitiator, it can be produced by finely dispersing in a pigment carrier using various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor. The colored composition of the present invention can also be produced by mixing several types of pigments separately dispersed on a pigment carrier.

  The colored composition for a color filter of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. When dispersing the pigment in the pigment carrier, a dispersion aid such as a resin-type pigment dispersant and a surfactant can be appropriately used. The dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when a coloring composition obtained by dispersing the pigment in the pigment carrier using the dispersion aid is used. Provides a color filter excellent in transparency.

  The resin-type pigment dispersant has a pigment affinity part having a property of adsorbing to the pigment and a part compatible with the pigment carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the pigment carrier. It works. Specific examples of resin-type pigment 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 alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Salt 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 Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and the like are used. These can be used alone or in admixture of two or more.

  Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid. Anionic surfactants such as sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, Polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol monora Nonionic surfactants such as rate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaines; and amphoteric surfactants such as alkylimidazolines These can be used alone or in admixture of two or more.

  In the coloring composition for a color filter of the present invention, a pigment is sufficiently dispersed in a pigment carrier, and applied to a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. A solvent can be included to facilitate formation. 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.

  In addition, the colored composition for a color filter of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. 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. The pigment is preferably contained in the coloring composition at a ratio of 1.5 to 7% by weight. Further, the pigment is preferably contained in the final filter segment in a proportion of 10 to 40% by weight, more preferably 20 to 40% by weight, and the remainder substantially consists of a resinous binder provided by the pigment carrier. .

  The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, or at least one magenta filter segment, at least one cyan filter segment, and at least It comprises one yellow filter segment, wherein at least one filter segment is formed using the colored composition of the present invention.

  The color filter of this invention can be manufactured by forming the filter segment of each color on a transparent substrate using the coloring composition of this invention by the photolithographic method. 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 color filter coloring composition prepared as the solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, etc. It applies so that it may become 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided 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 the polymerization of the colored resist material, heating can be performed as necessary. 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 coating and drying the colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method or the like in addition to the photolithography method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there. The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “parts” means “parts by weight” and “%” means “% by weight”. First, preparation of the triazine ring-containing epoxy resin solution, triazine ring-containing phenol resin solution, acrylic resin solution, and polyamic acid resin solution used in Examples and Comparative Examples will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography). The triazine ring concentration is the weight percent of the triazine ring in the resin solid content calculated from the raw material charge ratio.

(Preparation of triazine ring-containing epoxy resin solution)
[Production Example 1]
2-Dibutylamino-4,6-dimercapto-1,3,5-triazine (Disnet DB, Sankyo Chemical Co., Ltd.) was added to a four-necked flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel. 7.02 parts (made by company), 4.94 parts ethylene glycol diglycidyl ether (Denacol EX-811, manufactured by Nagase ChemteX Corporation) and 17.93 parts cyclohexanone were charged and heated to 90 ° C. Next, 0.12 part of N, N-dimethylbenzylamine was added as a catalyst and stirred for 3 hours. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 200 ° C. for 20 minutes to measure the nonvolatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. A triazine ring-containing epoxy resin solution (A-1) was obtained.

[Production Examples 2, 3, 6]
The raw materials were charged according to Table 1 and reacted in the same manner as in Production Example 1 to obtain triazine ring-containing epoxy resin solutions (A-2), (A-3) and (A-6).

[Production Example 4]
A 4-neck flask equipped with a stirrer, a reflux condenser, a gas inlet tube, a thermometer, and a dropping funnel was charged with 6.46 parts of DISNET DB, 4.54 parts of Denacol EX-811, and 16.51 parts of cyclohexanone at 90 ° C. The temperature was raised to. Next, 0.11 part of N, N-dimethylbenzylamine was added as a catalyst and stirred for 3 hours. Subsequently, 2.37 parts of succinic anhydride was added and stirred for 2 hours. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 200 ° C. for 20 minutes to measure the nonvolatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. A triazine ring-containing epoxy resin solution (A-4) was obtained.

[Production Example 5]
A 4-neck flask equipped with a stirrer, a reflux condenser, a gas inlet tube, a thermometer, and a dropping funnel was charged with 6.05 parts of dysnet DB, 4.26 parts of Denacol EX-811 and 15.46 parts of cyclohexanone at 90 ° C. The temperature was raised to. Next, 0.10 parts of N, N-dimethylbenzylamine was added as a catalyst and stirred for 3 hours. Subsequently, 2.22 parts of succinic anhydride was added and stirred for 2 hours. Subsequently, 1.89 parts of glycidyl methacrylate and 0.01 part of hydroquinone were added and stirred for 4 hours. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 200 ° C. for 20 minutes to measure the nonvolatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. A triazine ring-containing epoxy resin solution (A-5) was obtained.

