TW201343806A - Coloring composition for color filter, and color filter - Google Patents

Abstract

The present invention solves the technical problem by a coloring composition for a color filter. The coloring composition for the color filter comprises a colorant, a resin binder, and an organic solvent. The composition at least comprises at least one of the following halides: a halide obtained by reacting an acrylic resin with an anionic dye, wherein the acrylic resin has a side chain having a cationic group and a thermally crosslinkable functional group; or a halide obtained by reacting an acrylic resin with an anionic dye, wherein the acrylic resin has a glass transition temperature being 50 DEG C or more and a side chain having a cationic group.

Description

Color filter coloring composition and color filter

The present invention relates to a coloring composition for a color filter and a color filter having the filter segment formed thereby, and the coloring composition for the color filter is used for manufacturing a color liquid crystal display device Color filters used in color camera components, etc.

In recent years, liquid crystal display devices have been evaluated for their space saving, weight reduction, power saving, and the like, and have recently been rapidly popularized for television use. If it is intended to be suitable for television use, it is required to further improve the brightness or contrast performance. In view of the color filter constituting the components of the color liquid crystal display device, it is expected to further improve the transmittance and improve the contrast.
The method for producing a color filter is known to include: a dyeing method for dyeing a pattern after patterning by a resist; or a transparent electrode having a specific pattern formed in advance, and dissolving and dissolving in a solvent by applying a voltage a plating method in which a pigment-containing resin is ionized to form a pattern; a printing method using offset printing or the like using an ink containing a thermosetting resin or an ultraviolet curing resin; and a color resist obtained by dispersing a coloring agent such as a pigment on a resist material The pigment dispersion method of the agent. Recently, the pigment dispersion method has been the mainstream. However, the color filter used as a coloring agent is caused by light scattering or the like by the pigment particles, so that the degree of polarization controlled by the liquid crystal is disturbed, and as a result, the brightness or contrast of the color liquid crystal display device is lowered. .

As a technique for solving this problem, a dye-based curable composition using a dye as a colorant has been proposed, and the dye can be present in a dissolved state in a medium of a curable composition (refer to, for example, Patent Document 1). . However, dyes used for color resists have problems with heat resistance, light resistance, and solubility in resins and organic solvents used in resins.
Therefore, in order to improve the solubility, a color filter using a salt of an anionic dye and a cationic surfactant as a coloring agent has been proposed (see, for example, Patent Documents 2 and 3). In general, it is known that the solubility of an anionic dye in an organic solvent is improved by changing a sodium sulfonate group (-SO ₃ Na) of an anionic dye to a salt of an organic amine. The above coloring agent enhances the solubility of the anionic dye in an organic solvent by changing the sodium sulfonate group of the anionic dye to a matrix salt of a cationic surfactant. However, these methods are incapable of obtaining sufficient solubility for the solvent used in the production of the color filter. Further, since the compatibility with the resin is also poor, it is difficult to impart long-term storage stability to the coloring composition for a color filter, and it is difficult to provide strong adhesion between the coating film and a transparent substrate such as glass, and it is impossible to solve the problem. The solvent resistance or alkali developability of the coating film is an important issue in color filters.
In addition, as a crystalline water-based coloring material, a halide resin is used as a counter-charged material as a halide of an anionic dye (see, for example, Patent Document 4), and the purpose of the dye is to use the dye in a particle state. The use of color filters that are required to be used in a dissolved state has not been reviewed in detail.
Further, a colored resin composition is proposed which is obtained by adding an anionic dye to a copolymer solution obtained by copolymerizing a monomer having a guanamine structure (see, for example, Patent Document 5). This is achieved by the action of the guanamine structure as a dyeing point on the anionic dye to stabilize the dye in the coating film and improve the tolerance. However, in the method disclosed herein, since the copolymer and the anionic dye are mixed in an organic solvent, the dye having high polarity is not sufficiently dissolved and there is a problem that foreign matter is generated.
Further, in order to improve heat resistance and light resistance, a colored composition in which a dye is chemically bonded to a polymer has been proposed (refer to, for example, Patent Document 6). However, if the polymer and the dye are simply collected, the solvent resistance or the resistance is still insufficient, and the alkali developability does not meet the requirements of recent years.
Advanced technical literature patent literature
[Patent Document 1] Japanese Patent Laid-Open Publication No. 1994-75375
[Patent Document 2] Japanese Patent Laid-Open Publication No. 1993-333207
[Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-307391
[Patent Document 4] Japanese Patent Laid-Open Publication No. 2005-350648
[Patent Document 5] Japanese Patent Laid-Open Publication No. 2000-352819
[Patent Document 6] Japanese Patent Laid-Open Publication No. 2000-162429

Problem to be solved by the invention

An object of the present invention is to provide a coloring composition for a color filter having good storage stability, and a coating film which does not generate foreign matter, and which has strong adhesion to a transparent substrate such as glass, heat resistance and solvent resistance. A color filter with high solubility and good alkali solubility.
Means for Solving the Problems The present inventors focused on cumulative research in order to solve the various problems described above, and as a result, found that a coloring composition for a color filter has high storage stability and does not generate foreign matter for ink application. Good adhesion, high heat resistance in heat resistance test, and the present invention is completed according to the discretion, and the coloring composition for a color filter contains a resin (B) having an aromatic group in a side chain and an anion. The halide (D) obtained by the reaction of the dye (C), the resin (B) having the cationic group, that is, the side chain having a cationic group, and having at least one of a bridging functional group or a glass transition temperature of 50 ° C or higher. Acrylic resin.
That is, the present invention relates to a coloring composition for a color filter, characterized in that it is composed of at least a coloring agent (A), a resin binder, and an organic solvent;
The coloring agent (A) contains a halide (D) obtained by reacting a resin (B) having a cationic group in a side chain with an anionic dye (C);
The resin (B) having a cationic group in the side chain is an acrylic resin containing a structural unit represented by the following general formula (1); the acrylic resin is selected from an acrylic resin having a thermal bridging functional group, and a glass transition temperature of 50 An acrylic resin having a temperature above °C and an acrylic resin having a heat-bridged functional group and having a glass transition temperature of 50 ° C or higher.

(In the general formula (1), R ₁ represents a hydrogen atom, or a substituted or unsubstituted alkyl group. R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group which may be substituted, or may be substituted. An alkenyl group or an aryl group which may be substituted, and _{two of} R ₂ , R ₃ and R ₄ may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, -CONH-R ₅ - or -COO-R ₅ -, R ₅ represents an alkylene group. Y ^- represents an inorganic or organic anion.)
Further, the present invention relates to the coloring composition for a color filter, characterized in that the thermally bridged functional group is selected from the group consisting of a hydroxyl group, a carboxyl group, an oxetanyl group, a tertiary butyl group, an isocyanate group, and At least one of the group consisting of (meth)acrylonitrile groups.

Further, the present invention relates to the coloring composition for a color filter described above, characterized in that the acrylic resin comprising the structural unit represented by the above general formula (1) is a copolymer comprising a structural unit having a thermal bridging functional group. The copolymer is contained in an amount of 100% by weight in total, and includes 10 to 35% by weight of the structural unit having the aforementioned thermally bridged functional group.
Further, the present invention relates to the coloring composition for a color filter described above, characterized in that the thermally bridged functional group contains a hydroxyl group.
Further, the present invention relates to the coloring composition for a color filter described above, characterized in that the thermally bridged functional group is a hydroxyl group and a carboxyl group.

Further, the present invention relates to the coloring composition for a color filter, characterized in that the ammonium salt having an acrylic resin having a structural unit represented by the above formula (1) has an ammonium salt value of 10 to 200 mgKOH/g.
Further, the present invention relates to the coloring composition for a color filter characterized in that the halide (D) is in an aqueous solution, and a resin (B) having a cationic group in a side chain and an anionic dye are mixed ( C) A compound obtained by removing a salt composed of a counter anion of a resin (B) having a cationic group in a side chain and a counter cation of an anionic dye (C).
Further, the present invention relates to the coloring composition for a color filter, characterized in that the main component of the organic solvent is Propylene glycol monomethyl ether acetate.
Moreover, the present invention relates to the coloring composition for a color filter, characterized in that the coloring agent further contains a pigment.
Furthermore, the present invention relates to the coloring composition for a color filter, which further comprises a photopolymerizable monomer and/or a photopolymerization initiator.
Further, a color filter is formed by the coloring composition for the color filter.
Advantageous Effects of Invention According to the present invention, by using a coloring composition for a color filter containing a halide (D), it is possible to obtain a high storage stability, and a foreign matter is not generated when a coating film is formed, and the adhesion is good. Further, a color filter exhibiting high heat resistance and solvent resistance and exhibiting good alkali developability, and the above halide (D) is a resin (B) having a cationic group in a side chain, that is, a side The chain has a cationic group and is obtained by reacting an anionic dye (C) with an acrylic resin having a bridging functional group or at least one glass transition temperature of 50 ° C or higher.

Form for implementing the invention
The invention is described in detail below.
The coloring composition for a color filter of the present invention contains a coloring composition for a color filter of a halide (D), and the coloring composition for the color filter is a coloring agent carrier containing a resin binder and an organic solvent. In the middle, a resin (B) having a cationic group in a side chain is obtained by reacting with an anionic dye (C). First, the resin (B) having a cationic group in the side chain will be described.
<Resin having a cationic group in the side chain (B)>
The resin (B) having a cationic group in the side chain of the present invention is an acrylic resin comprising a structural unit represented by the following general formula (1), which is selected from an acrylic resin having a thermal bridging functional group, and has a glass transition temperature of 50 ° C or higher. An acrylic resin and an acrylic resin having a heat-branched functional group and having a glass transition temperature of 50 ° C or higher. The acrylic resin is preferably an acrylic resin having a heat-bridged functional group and having a glass transition temperature of 50 ° C or higher.
The cationic group represented by the following general formula (1) is salted with the anionic group of the anionic dye (C), whereby the halide (D) of the present invention can be obtained.

(In general formula (1), R ₁ An alkyl group representing a hydrogen atom, or a substitution or no substitution. R ₂ , R ₃ And R ₄ Each of which independently represents a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an aryl group which may be substituted, R ₂ , R ₃ And R ₄ Two of them are combined to form a ring. Q represents an alkylene group, an arylene group, -CONH-R ₅ -or-COO-R ₅ -,R ₅ Indicates an alkylene group. Y ^- Represents an inorganic or organic anion. )
In the general formula (1), R ₁ An alkyl group representing a hydrogen atom, or a substitution or no substitution. R ₁ Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a n-butyl group, an i-butyl group, a tributyl group, a n-hexyl group, and a cyclohexyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 4 carbon atoms is particularly suitable.
R ₁ When the alkyl group shown has a substituent group, examples of the substituent group include a hydroxyl group, an alkoxy group and the like.
Among the above, R ₁ Most preferably a hydrogen atom or a methyl group.