  Table 1 shows the properties of the triazine ring-containing epoxy resins prepared in Production Examples 1 to 6.

Disnet DB: 2-dibutylamino-4,6-dimercapto-1,3,5-triazine (Sankyo Kasei Co., Ltd.)
Disnet AF: 2-phenylamino-4,6-dimercapto-1,3,5-triazine (Sankyo Kasei Co., Ltd.)
EX-811: Ethylene glycol diglycidyl ether (Nagase ChemteX Corporation trade name Denacol EX-811)
EX-201: Resorcinol diglycidyl ether (Nagase ChemteX Corporation trade name Denacol EX-201)
EX-832: Polyethylene glycol diglycidyl ether (Nagase ChemteX Corporation trade name Denacol EX-832)
Succinic anhydride: Wako Pure Chemical Industries, Ltd. GMA: Glycidyl Methacrylate (NOF Corporation, trade name BLEMER G)
Dimethylbenzylamine: N, N-dimethylbenzylamine (Wako Pure Chemical Industries, Ltd.)
Hydroquinone: Wako Pure Chemical Industries, Ltd. Cyclohexanone: Wako Pure Chemical Industries, Ltd.

(Preparation of triazine ring-containing phenol resin solution)
[Production Example 7]
A 4-necked flask equipped with a stirrer, reflux condenser, gas inlet tube, and thermometer was charged with 3.79 parts of orthocresol, 2.84 parts of 37% formalin and 28.21 parts of cyclohexanone, and the temperature was raised to 70 ° C. . Next, 0.52 parts of oxalic acid was added as a catalyst and stirred for 2 hours. Next, 15.16 parts of methylated melamine resin (Nicalac MW-30M, manufactured by Nippon Carbide Industries Co., Ltd.) was added and stirred for 2 hours. After adding 0.88 parts of triethylamine and neutralizing, dehydration under reduced pressure was performed at 150 ° C. for 1 hour. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 200 ° C. for 20 minutes to measure the nonvolatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. A triazine ring-containing phenol resin solution (B-1) having a triazine ring concentration of 16% and a weight average molecular weight of 1900 was obtained.

[Production Example 8]
A four-necked flask equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer was charged with 8.26 parts of melamine and 15.94 parts of 37% formalin and heated to 70 ° C. Next, 1.16 parts of oxalic acid was added as a catalyst and stirred for 2 hours. Next, 24.64 parts of phenol and 48.15 parts of cyclohexanone were added and stirred for 2 hours. After neutralizing by adding 1.31 parts of triethylamine, vacuum dehydration was performed at 150 ° C. for 1 hour. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 200 ° C. for 20 minutes to measure the nonvolatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. A triazine ring-containing phenol resin solution (B-2) having a triazine ring concentration of 13% and a weight average molecular weight of 2,100 was obtained.

[Production Example 9]
In a four-necked flask equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer, 39.82 parts of aminotriazine novolac resin solution (Phenolite LA-1356, MEK solution having a nonvolatile content of 59%, manufactured by DIC Corporation) , 6.51 parts of glycidyl methacrylate, 3.67 parts of cyclohexanone, and 0.02 part of hydroquinone were charged and heated to 90 ° C. Next, 0.60 part of N, N-dimethylbenzylamine was added as a catalyst and stirred for 20 hours. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 200 ° C. for 20 minutes to measure the nonvolatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. Thus, a triazine ring-containing phenol resin solution (B-3) having a triazine ring concentration of 14%, a weight average molecular weight of 600, a double bond equivalent of 655 g / eq, and an acid value of 0 mgKOH / g in the solid content was obtained.

[Production Example 10]
In a four-necked flask equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer, 31.82 parts of aminotriazine novolak resin solution (Phenolite LA-1356, MEK solution having a nonvolatile content of 59%, manufactured by DIC Corporation) , Glycidyl methacrylate 6.51 parts, cyclohexanone 6.96 parts, hydroquinone 0.02 parts were charged, and the temperature was raised to 90 ° C. Next, 0.51 part of N, N-dimethylbenzylamine was added as a catalyst and stirred for 20 hours. Next, 4.72 parts of succinic anhydride was added and stirred for 2 hours. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 200 ° C. for 20 minutes to measure the nonvolatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. Thus, a triazine ring-containing phenol resin solution (B-4) having a triazine ring concentration of 11%, a weight average molecular weight of 800, a double bond equivalent of 655 g / eq, and an acid value of 88 mgKOH / g in the solid content was obtained.

(Preparation of acrylic resin solution)
[Production Example 11]
A 4-necked flask equipped with a stirrer, reflux condenser, gas inlet tube, and thermometer was charged with 450 parts of cyclohexanone and heated to 80 ° C. while injecting nitrogen gas into the container. The mixture of initiators was dropped over 1 hour to carry out the polymerization reaction.

  20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate, 15.0 parts of 2-hydroxyethyl methacrylate, 4.0 parts of 2,2′-azobisisobutyronitrile are added dropwise. did. After completion of dropping, the reaction was allowed to proceed at 80 ° C. for 3 hours. Further, 1.0 part of 2,2′-azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was continued at 80 ° C. for 1 hour to obtain an acrylic resin solution. The weight average molecular weight of the acrylic resin was 40000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. An acrylic resin solution (C-1) was prepared.

(Preparation of polyamic acid resin solution)
[Production Example 12]
In a four-necked flask equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer, 33.06 parts of fluorenediamine, 1.24 parts of bis-3- (aminopropyl) tetramethylsiloxane, 260.6 of γ-butyrolactone The temperature was raised to 70 ° C. Next, 30.69 parts of 4,4′-oxydiphthalic dianhydride was added and stirred for 3 hours. Next, 0.195 parts of maleic anhydride was added and stirred for 2 hours. After cooling to room temperature, sample approximately 2g of the resin solution, heat dry at 200 ° C for 20 minutes, measure the nonvolatile content, and add γ-butyrolactone to the previously synthesized resin solution so that the nonvolatile content is 20% Thus, a polyamic acid resin solution (PA-1) having a viscosity of 120 centipoise (25 ° C.) was obtained.

[Pigment Dispersion Production Example 1]
Brominated copper phthalocyanine pigment (CI Pigment Green 36) (“Lionol Green 6Y-501” manufactured by Toyo Ink Manufacturing Co., Ltd.) 10.0 parts, phthalocyanine pigment derivative (derivative 48) 2.0 parts, acrylic resin solution ( C-1) A mixture of 40.0 parts and 48.0 parts of cyclohexanone was uniformly stirred and mixed, then dispersed with a glass mill having a diameter of 1 mm for 5 hours with a sand mill, and then filtered with a 5 μm filter to disperse the green pigment. The body was made.

[Pigment dispersion production example 2]
8.33 parts of diketopyrrolopyrrole pigment (CI Pigment Red 254) ("Irga Four Red B-CF" manufactured by Ciba Geigy), 1.33 parts of anthraquinone pigment (CI Pigment Red 177) ( Ciba Geigy "Chromophthal Red A2B"), anthraquinone pigment (CI Pigment Yellow 199) 0.34 parts (Ciba Geigy "Chromophthal tar GT-AD"), anthraquinone derivative (derivative 4) 2 A mixture of 0.0 part, 40.0 parts of acrylic resin solution (C-1) and 48.0 parts of cyclohexanone was uniformly stirred and mixed, and then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm, then 5 μm. A red pigment dispersion was prepared by filtration through a filter.

[Pigment Dispersion Production Example 3]
10.0 parts of brominated copper phthalocyanine pigment (CI Pigment Green 36) (“Lionol Green 6Y-501” manufactured by Toyo Ink Co., Ltd.) was added to ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) ( A blue pigment dispersion was prepared in the same manner as in Pigment Dispersion Production Example 1 except that the amount was changed to 10.0 parts of “Heliogen Blue L-6700F” manufactured by BASF.

[Example 1]
45.0 parts of the green pigment dispersion produced in Pigment Dispersion Production Example 1, 15.0 parts of the triazine ring-containing epoxy resin solution (A-1) synthesized in Production Example 1, 5.6 parts of trimethylolpropane triacrylate ( Shin-Nakamura Chemical "NK ester ATMPT"), photoinitiator (Ciba Geigy "Irgacure 907") 2.0 parts, sensitizer (Hodogaya Chemical "EAB-F") 0.2 parts, cyclohexanone After stirring and mixing 32.2 parts of the mixture so as to be uniform, the mixture was filtered through a 1 μm filter to obtain a green coloring composition (hereinafter referred to as a resist).

[Examples 2 to 16 and Comparative Examples 2 and 3]
Each color resist was obtained in the same manner as in Example 1 with the proportions shown in Table 2 and Table 3 below.

[Comparative Example 1]
15.0 parts of the triazine ring-containing epoxy resin solution (A-1) synthesized in Production Example 1 was added to 15.0 parts of a cyclohexanone solution (non-volatile content 20%) of phenolite TD-2131 (phenol novolac resin, DIC Corporation). A green resist was obtained in the same manner as in Example 1 except that it was changed to.