In the general formula (1), R ₂ , R ₃ And R ₄ Each of them independently represents a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an aryl group which may be substituted.
Here, R ₂ , R ₃ And R ₄ The alkyl group may, for example, be a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-dodecyl, n-tetradecyl, n-hexadecanyl, and Octadecyl, etc., branched alkyl (isopropyl, isobutyl, secondary butyl, tert-butyl, isopentyl, neopentyl, tertiary pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethylbutyl, etc.), cycloalkyl (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, etc.), and bridged cyclic alkyl (norbornyl, adamantane) Base and base). The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.
R ₂ , R ₃ And R ₄ Examples of the alkenyl group include a linear or branched alkenyl group (vinyl group, allyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group). , 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl, etc., cycloalkenyl (2-ring) Hexyl and 3-cyclohexenyl, etc.). The alkenyl group is preferably an alkyl group having 2 to 18 carbon atoms, and more preferably an alkyl group having 2 to 8 carbon atoms.
R ₂ , R ₃ And R ₄ Examples of the aryl group include a monocyclic aryl group (such as a phenyl group), a condensed polycyclic aryl group (naphthyl group, an anthracenyl group, a phenanthryl group, an anthranquinolyl group, an anthracenyl group, a naphthylquinolyl group, etc.), and Aromatic heterocyclic hydrocarbon group (thienyl group (derived from thiophene)), furyl group (derived from furan), pipenyl (group derived from piper), pyridyl (group derived from pyridine) , 9-carbonyl fluorenyl (based on xanthene) and 9-carbonyl thioxyl (based on thioxan).
R ₂ , R ₃ And R ₄ When the alkyl group, the alkenyl group and the aryl group shown have a substituent group, the substituent group may be exemplified by a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an alkenyl group, a decyl group, an alkoxycarbonyl group, a carbonyl group and a benzene group. The substituent selected by the base or the like. Among these substituents, a halogen atom, a hydroxyl group, an alkoxy group or a phenyl group is particularly preferable.
From the perspective of stability, R ₂ , R ₃ And R ₄ It is preferably an alkyl group which may be substituted, and more preferably an alkyl group which is not substituted.
Also, R ₂ , R ₃ And R ₄ Two of them are combined to form a ring.
In the general formula (1), the Q group linking the propenyl group and the ammonium salt group means an alkylene group, an arylene group, -CONH-R ₅ -or-COO-R ₅ -,R ₅ Indicates an alkylene group. Among them, from the viewpoint of polymerization and difficulty in obtaining, Q should be -CONH-R ₅ -or-COO-R ₅ -. Also, R ₅ More preferably, it is a methyl group, an ethane group, a propane group or a butane group, and particularly preferably an ethane group.
Y in the general formula (1) which constitutes a counter anion of the resin ^- The component is an inorganic or organic anion. The counter anion can be any conventionally used, and specific examples thereof include halide ions such as hydroxide ions, chloride ions, bromide ions, and iodide ions; and carboxylic acid ions such as formic acid ions and acetate ions; Carbonate ion, hydrogen carbonate ion, nitrate ion, sulfate ion, sulfite ion, chromic acid ion, potassium dichromate ion, phosphate ion, permanganic acid ion, etc., and further, such as iron (III) hexanoate (III) acid ion Complex ions and so on. From the standpoint of synthetic suitability or stability, it is preferably a halide ion and a carboxylate ion, and most preferably a halide ion. When the counter anion is an organic acid ion such as a carboxylic acid ion, the organic acid ion may be bonded to the resin to form an intramolecular salt.
The acrylic resin containing the structural unit represented by the general formula (1) can be obtained by copolymerization using an ethylenically unsaturated monomer having an ammonium salt group as a monomer component. Alternatively, the acrylic resin can be copolymerized by using an ethylenically unsaturated monomer having an amine group as a monomer component to synthesize an acrylic resin having an amine group, and then reacting with a hydrazine chlorinating agent to carry out ammonium. Obtained by chlorination.
Specific examples of the ethylenically unsaturated monomer having an ammonium salt group, the ethylenically unsaturated monomer having an amine group, and the hydrazine chlorinating agent are shown below. In addition, in the present specification, when one or both of "acryloyl group and methacryl group" are shown, it may be described as "(meth)acrylyl group". Similarly, when one or both of "acrylonitrile and methacryl" are indicated, "(meth)acrylamide" may be described.
Examples of the ethylenically unsaturated monomer having an ammonium salt group include (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltriethylammonium chloride, (A) Alkyl (meth) acrylate type 4th ammonium salt such as propylene oxime oxyethyl dimethyl ammonium chloride or (meth) propylene oxiranyl morpholine ammonium chloride; (meth) propylene oxime Alkyl (methyl) such as aminopropyltrimethylammonium chloride, (meth)acrylamide, ethyltriethylammonium chloride, (meth)acrylamide, ethyldimethylbenzylammonium chloride, etc. Acrylamide amine grade 4 ammonium salt; dimethyl diallyl ammonium methyl sulfate; and trimethylvinylphenyl ammonium chloride.
Examples of the ethylenically unsaturated monomer having an amine group include dimethylamine ethyl (meth) acrylate, diethyl amine ethyl (meth) acrylate, and dipropyl amine ethyl (methyl). Acrylate, diisopropylamine ethyl (meth) acrylate, dibutylamine ethyl (meth) acrylate, diisobutylamine ethyl (meth) acrylate, di-tertiary-butyl Amine ethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethyl amine ethyl (meth) acrylate, diethyl propyl propyl (meth) acrylamide, Dipropylaminopropyl (meth) acrylamide, diisopropylamine propyl (meth) acrylamide, dibutylamine propyl (meth) acrylamide, diisobutylamine propyl a (meth) acrylate or (meth) acrylamide having a dialkylamino group such as (meth) acrylamide or di-tert-butylaminopropyl (meth) acrylamide; : styrenes having a dialkylamine group such as dimethylamine styrene and dimethylamine methyl styrene; dienamine compounds such as dienylmethylamine and dienamine; N-vinylpyrrolidine , N-vinylpyrrolidone, N-vinylcarbazole, etc. containing amine The aromatic vinyl monomers.
Examples of the hydrazine chlorinating agent include alkyl sulphates such as dimethylsulfuric acid, diethylsulfonic acid or dipropylsulfuric acid; sulfonic acid esters such as p-toluenesulfonic acid methyl or benzenesulfonic acid methyl; methane bromide and bromine; An alkyl bromide such as ethane, propane bromide or octyl bromide; or benzyl chloride or benzyl bromide.
The reaction of an ethylenically unsaturated monomer having an amine group with a hydrazine chlorinating agent can generally be carried out by dropping a solution of an ethylenically unsaturated monomer having an amine group with a hydrazine chlorinating agent having a molar ratio of less than or equal to the amine group. get on. The temperature at the time of the ammonium chlorination reaction is about 90 ° C or less, and particularly when the vinyl monomer is ammonium chlorinated, it is preferably about 30 ° C or less, and the reaction time is about 1 to 4 hours.
Further, an alkoxycarbonylalkyl halide can also be used as the hydrazine chlorinating agent. The alkoxycarbonylalkyl halide can be represented by the following general formula (2).
ZR ⁶ -COOR ⁷ General formula (2)
(In general formula (2), Z is a halogen such as chlorine or bromine, preferably bromine; R ⁶ An alkylene group having 1 to 6, preferably 1 to 5, more preferably 1 to 3 carbon atoms; ⁷ It is a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. )
The reaction of an amine group-containing ethylenically unsaturated monomer with an alkoxycarbonylalkyl halide can be carried out by the same alkoxycarbonylalkyl halide as the above-mentioned oxime chlorinating agent with respect to the amine group. After the reaction, the -COOR ⁷ Hydrolysis to carboxylate (-COO) ^- ) and get. Thereby, an ethylenically unsaturated monomer having a carbonyl betaine structure represented by the general formula (2) and having an ammonium salt group can be obtained.
Next, the thermal bridging functional group in the resin (B) having a cationic group in the side chain used in the present invention will be described.
(bridged functional group)
The acrylic resin having a thermally bridged functional group of the present invention is formed in a heating step for producing a color filter to form an bridge of acrylic resin having a heat-bridgeable functional group or a resin binder. Thereby, a strong film is formed to prevent color change of the coating film. It can also improve heat resistance. Moreover, the solvent resistance can also be improved.
The suitable structure of the above-mentioned heat-bridged functional group is not particularly limited, and examples thereof include a hydroxyl group, a carboxyl group, a carboxylic anhydride, a primary or secondary amine group, an imido group, an oxetanyl group, a tertiary butyl group, and a ring. An oxy group, a decyl group, an isocyanate group, an allyl group, a (meth) propylene group or the like.
Among them, from the viewpoints of preservation stability or reactivity with other materials for use of a color filter for a coloring composition, it is preferably a hydroxyl group, a carboxyl group, an oxetanyl group, a tertiary butyl group, an isocyanate group, or Methyl)propenyl, especially preferably having a hydroxyl group.
Further, from the viewpoint of alkali developability, it is preferred to have a carboxyl group.
One method of introducing a thermally bridged functional group to an acrylic resin is to use an ethylenically unsaturated monomer having a heat-bridged functional group and an ethylenically unsaturated monomer corresponding to a cationic group represented by the general formula (1). The method of copolymerization.
Examples of the ethylenically unsaturated monomer having a hydroxyl group are not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxy butyl (A). Acrylate, glycerol mono(meth)acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate or caprolactone addenda of these monomers (additional mo The number of ears should be 1 to 5).
Examples of the ethylenically unsaturated monomer having a carboxyl group include, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc., and an ethylenic unsaturated group having a carboxylic anhydride group. Examples of the compound include maleic anhydride and itaconic anhydride.
The ethylenically unsaturated monomer having an oxetane group may, for example, be 3-(acrylomethoxymethyl)3-methyloxetane or 3-(methacryloxymethyl)3-methyl Oxycyclobutane, 3-(acrylomethoxymethyl) 3-ethyloxetane, 3-(methacrylomethoxymethyl) 3-ethyloxetane, 3-( Propylene oxime methyl) 3-butyl oxetane, 3-(methacrylomethoxymethyl) 3-butyl oxetane, 3-(acryloxymethyl) 3-hexyloxy Heterocyclic butane and 3-(methacryloxymethyl) 3-hexyloxycyclobutane.
Examples of the ethylenically unsaturated monomer having a tertiary butyl group include a tertiary butyl acrylate, a tertiary butyl acrylate, and the like.
Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-isocyanate methyl acrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl acrylate, 4-isocyanate butyl acrylate, and the like.
The isocyanate group of the present invention also contains a blocked isocyanate, which is suitably used. Block isocyanate refers to an isocyanate block which, under normal conditions, inhibits the reactivity of the isocyanate group by protecting the isocyanate group with other functional groups, and on the other hand, can be deprotected by heating to regenerate the active isocyanate group. .
A commercially available product of such an ethylenically unsaturated monomer having a blocked isocyanate group may, for example, be 2-[(3,5-dimethylpyrazolyl)carboxyamine]ethyl methacrylate (Karenz MOI-BP). , manufactured by Showa Denko); 2-(O-[1'methylpropylidene]carboxylamine)ethyl methacrylate (Karenz MOI-BM, manufactured by Showa Denko).
Further, the ethylenically unsaturated monomer having a blocked isocyanate group can be used by a conventional method in addition to a commercially available product. For example, an isocyanate compound having an ethylenically unsaturated bond and a block agent can be stirred at a temperature of from 0 to 200 ° C in a solvent, and a conventional separation and purification means such as concentration, filtration, extraction, crystallization, distillation, and the like can be used. It is obtained by separation.
Another method for introducing a thermally bridged functional group to an acrylic resin is to obtain a functional group based on the acrylic resin after reacting the functional group having the functional group reactive with the functional group with a thermally bridged functional group. method. For example, an acrylic resin having a glycidyl group is reacted with a carboxyl group in an acrylic resin having a carboxyl group, whereby an acrylic resin having a (meth)acrylonitrile group can be obtained.
The above-mentioned heat-bridged functional group must be contained in at least one kind of resin, and may contain two or more types.
Further, when the thermal bridging functional group contains two or more kinds, the thermal bridging functional groups are suitably combined with each other. This combination of thermal bridging functional groups that are easily reacted with each other upon heating increases the bridging effect. For example, it may be effective to use both oxetane and carboxyl groups. Similarly, since the tertiary butyl group becomes a carboxyl group upon heating, the combination of an oxetane group and a tertiary butyl group is also effective. Further, a combination of a hydroxyl group and a blocked isocyanate group and an isocyanate group is also effective. In particular, the combination of a hydroxyl group and a carboxyl group can not only obtain a strong film by thermal bridging, but also enhances alkali developability due to the presence of a carboxyl group in the alkali development step before the thermal bridging, and thus is most suitable.
Next, the glass transition temperature of the resin (B) having a cationic group in the side chain will be described.
(glass transition temperature)
When the resin (B) having a cationic group in the side chain used in the present invention is synthesized, an acrylic resin having a glass transition temperature (hereinafter abbreviated as Tg) of 50 ° C or higher can be obtained by selecting an ethylenically unsaturated monomer. The Tg of the acrylic resin can be controlled by appropriately selecting the ethylenically unsaturated monomer to be used without affecting other physical properties. The Tg of the acrylic resin directly affects the heat resistance of the color filter. Therefore, when the Tg is less than 50 ° C and the thermal bridging functional group is not present, color change at a high temperature occurs, that is, heat resistance is poor.
When it is considered to be used in an electronic field having a heating step of 200 ° C or higher, such as a color filter, the Tg of the propylene-based portion is more preferably 70 ° C or higher. Tg is not particularly limited. However, if it exceeds 150 ° C, practical problems occur in processability or film formation, and therefore it is preferably less than 150 ° C.
The Tg of the acrylic resin of the present invention means a value calculated from the Fox number represented by the Tg of the individual polymer of each of the copolymerized ethylenically unsaturated monomers.
Fox number