  For each color resist in Tables 2 and 3, the viscosity, storage stability with time, heat resistance, haze, visibility in the oblique direction and substrate adhesion were evaluated by the following methods, and the evaluation results are shown in Tables 2 and 3. .

(1) Evaluation of initial viscosity The viscosity of each color resist in Tables 2 and 3 was measured with an E-type viscometer (at 10 rpm, 25 ° C) on the next day of resist preparation. The lower the initial viscosity, the better.

(2) Storage stability over time For each color resist in Tables 2 and 3, after storing for 1 week in a thermostat at 40 ° C. and accelerating the time, the viscosity of the resist after aging was measured by the same method as the initial viscosity, The rate of change in viscosity before and after storage at 40 ° C. for 1 week was calculated and evaluated in two stages according to the following criteria.

○: “When the viscosity change rate is within ± 10% and no sediment is formed.”
X: “When the viscosity change rate exceeds ± 10%, or when a precipitate is formed even when the viscosity change rate is within ± 10%.”

(3) Evaluation of heat resistance Each color resist of Table 2 and Table 3 was apply | coated on the glass substrate of 100 mm x 100 mm and 1.1 mm thickness using the spin coater, and the application board | substrate was obtained. Next, after drying at 70 ° C. for 20 minutes, using an ultrahigh pressure mercury lamp, UV exposure was performed with an integrated light amount of 150 mJ, and heating was performed at 230 ° C. for 20 minutes to obtain each color coating film [C]. The film thickness of the dried coating film was 2 μm in all cases. Furthermore, each color coating film [C] was heated at 260 ° C. for 1 hour to obtain each color coating film [D]. Chromaticity measurement is performed with a microspectrophotometer (Olympus Optical “OSP-SP100”) using a C light source, and the color difference (ΔE) between each color coating film [C] and [D] is calculated to evaluate heat resistance. Went. Evaluation was made in two stages according to the following criteria.

○: “When ΔE is 3 or less.”
X: “When ΔE is a value exceeding 3”

(4) Evaluation of haze About each color coating film [C], the haze value was measured using the haze meter NDH-2000 (made by Tokyo Denshoku Co., Ltd.), and it evaluated in two steps according to the following references | standards.

○: “When the haze value is 0.5% or less.”
X: “When the haze value exceeds 0.5%.”

(5) Visibility in oblique direction For each color coating film [C], using a spectrophotometer ("OSP-200" manufactured by Olympus Corporation), spectral transmittance T ( λ) was measured. Moreover, about each color coating film [C], 400 nm-700 nm from the direction inclined 45 degrees from the normal line direction of the board | substrate in which the coating film was formed using the transmission type | mold spectroscopic ellipsometer ("M-220" by JASCO Corporation). In the range of 5 nm, and the ellipso parameter δ was obtained. The phase difference value Δ (λ) was calculated from Δ = δ / 360 × λ. The spectral radiance at the wavelength λ of the C light source is S (λ), and the value ξ relating to the thickness direction retardation is obtained from the sum of Δ (λ) × T (λ) × S (λ) in the wavelength range of 400 nm to 700 nm. Was calculated. The smaller the absolute value of ξ, the better the visibility in the oblique direction.

(6) Substrate adhesion Each color resist shown in Tables 2 and 3 was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater at a rotation speed at which the film thickness after drying was 2.0 μm. The substrate was dried at 70 ° C. for 20 minutes, and then exposed to ultraviolet light with an integrated light amount of 150 mJ using a super high pressure mercury lamp through a photomask having a stripe-shaped opening having a width of 100 μm, and a 5% aqueous sodium carbonate solution was used. The unexposed portion was washed away and baked in a hot air oven at 230 ° C. for 30 minutes to form a stripe pattern having a width of 100 μm on the substrate. As a test for adhesion to glass, the chemical resistance of the obtained coating film was evaluated. As a test method, it was immersed in a 5% aqueous sodium hydroxide solution at 25 ° C. for 30 minutes, and the adhesion to the glass before and after immersion was evaluated by visual observation. Evaluation was made in three stages according to the following criteria.

○: “No peeling at all”
Δ: “Slight peeling is observed”
X: “Peeling is recognized”

Monomer: Trimethylolpropane triacrylate (Shin Nakamura Chemical "NK Ester ATMPT")
Photoinitiator: “Irgacure 907” manufactured by Ciba Geigy
Sensitizer: Hoabaya Chemical "EAB-F"
Solvent: cyclohexanone

  As shown in Tables 2 and 3, Examples 1 to 16, which are the color filter coloring compositions of the present invention, all had good viscosity characteristics, heat resistance, oblique visibility, and adhesion. On the other hand, Comparative Examples 1 to 3 are poor in heat resistance, oblique visibility, and adhesion, and in Comparative Example 3, the compatibility between the resins PA-1 and C-1 is poor. In addition, the haze deteriorated, and everything that was good was not obtained.