W1 to Wn represent the weight fraction of the monomer used, and Tg1 to Tgn represent the glass transition temperature (unit: absolute temperature "K") of the individual polymer of the monomer.
The Tg (glass transition temperature) of the individual polymer used for the main monomer to be calculated is exemplified below.
Ethyl acrylate: -22 ° C (251 K)
Butyl acrylate: -54 ° C (219 K)
Methyl benzyl acrylate: 55 ° C (328 K)
Acrylic acid: 106 ° C (379K)
Methyl methacrylate: 105 ° C (378 K)
Methyl n-butyl acrylate: 20 ° C (293 K)
Methyl 2-ethylhexyl acrylate: -10 ° C (263 K)
Methyl hydroxyethyl acrylate: 55 ° C (328 K)
Methacrylic acid: 130 ° C (403K)
3-(Methacryloxymethyl) 3-methyloxetane: 105 ° C (378 K)
2-Iocyanate ethyl methacrylate: 60 ° C (333 K)
Methyl n-butyl acrylate: 107 ° C (380K)
Dimethylamine ethyl methacrylate: 58 ° C (331 K)
For example, if the above method is used for calculation, a 90-fold portion of methyl methacrylate and 10 parts by weight of ethyl acrylate are used to synthesize an ethylenically unsaturated monomer, and a glass polymer of a vinyl polymer portion obtained by radical polymerization is used. The temperature was 86.8 °C.
In order to increase the Tg, a copolymer having a Tg high ethylenically unsaturated monomer of a single polymer is required. Among the above ethylenically unsaturated monomers, the following Tg is high, which is effective for increasing the Tg of the acrylic resin.
List the monomers with higher Tg of the individual polymers.
Methyl methacrylate: 105 ° C (378 K)
Tertiary butyl methacrylate: 107 ° C (380K)
Methacrylic acid: 130 ° C (403K)
Acrylic acid: 106 ° C (379K)
3-(Methacryloxymethyl) 3-methyloxetane: 105 ° C (378 K)
Isobornyl acrylate: 94 ° C (367 K)
Isobornyl acrylate: 180 ° C (453 K)
Cyclopentyl acrylate: 120 ° C (393 K)
Methyl cyclopentyl acrylate: 175 ° C (448 K)
Amanta acrylate: 153 ° C (426 K)
Amanta methyl acrylate: 250 ° C (523 K)
Among them, in particular, tertiary butyl methacrylate and methacrylic acid are particularly suitable because they can increase the Tg and can introduce a heat-bridged functional group. Further, from the viewpoint of versatility, methyl methacrylate is preferred.
Further, the ethylenically unsaturated monomer which can be used other than the above ethylenically unsaturated monomer is preferably, for example, a (meth) acrylate, a crotonate, a vinyl ester, a maleic acid diester or the like. Butylene diacid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylonitrile, and the like.
Specific examples of such a vinyl monomer include, for example, the following compounds.
Examples of the (meth) acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (methyl). N-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butyl (meth)acrylate Hexyl, 2-ethylhexyl (meth)acrylate, trioctyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, ethoxylated (meth)acrylate Ethyl, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (A) 2-(2-methoxyethoxy)ethyl, 3-phenoxy-2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, diethyl (meth)acrylate Glycol monomethyl ether, diethylene glycol monoethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, Methyl)acrylic acid polyethylene glycol monomethyl ether, (meth)acrylic acid poly Ethylene glycol monoethyl ether, (meth)acrylic acid -phenoxyethoxyethyl, nonylphenoxy polyethylene glycol (meth)acrylate, dicyclopenteneoxyethyl (meth)acrylate, trifluoroethyl (meth)acrylate, (a) Base) octylfluoropentyl acrylate, perfluorooctyl (meth) acrylate, dicyclopentyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenoxy (meth) acrylate Base.
Examples of the crotonate include crotonate butyl and crotonate hexyl groups.
Examples of the vinyl esters include vinyl ethyl ester, ethylene propyl ester, vinyl butyl carbonate, vinyl methoxyethyl ester, and benzoic acid ethylene. Examples of the maleic acid diesters include dimethyl maleic acid, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.
Examples of the (meth)acrylamides include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, and N-propyl ( Methyl) acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-ring Hexyl (meth) acrylamide, N-(2-methoxyethyl)(meth) acrylamide, N,N-dimethyl(meth) acrylamide, N,N-diethyl ( Methyl) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) propylene morpholine, diacetone acrylamide, and the like.
Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether. Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethylstyrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxystyrene, and methoxy. Styrene, butoxystyrene, ethoxylated styrene, fluorostyrene, difluorostyrene, bromostyrene, fluoromethylstyrene, bases deprotected by acidic substances (eg tertiary Boc, etc.) Protected hydroxystyrene, ethylene benzoic acid methyl, and – methyl styrene and the like.
The resin (B) having a cationic group in the side chain can be obtained by a known method such as anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, radical polymerization, and living radical polymerization. Among them, radical polymerization or living radical polymerization is preferred.
In the case of living radical polymerization, a polymerization initiator is preferably used. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compound include 2, 2'-azobisisobutyronitrile, 2, 2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane). 1–carboxonitrile), 2, 2'-azobis(2,4-dimethylvaleronitrile), 2, 2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) , dimethyl 2, 2'-azobis(2-methylpropionate), 4, 4'-azobis(4-cyanovaleric acid), 2, 2'-azo double (2– Hydroxymethylvaleronitrile) and 2, 2'-azobis[2-(2-imidazoline-2-yl)propane]. Examples of the organic peroxides include benzammonium peroxide, tertiary hydrogen peroxide butadiene, diisopropyl peroxycarbonate, di-n-propyl peroxycarbonate, and di(2-ethoxyethyl). Peroxycarbonate, tertiary butyl peroxy neoacetate, (3, 5, 5 - trimethylhexyl) peroxide, dipropyl hydrazine peroxide and diethyl hydrazine peroxide . These polymerization initiators may be used singly or in combination of two or more. The reaction temperature is preferably from 40 to 150 ° C, more preferably from 50 to 110 ° C, and the reaction time is preferably from 3 to 30 hours, more preferably from 5 to 20 hours.
The living radical polymerization method suppresses side reactions which occur in general radical polymerization, and further increases the polymerization growth, so that a block polymer or a resin having a uniform molecular weight can be easily synthesized.
Among them, an atomic mobile radical polymerization method using an organic halide or a halogenated fluorenyl compound as a starting agent and a transition metal complex as a catalyst can be adapted to a wide range of monomers. It is more suitable in terms of the polymerization temperature of the equipment. The atomic mobile radical polymerization method can be carried out by the methods described in the following References 1 to 8.
(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al., J. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) WO96/030421
(Reference 6) WO97/018247
(Reference 7) Japanese Patent Laid-Open No. 9-208616
(Reference 8) Japanese Patent Laid-Open No. 8-41117
It is preferred to use an organic solvent for the above polymerization. The organic solvent is not particularly limited, but for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexanone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether B can be used. Ester, dipropylene glycol monomethyl ether ethyl ester, ethylene glycol monoethyl ether ethyl ester, ethylene glycol monobutyl ether ethyl ester, diethylene glycol monoethyl ether ethyl ester or ethylene glycol monobutyl ether Ester and the like. These polymerization solvents can be used by mixing two or more types.
The amount of the ammonium salt group present in the resin (B) having a cationic group in the side chain is not particularly limited, but the ammonium salt of the resin is preferably from 10 to 200 mgKOH/g, more preferably from 20 to 130 mgKOH/g. When the ammonium salt value is less than 10 mgKOH/g, the ratio of the reactive anionic dye (C) becomes small, so the coloring power is lowered, and more halide (D) is required in the resist material. Therefore, the resin binder, the curable resin, and the like which are originally added to the resist material are reduced, and the glass adhesion of the resist film may be deteriorated or the coating film resistance of the resist film may be deteriorated. On the other hand, when it is more than 200 mgKOH/g, the solvent solubility of the halide (D) is deteriorated, and it is precipitated as a foreign substance in the resist material.
In order to satisfy the above range, the content of the ammonium salt of the resin is preferably in the range of 100% by weight based on 100% by weight of the structural unit constituting the resin, and more preferably in the range of 4 to 47% by weight. 8 to 48% by weight.
The molecular weight of the resin (B) having a cationic group in the side chain used in the present invention is not particularly limited, but the converted weight average molecular weight measured by a gel permeation chromatography (GPC) is preferably from 1,000 to 500,000, more preferably It is preferably from 1,000 to 80,000, more preferably from 2,000 to 20,000, most preferably from 3,000 to 15,000.
Further, the resin (B) having a cationic group in the side chain to be used preferably has a property of being dissolved in a solvent widely used for a coloring composition for a color filter. Thereby, a coating film which does not generate foreign matter can be obtained. It is especially preferred to dissolve in propylene glycol monomethyl ether ethyl ester.
(anionic dye (C))
Next, the anionic dye (C) for obtaining the halide (D) of the present invention will be explained. The anionic dye (C) may be a coloring compound having an anionic group bonded to the above cationic group ion. The coloring compound is not particularly limited as long as it has a carboxylic acid group, a sulfonic acid group, a phenolic hydroxyl group, a phosphoric acid group or a metal salt thereof in the molecule, and the solubility in an organic solvent or a developer can be considered. The salt forming property, the absorbance, the other interaction with the composition, the light resistance, the heat resistance and the like are appropriately selected.
Examples of the anionic dye (C) include an anthraquinone anionic dye, a monoazo anionic dye, a diazo anionic dye, an oxazine anionic dye, an amine ketone anionic dye, and a xanthene system. An anionic dye, a quinoline anionic dye, a triphenylmethane anionic dye, or the like. Specific examples of the anionic dye which can be used for synthesizing the halide (D) are indicated by color index numbers.
The red dyes include CI acid red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22 , 23, 24, 25:1, 26, 26:1, 26:2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44 , 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76: 1, 80 , 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120 , 123, 125, 127, 128, 131, 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161 ,163,164,167,170,171,172,173,175,176,177,181,229,231,237,239,240,241,242,249, 252,253,255,257 , 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 334, 335, 336, 337, 340, 343, 344, 347, 348 , 350, 351, 353, 354, 356, 388, etc. .
Also, CI direct red 1, 2, 2: 1, 4, 5, 6, 7, 8, 10, 10: 1, 13, 14, 15, 16, 17, 18, 21, 22, 23 can also be used. 24, 26, 26: 1, 28, 29, 31, 33, 33: 1, 34, 35, 36, 37, 39, 42, 43, 43: 1, 44, 46, 49, 52, 53, 54 55, 56, 57, 58, 59, 60, 61, 62, 7, 67: 1, 68, 72, 72: 1, 73, 74, 75, 77, 78, 79, 81, 81:1, 85, 86, 88, 89, 90, 97, 100, 101, 101: 1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 122: 1, 124, 125, 127, 127:1 127: 2, 128, 129, 130, 132, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238, etc. .
The yellow dyes include CI acid yellow 2, 3, 4, 5, 6, 7, 8, 9, 9:1, 10, 11, 11:1, 12, 13, 14, 15, 16, 17, 17 : 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40:1, 41, 42, 42:1, 43 , 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115 , 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187 , 189, 190, 191, 192, 199, etc.
Also, CI direct yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44:1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134, and the like.
The orange dyes include CI acid orange 1, 1, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 17, 18, 19, 20, 20: 1, 22, 23 , 24, 24, 1, 25, 27, 28, 28: 1, 30, 31, 33, 36, 37, 38, 41, 45, 49, 50, 51, 54, 55, 56, 59, 79, 83 , 94, 95, 102, 106, 116, 117, 119, 128, 131, 132, 134, 136, 138, and the like.
Also, CI direct orange 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 17, 19, 20, 21, 24, 25, 26, 29, 29:1, 30, 31, 32, 33, 43, 49, 51, 56, 59, 69, 72, 73, 74, 75, 76, 79, 80, 83, 84, 85, 87, 88, 90, 91, 92, 95, 96, 97, 98, 101, 102, 102: 1, 104, 108, 112, 114, and the like.
The blue dye may be CI Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 18, 19, 21, 22, 23, 24, 25 , 26, 27, 29, 34, 35, 37, 40, 41, 41:1, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57 , 58, 62, 62: 1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 84, 85, 86, 88, 89, 90, 90:1 , 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127 : 1,128,129,135,137,138,143,145,147,150,155,159,169,174,175,176,183,198,203,204,205,206,208,213,227 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280, and the like.
Also, CI Direct Blue 1, 2, 3, 4, 6, 7, 8, 8, 1:1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21:1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98: 1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129, 130, 130: 1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158: 1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 213, 215, 225, 226, 229, 230, 231, 242, 244, 253, 254, 260, 263, and the like.
The purple dye may be CI acid violet 1, 2, 3, 4, 5, 5: 1, 6, 7, 7: 1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, etc.
Also, CI Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27 may also be used. 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97, and the like.
The green dye may be CI Acid Green 2, 3, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 25:1. 27, 34, 36, 37, 38, 40, 41, 42, 44, 54, 55, 59, 66, 69, 70, 71, 81, 84, 94, 95, and the like.
Further, CI direct greens 11, 13, 14, 24, 30, 34, 38, 42, 49, 55, 56, 57, 60, 78, 79, 80 and the like can also be used.
(formation of salt)
The halide (D) of the present invention can be easily stirred or vibrated to cause a resin having a cationic group in a side chain (B)), an aqueous solution which is dissolved with an anionic dye (C), or under stirring or vibration. An aqueous solution of a resin having a cationic group (B) is mixed with an aqueous solution of an anionic dye (C) to obtain it. In the aqueous solution, the cationic group of the resin and the anionic group of the dye are ionized, and these are ion-bonded, and the ion-bonding portion is precipitated as water-insoluble. Conversely, since the salt composed of the reverse anion of the resin and the counter cation of the acid dye is water-soluble, it can be removed by washing with water or the like. The resin (B) having a cationic group in the side chain to be used and the anionic dye (C) may be used in a single type or in a plurality of types having different structures.
The aqueous solution used for forming the salt is a resin (B) having a cationic group in the side chain, and an anionic dye is dissolved. Therefore, a mixed solution of water and a water-soluble organic solvent can also be used. The water-soluble organic solvent may, for example, be methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol or 2-( Methoxymethoxy)ethanol, 2 -butoxyethanol, 2 - (isopropoxy)ethanol, 2 - (hexyloxy) ethanol, 2 - (hexyloxy) ethanol, diethylene glycol, diethyl Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol , dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, propyl acetate, methyl ethyl ketone, N, N-dimethylformamide, dimethyl hydrazine, tetrahydrofuran (THF), Dioxane, 2-oxanone, 2-methylxanthone, N-methyl-2-indole ketone, 1,2-hexanediol, 2,4,6-hexanetriol, Tetrafuranmethanol, 4-methoxy-4-pentanone, and the like. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, and most preferably 5 to 20% by weight based on the total weight of the mixed liquid (100% by weight).
The ratio of the resin having a cationic group (B) to the anionic dye (C) in the side chain is 10:1 to 1:4 when the total anionic group of the total cationic unit of the resin and the anionic dye (C) is 10:1 to 1:4. The range of the halide (D) of the present invention can be suitably adjusted, and it is more preferably in the range of 2:1 to 1:2.
<pigment>
Further, a pigment for coloring the color filter of the present invention can be further used as a coloring composition for a color filter.
The pigment may be used singly or in combination of two or more organic or inorganic pigments. The pigment is preferably a pigment having high color rendering property and high heat resistance, and particularly preferably a pigment having high heat decomposition resistance, and an organic pigment is generally used. The following is a specific example of the organic pigment which can be used for a color filter by using a color index number.
For the red coloring composition used to form the red filter segments, for example, CI Pigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 81:1, 81 can be used. : 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, 242, 246, 254, 255, 264, 268, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285 Or 287 and other red pigments. Further, in the red coloring composition, an orange pigment such as CI pigment orange 36, 38, 43, 51, 55, 59, 61, 71 or 73 and/or CI pigment yellow 1, 2, 3, 4, 5 may be used at the same time. 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, 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 Yellow pigment such as 198, 199, 213, 214, 218, 219, 220 or 221.
For the green coloring composition for forming the green filter segment, a green pigment such as CI Pigment Green 7, 10, 36, 37, 58 can be used. Further, in the green coloring composition, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32 can be used at the same time. , 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, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174 Yellow pigments such as 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221.
For the blue colored composition for forming the blue filter segment, for example, CI Pigment Blue 1, 1:2, 1:3, 2, 2:1, 2:2, 3, 8, 9, 10 can be used. , 10:1, 11, 12, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 18, 19, 22, 24, 24:1, 53, 56, 56 : 1,57, 58, 59, 60, 61, 62, 64 and other blue pigments. Further, in the blue coloring composition, a violet pigment such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 45 may be used at the same time.
For the cyan coloring composition for forming the cyan filter section, for example, CI Pigment Blue 15:1, 15:2, 15:4, 15:3, 15:6, 16, 81, etc. may be used alone or in combination. Color pigments.
For the magenta colored composition for forming the magenta filter segment, a violet pigment such as CI Pigment Violet 1, 19, CI Pigment Red 144, 146, 177, 169, 81, or the like, and a red pigment may be used singly or in combination. In the magenta colored composition, a yellow pigment can be used at the same time.
Further, the inorganic pigment is, for example, titanium oxide, palladium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, purple red paint (red iron oxide (III)), cadmium red, ultramarine blue, indigo, chrome oxide green, cobalt green, brown Soil and synthetic iron black. The inorganic pigment is used in combination with an organic pigment in order to achieve a balance between chroma and brightness while ensuring good coatability, sensitivity, developability, and the like.
(pigment refinement)
The pigment added to the colored composition of the present invention is preferably made fine by salt milling in order to correspond to high penetration and high contrast. From the viewpoint of good dispersion in the colorant carrier, the primary particle diameter of the pigment is preferably 10 nm or more. Further, it is preferably 80 nm or less from the viewpoint of forming a filter segment having a high contrast ratio. A particularly suitable range is in the range of 20 to 60 nm.
The salt milling treatment refers to heating a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent using a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, and a sand mill. After mechanically mixing and stirring, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt functions as a pulverization aid. In salt milling, the high hardness of the inorganic salt is used to pulverize the pigment. By optimizing the conditions in which the pigment is subjected to a salt milling treatment, it is possible to obtain a pigment having a very fine primary particle diameter, or a narrow distribution range thereof and a clear particle size distribution.
As the water-soluble inorganic salt, for example, sodium chloride, cesium chloride, potassium chloride or sodium sulfate can be used. From the price point of view, sodium chloride (salt) should be used. From the viewpoints of both the treatment efficiency and the production efficiency, the water-soluble inorganic salt is preferably used in an amount of from 50 to 2,000 parts by weight based on the total weight of the pigment (100 parts by weight), and most preferably from 300 to 1,000 parts by weight.