Claims (12)

At least one resin selected from a triazine ring-containing epoxy resin [A] and a triazine ring-containing phenol resin [B];
Pigments,
At least one basic group-containing derivative selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group; ,
A coloring composition for a color filter comprising a pigment carrier containing a monomer.   The triazine ring-containing epoxy resin [A] has an epoxy compound (a1) having two or more epoxy groups in the molecule, and a triazine compound (a2) having two or more functional groups capable of reacting with the epoxy group in the molecule; The colored composition for a color filter according to claim 1, which is a hydroxyl group-containing resin [A1] obtained by reacting the above. The triazine ring-containing epoxy resin [A] has an epoxy compound (a1) having two or more epoxy groups in the molecule, and a triazine compound (a2) having two or more functional groups capable of reacting with the epoxy group in the molecule; To produce a hydroxyl group-containing resin [A1],
2. The carboxyl group-containing resin [A2] obtained by reacting the hydroxyl group in the obtained hydroxyl group-containing resin [A1] with the acid anhydride group in the acid anhydride (a3). The coloring composition for color filters as described. The triazine ring-containing epoxy resin [A] has an epoxy compound (a1) having two or more epoxy groups in the molecule, and a triazine compound (a2) having two or more functional groups capable of reacting with the epoxy group in the molecule; To produce a hydroxyl group-containing resin [A1],
Reacting the hydroxyl group in the obtained hydroxyl group-containing resin [A1] with the acid anhydride group in the acid anhydride (a3) to produce a carboxyl group-containing resin [A2],
Ethylenically unsaturated bond-containing resin obtained by reacting the carboxyl group in the obtained carboxyl group-containing resin [A2] with the epoxy group in the epoxy compound (a4) having an ethylenically unsaturated bond in the molecule [ The coloring composition for a color filter according to claim 1, wherein the coloring composition is A3]. The coloring composition for a color filter according to any one of claims 2 to 4, wherein the triazine compound (a2) is a compound represented by the general formula (1).
General formula (1)

(In the formula, T is SH or NR ¹ R ² , and R ¹ and R ² each independently represents a hydrogen atom, an optionally substituted alkyl group, an alkenyl group, or a phenyl group.)   The colored composition for a color filter according to any one of claims 2 to 5, wherein the epoxy compound (a1) is a glycidyl ether of a polyalcohol.   A phenolic hydroxyl group-containing resin obtained by reacting a phenol (b1), a triazine compound (b2), and an aldehyde (b3) in the presence of an acid catalyst and / or a base catalyst [triazine ring-containing phenol resin [B] [ It is B1], The coloring composition for color filters in any one of Claims 1-6 characterized by the above-mentioned. The triazine ring-containing phenol resin [B] reacts the phenols (b1), the triazine compound (b2), and the aldehydes (b3) in the presence of an acid catalyst and / or a base catalyst to give a phenolic hydroxyl group-containing resin [B1. ], And
Hydroxyl group-containing resin [B2] obtained by reacting the phenolic hydroxyl group in the obtained phenolic hydroxyl group-containing resin [B1] with the epoxy group in the epoxy compound (b4) having an ethylenically unsaturated bond in the molecule The coloring composition for a color filter according to claim 1, wherein the coloring composition is a coloring composition. The triazine ring-containing phenol resin [B] reacts the phenols (b1), the triazine compound (b2), and the aldehydes (b3) in the presence of an acid catalyst and / or a base catalyst to give a phenolic hydroxyl group-containing resin [B1. ],
By reacting the phenolic hydroxyl group in the obtained phenolic hydroxyl group-containing resin [B1] with the epoxy group in the epoxy compound (b4) having an ethylenically unsaturated bond in the molecule, the hydroxyl group-containing resin [B2] is reacted. Generate and
The carboxyl group-containing resin [B3] obtained by reacting the hydroxyl group in the obtained hydroxyl group-containing resin [B2] with the acid anhydride group in the acid anhydride (b5). The coloring composition for color filters in any one of -6.   The coloring composition for a color filter according to any one of claims 7 to 9, wherein the triazine compound (b2) is melamine and / or a melamine resin.   The coloring composition for a color filter according to any one of claims 1 to 10, wherein the pigment carrier containing a monomer further contains a resin.   A color filter comprising a filter segment formed from the colored composition for a color filter according to claim 1.