The water-soluble organic solvent functions as a wet pigment and a water-soluble inorganic salt, and is not particularly limited as long as it is dissolved (mixed) in water and the inorganic salt used is substantially insoluble in water. However, in the salt milling treatment, the temperature rises and the solvent is in a state of easy evaporation. Therefore, from the viewpoint of safety, it is preferably a high boiling point solvent having a boiling point of 120 ° C or higher. For example, 2-methoxymethoxyethane, 2-butoxyethane, 2-(isopropoxy)ethane, 2-(hexyloxy)ethane, 2-(hexyloxy)ethane can be used. , diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid poly Ethylene glycol, 1-methoxy-2-propane, 1-ethoxy-2-propane, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether or liquid polypropylene glycol. The water-soluble organic solvent is preferably used in an amount of from 5 to 1,000 parts by weight, based on the total weight of the pigment (100 parts by weight), and most preferably from 50 to 500 parts by weight.
When the pigment is subjected to salt milling, the resin may be added as needed. The kind of the resin to be used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified from a natural resin, or the like can be used. The resin to be used is preferably solid at room temperature and insoluble in water, and a part is soluble in the above organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight based on the total weight of the pigment (100 parts by weight).
<Resin Adhesive>
The resin binder is a coloring agent, in particular, a halide (D) and a pigment, or a halide, and a thermoplastic resin or a thermosetting resin.
The thermoplastic resin may, for example, be an acrylic resin, a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, or a polyvinyl acetate. , polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene (HDPE, LDPE), poly Butadiene and polyimine resin.
Examples of the thermosetting resin include an epoxy resin, a benzoamide resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, and a phenol resin.
The resin binder is preferably a resin having a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light region. Further, since the coloring composition for a color filter of the present invention is used in the form of an alkali-developing type colored resist material, it is preferred to use an alkali-soluble vinyl-based resin obtained by copolymerizing an ethylenically unsaturated monomer having an acidic group.
The vinyl base-soluble resin to which the ethylenic unsaturated monomer having an acidic group is copolymerized may, for example, be a resin having an acidic group such as a carboxyl group or a sulfo group. Specifically, the alkali-soluble resin may be an acrylic resin having an acidic group. An olefin-(anhydride) maleic acid copolymer, a styrene/styrenesulfonic acid copolymer, a styrene/(meth)acrylic acid copolymer or an isobutylene/(anhydride) maleic acid copolymer, or the like. Among them, at least one type of resin selected from the group consisting of an acrylic resin having an acidic group and a styrene/styrenesulfonic acid copolymer is used, and in particular, an acrylic resin having an acidic group is preferably used because it has high heat resistance and transparency.
In order to enhance the light sensitivity of the alkali-soluble resin copolymerized with the ethylenically unsaturated monomer having an acidic group, an active energy ray-curable resin which also has an ethylene-unsaturated double bond may be used. Moreover, it is preferable to use an active energy ray-curable resin having a side chain having an ethylenically unsaturated double bond, which has an effect of improving the solvent resistance of the resist material.
The active energy ray-curable resin having a double bond of ethylenic unsaturation may, for example, be a resin in which an unsaturated ethylenic double bond is introduced by the method (a) or (b) shown below.
[method (a)]
As the method (a), for example, by copolymerizing an ethylenically unsaturated ethylenic monomer having another epoxy group with one or more other monomers, the side chain epoxy group of the obtained copolymer is rendered unsaturated. The ethylenic double-bonded unsaturated carboxyl group of the monovalent acid is subjected to an additional reaction, and the polyhydroxy acid anhydride is reacted with the generated hydroxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.
Examples of the unsaturated ethylenic monomer having an epoxy group include a glycidyl (meth) acrylate, a methyl epoxypropyl (meth) acrylate, and a 2-epoxypropoxy group (A). Acrylate, 3,4 epoxybutyl (meth) acrylate and 3,4 epoxy cyclohexyl (meth) acrylate. These may be used alone or in combination of two or more. From the standpoint of reactivity with an unsaturated monovalent acid in the next step, it is preferably a propylenepropyl (meth) acrylate.
Examples of the unsaturated monovalent acid include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and (meth)acrylic acid. A monocarboxylic acid such as a halogen or alkane, a halogen, a nitrate or a cyanide substitution. These may be used alone or in combination of two or more.
Examples of the polyvalent acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more. If necessary, the number of carboxyl groups and the like may be increased, and a tricarboxylic acid anhydride such as trimellitic anhydride may be used, or a tetracarboxylic dianhydride such as pyromellitic dianhydride may be used, or the residual anhydride group may be hydrolyzed or the like. Further, as the polyvalent acid anhydride, if tetrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used, the unsaturated ethylenic double bond can be further increased.
A similar method of the method (a) includes, for example, a part of a side chain carboxyl group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group with one or more other monomers, and having an epoxy group. The ethylenically unsaturated ethylenic monomer is subjected to an additional reaction to introduce an unsaturated ethylenic double bond and a carboxyl group.
[method (b)]
As the method (b), comprising using an unsaturated ethylenic monomer having a hydroxyl group, copolymerizing with another unsaturated monovalent acid having a carboxyl group or another monomer, and having a side chain hydroxyl group of the obtained copolymer, having an isocyanate A method of reacting an isocyanate group of a ethylenically unsaturated ethylenic monomer.
Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2 - or 3 - or 4 - hydroxy butyl a hydroxyalkyl (meth) acrylate such as a (meth) acrylate, a glycerol (meth) acrylate or a cyclohexane dimethanol mono (meth) acrylate, which are used alone or in combination All of the above are fine. Further, it can also be used in the above-mentioned hydroxyalkyl (meth) acrylate, and polyether mono(meth)acrylic acid obtained by additionally polymerizing an ethylene peroxide, a propylene peroxide, and/or a butyl peroxide. Ester, or (poly)ester mono(meth)acrylate with (poly)g-valerolactone, (poly)e-caprolactone and/or (poly)12-hydroxystearic acid. From the viewpoint of suppressing the coating film foreign matter, it is preferably 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate.
Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate or 1,1-bis[(meth)acrylofluoreneoxy]ethyl isocyanate, but are not limited thereto. Wait. Further, two or more types may be used at the same time.
The weight average molecular weight (Mw) of the resin binder is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000, in order to suitably disperse the colorant. Further, the number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw/Mn is preferably 10 or less.
The resin binder is based on the viewpoint of dispersibility, permeability, developability, and heat resistance of the pigment and the halogenated product, and adsorbs a carboxyl group, a carboxyl group serving as an alkali-soluble group, a colorant carrier, and The balance between the aliphatic group and the aromatic group in which the affinity group of the solvent functions is a dispersibility, permeability, and developability of the pigment and the halogenated product, and further important for durability, and it is preferable to use an acid value of 20 to 300 mg KOH / g of resin. When the acid value is less than 20 mgKOH/g, the solubility in the developer is not good, and it is difficult to form a fine pattern. If it exceeds 300 mgKOH/g, a fine pattern cannot be left.
The resin binder is preferably used in an amount of 30% by weight or more based on the total weight of the colorant from the viewpoint of good film formability and various resistances, and is excellent in colorant concentration. The color characteristics are therefore preferably used in an amount of 500% by weight or less.
<organic solvent>
The colored composition of the present invention may contain an organic solvent such that the colorant is sufficiently dispersed and infiltrated into the colorant carrier, and is applied to a substrate such as a glass substrate to have a dry film thickness of 0.2 to 5 It is easy to form a filter segment.
The organic solvent may, for example, be ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol diacetic acid. Salt, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,3,5-trimethyl-2-cyclohexene-1-one, 3, 5, 5 trimethylcyclohexanone, ethyl 3-ethoxypropionate, butyl 3-methoxy-3-methylacetate, 3-methoxybutanol, butyl 3-methoxyacetate, 4 – heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, n-butylbenzene, propyl orthoacetate, N-pyrrolidone, o-xylene, o-chlorotoluene , o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, secondary butylbenzene, tertiary butylbenzene, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol Monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, diisobutyl ketone, cyclohexanol acetate, dipropylene glycol dimethyl ether, dipropylene glycol Ether acetate, dipropylene glycol monobutyl ether, diacetone alcohol, propylene glycol diacetate, propylene glycol phenyl ether, C Alcohol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, phenyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-aminoacetate, N-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, divalent acid ester, and the like.
Among them, from the viewpoint of dispersing and dissolving the pigment and the halogenated product (D) of the present invention, it is preferred to use ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethylene glycol. An alcohol acetate such as monomethyl ether acetate or ethylene glycol monoethyl ether acetate; an aromatic alcohol such as benzyl alcohol; or a ketone such as cyclohexanone. In particular, from the viewpoint of safety and hygiene and low viscosity, it is more preferably propylene glycol monomethyl ether acetate.
These organic solvents may be used alone or in combination of two or more. Further, it is preferred to mix the two or more mixed solvents used in an amount of from 65 to 95% by weight based on the above-mentioned preferred organic solvent.
Further, since the organic solvent can adjust the coloring composition to an appropriate viscosity to form a filter segment having a uniform film thickness, the total weight of the coloring agent (100 parts by weight) is preferably 800 to 4000 weights. The amount of the department is used.
<scatter>
The coloring composition of the present invention is a colorant carrier composed of a resin (B) having a cationic group in a side chain and a halide (D) obtained by reacting an anionic dye (C), the above-mentioned resin binder and a solvent. When the pigment is further contained, it is preferable to disperse the pigment together with a dispersing aid such as a pigment derivative by a dispersing mechanism such as a three-roll mill, a two-roll mill, a sand mill, a kneader or an attritor. A coloring composition can be produced. Further, the colored composition of the present invention may be produced by mixing a pigment, a halide (D), and other coloring agents, which are separately dispersed in a colorant carrier.
(dispersion aid)
When the colorant is dispersed in the colorant carrier, a dispersion aid such as a dye derivative, a resin type pigment dispersant, or a surfactant can be suitably used. The dispersing aid has a good ability to disperse the coloring agent, and the effect of preventing re-coagulation of the dispersing coloring agent is very large. Therefore, when a dispersing aid is used to disperse the coloring agent in the coloring agent carrier, the coloring composition can be obtained. A color filter with high penetration.
In the present invention, it is also expected that the halide (D) functions as a pigment dispersing aid.
The dye derivative may be a compound in which an organic substituent, an anthracene, an acridone or a triazine is introduced, and a basic substituent, an acidic substituent or a phthalimine methyl group which may have a substituent is introduced. For example, JP-A-63-305173, JP-A-57-15620, JP-A-59-40172, JP-A-63-17102, JP-A-5-9469, and the like can be used. Recorded things. These may be used alone or in combination of two or more.
When the amount of the pigment derivative is adjusted based on the total amount of the added pigment (100 parts by weight), it is preferably 0.5 parts by weight or more, and more preferably 1 part by weight or more, and most preferably from the viewpoint of improving the dispersibility of the added pigment. It is 3 parts by weight or more. In addition, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, and more preferably 35 parts by weight or less based on the total amount of the added pigment (100 parts by weight).
The resin type dispersant has a pigment affinity site having a property of adsorbing on a pigment and a site compatible with a pigment carrier, and has a function of adsorbing to a colorant to stabilize the dispersion of the colorant with respect to the pigment carrier. The specific resin type dispersant may be a polycarboxylate such as polyurethane or polyacrylate, an unsaturated polyamine, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, a polycarboxylic acid ammonium salt, or a polycarboxylic acid alkylamine salt. , polyoxyalkylene oxide, long-chain polyamine decylamine phosphate, hydrocarbon-containing polycarboxylate or the like, by reacting with a polyester having a polymerized (lower alkylenimine) and a free carboxyl group An oily dispersant such as a guanamine or a salt thereof, a (meth)acrylic acid-(meth) acrylate copolymer, a styrene-maleic acid copolymer, a polyvinyl alcohol, a polyvinylpyrrolidone, or the like a resin, a water-soluble polymer compound, a polyester-based dispersant, a modified polyacrylate-based dispersant, an ethylene oxide/propylene oxide-addition compound, a phthalate-based dispersant, etc., which may be used alone or in combination. It is used above, but it is not necessarily limited to these.
Commercially available resin-type dispersing agents include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by BYK-Chemie Japan Co., Ltd. , 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203 and 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimom-WS, and Bykumen, etc., SOLSPERSE-3000, 9000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, manufactured by Lubrizol, Japan. , 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, 55000, and 76500, EFKA-46, 47, 48, 452, 4008, manufactured by Chiba Corporation, Japan. 4009, 4010, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Fine-Tech AJISPER-PA111, PB711, PB821, PB822, PB824, etc. manufactured by no company.
Examples of the surfactant include polyethylene oxide ether sulfate, sodium dodecylbenzenesulfonate, styrene-acrylic acid copolymer acrylate, alkylnaphthalenesulfonate sodium, and alkyl diphenyl ether disulfonic acid. Sodium, lauryl ethanolamine, lauryl triethanolamine, ammonium lauryl sulfate, stearic acid ethanolamine, ammonium stearate, sodium lauryl sulfate, styrene-acrylic acid copolymer ethanolamine, polyoxyethylene ether phosphate ether And other anionic surfactants; polyethylene oxide oleyl ether, polyethylene oxide lauryl ether, polyethylene oxide nonylphenyl ether, polyethylene oxide ether phosphate, polyethylene oxide sorbitan glycerol hard fat a cationic surfactant such as an acid; an alkyl quaternary ammonium salt; an alkyl quaternary ammonium carboxylic acid such as a quaternary ammonium salt; An amphoteric surfactant such as a carboxylic acid inner salt or an alkyl imidazoline may be used singly or in combination of two or more kinds, but it is not necessarily limited thereto.
When a resin-type dispersant or a surfactant is added, the amount is preferably 0.1 to 55 parts by weight, and more preferably 0.1 to 45 parts by weight, based on the total amount of the added pigment (100 parts by weight). When the amount of the resin-type dispersant or the surfactant is less than 0.1 part by weight, it is difficult to obtain an effect of addition, and when the amount is more than 55 parts by weight, excessive dispersion may affect the dispersion.
<Photopolymerizable monomer>
Further, a photopolymerizable monomer and/or a photopolymerization initiator may be further added to the colored composition of the present invention to be used as a photosensitive coloring composition for a color filter.
The photopolymerizable monomer of the present invention contains a monomer or oligomer which is cured by ultraviolet rays or heat to form a transparent resin. These may be used alone or in combination of two or more. The amount of the monomer is preferably from 5 to 400 parts by weight based on the total weight of the colorant (100 parts by weight), and is preferably from 10 to 300 parts by weight from the viewpoint of photocurability and developability.
Examples of the monomer or oligomer which forms a transparent resin by curing by ultraviolet rays or heat include methyl (meth) acrylate, ethyl (meth) acrylate, and 2-hydroxyethyl (methyl). Acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, -carboxy (meth) acrylate, polyethylene glycol mono (meth) acrylate, hexamethylene di(meth) acrylate, triethylene glycol di (meth) acrylate, and Propylene glycol di(meth)acrylate, trimethylolpropane (meth) acrylate, neopentyl alcohol (meth) acrylate, neopentyltetrakis (meth) acrylate, dipentaerythritol (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-butanediol diglycidyl ether, bisphenol A diglycidyl ether, neopentyl glycol glyceryl ether, Various methyl acrylates such as melamine and methacrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, neopentyl alcohol trivinyl ether, Methyl) acrylamide, N-hydroxymethyl (meth) acrylamide, N-ethylene formamide, acrylonitrile, etc., but is not necessarily limited to these.
<Photopolymerization initiator>
In the colored composition for a color filter of the present invention, the composition is cured by ultraviolet irradiation, and when a filter segment is formed by photolithography, a photopolymerization initiator or the like may be added to form a solvent development type. Or the form of the alkali-developing type coloring resist material is adjusted. The amount of the photopolymerization initiator to be used is preferably from 5 to 200 parts by weight, based on the total amount of the coloring agent, and is preferably from 10 to 150 parts by weight from the viewpoint of photocurability and developability.
As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, diethoxyacetophenone, 1–(4-isopropylphenyl) can be used. )–2–Hydroxy-2–methylpropane–1-ketone, 1-hydroxycyclohexylbenzophenone, 2-benzyldimethylamine-1–(4-morpholinylphenyl)-butane-1-ketone An acetophenone compound; a benzo compound such as benzo, benzoxyl ether, benzoether, benzoisopropyl ether or benzyldimethylketal; benzophenone, benzoquinone benzoic acid, benzoquinone Benzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoquinone-4'-methyldiphenyl sulfide, 3, 3', 4 , benzophenone-based compounds such as 4'-tetrakis(t-butylperoxycarboxy)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxan a thioxanthone compound such as a ketone, 2,4-diisopropylthioxanthone or 2,4-diethylthioxanthone; 2, 4, 6-trichloro-o-triazine, 2-phenyl-4 , 6-bis(trichloromethyl)-orthotriazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-o-triazine, 2–(p-toluene )–4, 6–bis(trichloromethyl)-o-triazine, 2-pipeline--4,6-bis(trichloromethyl)-o-triazine, 2,4-bis(trichloromethyl) –6– Styryl-o-triazine, 2–(naphtho-l-yl)-4,6-bis(trichloromethyl)-o-triazine, 2–(4-methoxynaphtho--1 –yl) –4, 6–bis(trichloromethyl)-o-triazine, 2,4-trichloromethyl-(piperidinyl)-6-triazine, 2,4-trichloromethyl (4' -Methoxystyryl)-triazine-based compounds such as 6-triazine; 1,2-octanedione, 1–[4–(phenylthio)–, 2(O–benzopyrene)], O –(Ethylhydra)–N–(1–phenyl–2–carbonyl-2–(4′-methoxy-naphthyl)ethylidene)hydroxylamine and other oxime ester compounds; double (2, 4, 6– a phosphine compound such as trimethylbenzo)epoxyphenylphosphine or 2,4,6-trimethylbenzoepoxyphenylphosphine; an anthraquinone compound such as phenanthrenequinone, camphorquinone or ethylhydrazine; a borate compound; an oxazole compound; or an imidazole compound.
These photopolymerization initiators may be used alone or in combination of two or more kinds in any ratio as needed. When the photopolymerization initiator is based on the total weight of the coloring agent in the coloring composition for a color filter (100 parts by weight), it is preferably 5 to 200 parts by weight, and is photocurable and developable. The viewpoint is more preferably 10 to 150 parts by weight.
<sensitizer>
Further, in the colored composition for a color filter of the present invention, a sensitizer may be further contained.
Examples of the sensitizer include unsaturated ketones represented by flavonoid derivatives or dibenzylideneacetone, 1,2-dione derivatives represented by benzyl or camphorquinone, benzo derivatives, and hydrazine derivatives. , naphthoquinone derivatives, anthracene derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, coumarin derivatives a polymethine pigment such as a cyanine derivative, a merocyanine derivative, or a cyanine derivative, an acridine derivative, an azabenzene derivative, a diene terpene derivative, an oxazine derivative, or a porphyrin derivative. , anthracene derivative, sulfonium salt derivative, squaraine ylide derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazine porphyrin derivative , phthalocyanine derivative, tetrazoporphyrin derivative, tetraquinoxaline porphyrin derivative, naphthalocyanine derivative, phthalocyanine derivative, pyridinium salt derivative, thiopyridinium salt derivative, Tetraporphyrin derivative, olefin derivative, spiropyran derivative, spirooxazine derivative, thiospiropyran derivative, metal aryl Hydrocarbon complex, organic ruthenium complex, Michler's ketone derivative, a-methoxyl ether, decyl phosphide hydroxide, tolyl glyoxylic acid, benzyl-9,10-phenanthrene , camphor, ethyl hydrazine, 4,4'-diethyl phenol ketone, 3,3' or 4,4'-tetrakis (tertiary butylperoxycarboxy) benzophenone, 4,4' - dimethylamine benzophenone and the like.
Specifically, the "Pigment Handbook" (1986, Kodansha), and the "Chemistry of Functional Pigments" (1981, CMC) and Chisen-Sang Sanlang, etc., edited by Ohara Shinto et al. The sensitizers described in "Special Functional Materials" (1986, CMC) are not limited to these. Further, it may contain a sensitizer which exhibits absorption of light from the ultraviolet to the near-infrared region.
It is also possible to use two or more sensitizers at any ratio as needed. When the sensitizer is used, the amount is preferably from 3 to 60 parts by weight based on the total weight of the photopolymerization initiator contained in the coloring composition, from photohardenability and development. Sexual point of view, more preferably 5 to 50 parts by weight.
<Amine compound>
Further, the coloring composition for a color filter of the present invention may contain an amine compound having a function of reducing dissolved oxygen.
Examples of such amine-based compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminebenzoic acid methyl, 4-dimethylamine benzoic acid ethyl, 4-dimethylamine. Benzoic acid 2-ethylhexyl and N,N-dimethyl-p-toluidine and the like.
<leveling agent>
In the coloring composition of the present invention, in order to improve the leveling property of the composition on the transparent substrate, it is preferred to add a leveling agent. The leveling agent is preferably a dimethyl siloxane having a polyether structure or a polyester structure in the main chain. Specific examples of the dimethyl siloxane having a polyether structure in the main chain include FZ-2122 manufactured by TORAY‧Dow Corning Co., Ltd. and BYK-333 manufactured by BYK Corporation. Specific examples of the dimethyl methoxy olefin having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Corporation. It is also possible to use dimethyl methoxyoxane having a polyether structure in the main chain and dimethyl methoxy oxane having a polyester structure in the main chain. The content of the leveling agent is generally 0.003 to 0.5 parts by weight based on the total weight of the coloring composition (100 parts by weight).
The leveling agent is one of a so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, and has hydrophilicity and low solubility in water. When added to a colored composition, it is preferred that the surface tension is low. Further, even if the surface tension reducing ability is low, it is useful for a material having good wettability of a glass plate, and it is preferable to use a material which can sufficiently suppress the chargeability in the amount of addition of the coating film defect caused by foaming. A leveling agent having such a suitable property may, for example, be a dimethyloxysiloxane having a polyalkylene oxide unit. The polyalkylene oxide units include polyethylene oxide units and polyoxypropylene units. Dimethyloxane may also have both polyethylene oxide units and polypropylene oxide units.
Further, the combination of the polyalkylene oxide unit and the dimethyloxane may be any of the following types: a pendant type in which a polyalkylene oxide unit is combined in a repeating unit of dimethyloxane; a polyepoxy a terminal unit modified with an alkane unit bonded to a terminal end of dimethyloxane; and a linear block copolymer type in which a polyalkylene oxide unit is repeatedly and repeatedly bonded to dimethyloxane. A dimethyl methoxy olefin having a polyalkylene oxide unit is commercially available from TORAY‧Dow Corning Co., Ltd., and examples thereof include FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, and FZ-2203. FZ-2207, but is not limited to these.
Anionic, cationic, nonionic or amphoteric surfactants may also be added to the leveling agent. It is also possible to use two or more kinds of surfactants in combination.
Examples of the anionic surfactant which is auxiliaryly added to the leveling agent include polyethylene oxide ether sulfate, sodium dodecylbenzenesulfonate, styrene-acrylic acid copolymer acrylate, and alkylnaphthalenesulfonic acid. Sodium, sodium alkyl diphenyl ether disulfonate, ethanolyl lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, ethanolamine stearate, ammonium stearate, sodium lauryl sulfate, styrene-acrylic acid copolymer Monoethanolamine and polyethylene oxide ether phosphate.
The cationic surfactant of the auxiliary leveling agent may, for example, be an alkyl 4-based ammonium salt or an ethylene oxide addition thereof. Examples of the nonionic surfactant that is auxiliaryly added to the leveling agent include polyethylene oxide oleyl ether, polyethylene oxide lauryl ether, polyepoxy decyl phenyl ether, and polyethylene oxide ether phosphate. Bismuth of alkyl quaternary ammonium carboxylate and alkyl imidazoline, such as polyethylene oxide sorbitan glyceryl stearate, polyethylene glycol monolauryl ester, alkyl dimethylamine acetate quaternary ammonium carboxylate inner salt A surfactant, or a fluorine- or sulfhydryl surfactant.
<hardener, hardening accelerator>
Moreover, in order to assist the hardening of the thermosetting resin, the coloring composition of the present invention may contain a curing agent, a curing accelerator, and the like as needed. The effective curing agent is a phenol resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, or a sulfonic acid compound. However, the curing agent is not particularly limited thereto, and may be used in a reaction with a thermosetting resin. Any hardener can be used. In addition, among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are particularly preferable. The hardening accelerator may, for example, be an amine compound (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamine)-N,N-dimethylbenzylamine, 4-methoxy- N,N-dimethylbenzylamine and 4-methyl-N,N-dimethylbenzylamine, etc.); 4-stage ammonium chloride compound (for example, triethylbenzylammonium chloride, etc.); blocked isocyanate a compound (for example, dimethylamine or the like); an imidazolyl derivative bicyclic hydrazine compound and a salt thereof (for example, imidazolyl, 2-methylimidazolyl, 2-ethylimidazolyl, 2-ethyl-4-methyl Imidazolyl, 2-phenylimidazolyl, 4-phenylimidazolyl, 1-cyanoethyl-2-phenylimidazolyl and 1-(2-cyanoethyl)-2-ethyl-4-methyl a pyridyl group or the like; a phosphorus compound (for example, triphenylphosphine, etc.); a guanamine compound (for example, melamine, guanamine, acetamide, benzoguanamine, etc.); and an S-triazine derivative (for example, 2, 4) -diamine-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamine-6-triazine, 2-vinyl-4,6-diamine-S- Triazine ‧ isocyanate acid addenda and 2,4-diamine-6-methyl propylene oxyethyl-S-triazine ‧ isocyanate acid addenda, etc.). These may be used alone or in combination of two or more. The content of the hardening accelerator is preferably from 0.01 to 15% by weight based on the total amount of the thermosetting resin.
<Other additive ingredients>
In the colored composition of the present invention, a storage stabilizer may be contained in order to stabilize the viscosity of the composition over time. Further, in order to improve the adhesion to the transparent substrate, a adhesion promoter such as a decane coupling agent may be contained.
Examples of the storage stabilizer include 4-grade ammonium chlorides such as benzyltrimethyl chloride and dimethylhydroxylamine; organic acids such as lactic acid and oxalic acid, and ethyl ether; tertiary butyl pyrocatechol; Organic phosphines such as phosphines and tetraphenylphosphines; and phosphites. The storage stabilizer is preferably used in an amount of 0.1 to 10 parts by weight, based on the total amount of the coloring agent (100 parts by weight), more preferably 0.05 to 5 parts by weight.
The adhesion promoter can be exemplified by the following decane coupling agent: ethylene three ( a methoxy oxane such as an oxy) decane, an ethylene ethoxy decane or an ethylene trimethoxy decane; - (meth)acrylic acid decane such as methacryloxypropylene trimethoxy decane; –(3,4-epoxycycloalkyl)ethyltrimethoxydecane, –(3,4-epoxycycloalkyl)methyltrimethoxydecane, –(3,4-epoxycycloalkyl)ethyltriethoxydecane, –(3,4-epoxycycloalkyl)methyltriethoxydecane, – glycidoxypropyltrimethoxydecane, – epoxy decanes such as glycidoxypropyl triethoxy decane; N– (amine ethyl) –Aminopropyltrimethoxydecane, N– (amine ethyl) –Aminopropyltriethoxydecane, N– (amine ethyl) -Aminopropylmethyldiethoxydecane, -Aminopropyltriethoxydecane, –Aminopropyltrimethoxydecane, N–phenyl – –Aminopropyltrimethoxydecane, N–phenyl – - amine oxanes such as amine propyl triethoxy decane; – mercaptopropyltrimethoxydecane, - thiononanes such as mercaptopropyltrimethylethyl decane. The adhesion improving agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on the total amount of the coloring agent in the coloring composition (100 parts by weight).
<Remove coarse particles>
The coloring composition of the present invention is carried out by means of a mechanism such as a centrifugal separation, a sintering filter, or a membrane filter. The above coarse particles are more preferably 1 The above coarse particles, further 0.5 Removal of the above coarse particles and mixed dust. Thus, the coloring composition is preferably free of 0.5 The above particles. More preferably 0.3 the following.
<Color Filter>
Next, a color filter relating to the present invention will be described. The color filter of the present invention comprises a filter segment formed using the red colored composition of the color filter of the present invention. The color filter may include a red filter segment, a green filter segment, and a blue filter segment, or a magenta filter segment and a cyan filter segment. Yellow filter section.

As the transparent substrate, a glass plate such as soda lime glass, low alkali borosilicate glass or alkali-free aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate or polyethylene glycol can be used. Further, on the surface of the glass plate or the resin plate, a transparent electrode composed of indium oxide, tin oxide or the like may be formed in order to drive the liquid crystal after the panel is formed.
<Method of Manufacturing Color Filter>
The color filter of the present invention can be produced by a printing method or photolithography.
When the filter segment is formed by the printing method, only the printing and drying of the coloring composition prepared by the printing ink are repeated, and the patterning can be completed. Therefore, the color filter is manufactured at a low cost and mass production. Good sex. Further, by the development of printing technology, it is possible to perform printing of a fine pattern having high dimensional accuracy and smoothness. When printing, it is preferable that the ink does not dry and solidify on the printing plate or on the felt cloth. Moreover, the control of the fluidity of the ink on the printing press is also very important, and the viscosity of the ink can be adjusted by a dispersing agent or an extender pigment.
When the filter segment is formed by photolithography, the solvent development type or alkali development type coloring resistance is applied to the transparent substrate by a coating method such as spray coating or spin coating, slit coating or roll coating. The colored composition prepared by the etchant material is coated to a dry film thickness of 0.2 to 5 . The film which is dried as needed is subjected to ultraviolet light exposure through a mask having a specific pattern which is provided in contact with or non-contact with the film. Thereafter, the solution is immersed in a solvent or an alkali developer, or the developer is sprayed by a sprayer or the like to remove the uncured portion, and a desired pattern is formed, and then the same operation is repeated for other colors to produce a color filter. Further, in order to promote polymerization of the colored resist material, heating may be applied as needed. If the photolithography method is used, a color filter having a higher precision than the above printing method can be manufactured.
At the time of development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as the alkali developing solution, and an organic base such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant may be added to the developer. Further, in order to increase the ultraviolet exposure sensitivity, after drying and drying the coloring resist, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied to form a film which prevents oxygen from inhibiting polymerization. , UV exposure.
In addition to the above methods, the color filter of the present invention can also be produced by an electrodeposition method, a transfer method, an inkjet method, or the like, and the colored composition of the present invention can be used in any method. Furthermore, the electrodeposition method is formed by using a transparent conductive film formed on a substrate, and performing electrophoretic deposition of each color filter segment on the transparent conductive film by electrophoresis of colloidal particles, thereby fabricating a color filter. The method. Further, the transfer method is a method in which a filter segment is formed in advance on the surface of the transferable transfer substrate, and the filter segment is transferred to a desired substrate.
A black matrix may be formed in advance before forming the color filter segments on the transparent substrate or the reflective substrate. The black matrix is a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. Further, in the color filter of the present invention, a film, a transparent conductive film, or the like may be formed as needed.
[Examples]
Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In addition, unless otherwise specified, "part" means "weight".
First, the resin binder, the fine pigment, and the method for producing the resin (B) having a cationic group in the side chain and the halide (D) used in the examples and the comparative examples will be described.
<Modulation method of resin binder solution>
(Modulation of Resin Adhesive Solution 1)
A thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device were placed in a separate four-piece flask, and 70.0 parts of cyclohexanone was placed in the reaction container, and the temperature was raised to 80 ° C. After the reaction vessel was replaced with nitrogen, the tube was dropped. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, and p-cumyl epoxide modified acrylate (manufactured by Toagosei Co., Ltd.) were added over 2 hours. "ARONIX M110") A mixture of 7.4 parts, 2, 2'-azobisisobutyronitrile 0.4 parts. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26,000. After cooling to room temperature, the resin solution was sampled to about 2 g, which was heated at 180 ° C for 20 minutes to dry it, and the non-volatile component was measured, and methoxypropyl acetate was added to the previously synthesized resin solution to make it non-volatile. The component was made into a resin binder solution 1 at 20% by weight. Here, the weight average molecular weight (Mw) of the resin binder is measured by a gel permeation chromatography (GPC) using polystyrene as a standard material.
(Modulation of Resin Adhesive Solution 2)
In a separate four-stage flask equipped with a thermometer, a cooling tube, a nitrogen inlet tube, a dropping tube, and a stirring device, 207 parts of cyclohexanone were placed, and the temperature was raised to 80 ° C. After the reaction vessel was replaced with nitrogen, the tube was passed through the dropping tube. 20 parts of methacrylic acid, 20 parts of p-cumylphenol ethylene oxide modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.), 45 methyl methacrylate, and 2 - hydroxyethyl group were dropped in 2 hours. A mixture of 8.5 parts of acrylate and 1.33 part of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer solution.
Next, the supply of nitrogen gas was stopped, and the total amount of the resin solution obtained above was stirred while injecting dry air for 1 hour, and then cooled to room temperature, and then 2-methylpropenyloxyethyl isocyanate was dropped at 70 ° C for 3 hours ( A mixture of 6.5 parts of Karenz MOI), 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone.
The obtained resin solution was sampled by about 2 g, heated at 180 ° C for 20 minutes to be dried, and the non-volatile component was measured, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile component became 20% by weight to prepare a resin bond. Solution solution 2. The weight average molecular weight (Mw) was 18,000.
(Modulation of Resin Adhesive Solution 3)
In a separate four-stage flask equipped with a thermometer, a cooling tube, a nitrogen inlet tube, a dropping tube, and a stirring device, 207 parts of cyclohexanone were placed, and the temperature was raised to 80 ° C. After the reaction vessel was replaced with nitrogen, the tube was passed through the dropping tube. 20 parts of methacrylic acid, 20 parts of p-cumylphenol ethylene oxide modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.), 45 methyl methacrylate, and glycerol monomethyl group were dropped in 2 hours. A mixture of 8.5 parts of acrylate and 1.33 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer solution.
Next, the supply of nitrogen gas was stopped, and the total amount of the resin solution obtained above was stirred while being poured into dry air for 1 hour, and then cooled to room temperature, and then 2-methylpropenyloxyethyl isocyanate was dropped at 70 ° C for 3 hours. A mixture of 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone.
The resin solution was sampled by about 2 g, heated at 180 ° C for 20 minutes to dry it, and the non-volatile component was measured, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile component became 20% by weight to prepare a resin binder solution 3 . The weight average molecular weight (Mw) was 19,000.
(Modulation of Resin Adhesive Solution 4)
In a separate four-piece flask equipped with a thermometer, a cooling tube, a nitrogen inlet tube, a dropping tube, and a stirring device, 370 parts of cyclohexanone were placed, and the temperature was raised to 80 ° C. After replacing the inside of the reaction vessel with nitrogen, the tube was passed through the dropping tube. 18 parts of p-cumyl epoxide modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, and 18.2 parts of glycidyl methacrylate were added dropwise for 2 hours. A mixture of methyl methacrylate 25 and 2,2'-azobisisobutyronitrile 2.0. After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours, and then 1.0 portion of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and further reacted at 100 ° C for 1 hour. Next, the inside of the container was replaced with air, and 9.3 parts (100% of glycerol group), 0.5 part of trimethylaminophenol, and 0.1 part of hydroquinone were placed in the container, and the reaction was continued at 120 ° C for 6 hours. When the acid value of the solid component became 0.5, the reaction was terminated to obtain a copolymer solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the produced hydroxyl group) and 0.5 part of triethylamine were added, and the mixture was reacted at 120 ° C for 3.5 hours to obtain a carboxyl group and a copolymer solution.
After cooling to room temperature, the resin solution was sampled by about 2 g, heated at 180 ° C for 20 minutes to dry, and the non-volatile components were measured, and cyclohexanone was added to the previously synthesized resin solution to prepare the nonvolatile component to 20% by weight. Formed into acrylic resin solution 4. The weight average molecular weight (Mw) was 19,000.
<Method for Producing Micronized Pigment>
(blue fine pigment (P-1))
100 pieces of CI Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyo Ink Co., Ltd.), 800 parts of pulverized sodium chloride, and 100 parts of diethylene glycol were placed in stainless steel 1 A gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) was mixed and stirred at 70 ° C for 12 hours. The mixture was placed in 3000 parts of warm water, heated to 70 ° C, and stirred in a high-speed stirrer for about 1.5 hours to form a slurry. The mixture was repeatedly filtered, washed with water to remove sodium chloride and a solvent, and then dried at 80 ° C. In an hour, 98 parts of blue fine pigment (P-1) were obtained. The average primary particle diameter of the obtained pigment was 28.3 nm.
Here, the average primary particle diameter of the pigment is measured by a transmission electron microscope ("JEM-1200EX" manufactured by JEOL Ltd.), and the primary particle diameter of the entire pigment particles in the observation sample under 50,000 times is measured, and the average value thereof is used. . Further, when the particle shape is non-spherical, the long diameter and the short diameter are measured, and the numerical value obtained by (long diameter + short diameter)/2 is used as the particle diameter.
(Purple Micronized Pigment (P-2))
120 pieces of CI Pigment Violet 23 ("Fast Violet RL" manufactured by Toyo Ink Co., Ltd.), 1600 parts of pulverized sodium chloride, and 100 parts of diethylene glycol of dioxin-based purple pigment were placed in a 1-gallon kneading machine made of stainless steel. (manufactured by Inoue Seisakusho Co., Ltd.), and stirred and mixed at 90 ° C for 18 hours. The mixture was placed in 5000 parts of warm water, heated to about 70 ° C, and stirred in a high-speed stirrer for about 1 hour to form a slurry. The mixture was repeatedly filtered, washed with water to remove sodium chloride and a solvent, and dried at 80 ° C. In 24 hours, 118 parts of purple fine pigment (P-2) were obtained. The average primary particle diameter of the obtained pigment was 26.4 nm.
(Red micronized pigment (P-3))
200 parts of diketopyrrolopyrrole red pigment CI Pigment Red 254 ("IRGAZIN RED 2030" manufactured by Chiba Corporation, Japan), 1400 parts of pulverized sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel ( It was mixed and stirred at 80 ° C for 6 hours. The mixture was placed in 8000 parts of warm water, heated to about 80 ° C, and stirred in a high-speed stirrer for about 2 hours to form a slurry. The mixture was repeatedly filtered, washed with water to remove sodium chloride and a solvent, and dried at 85 ° C. For 24 hours, 190 red fine pigments (P-3) were obtained. The average primary particle diameter of the obtained pigment was 24.8 nm.
(Red micronized pigment (P-4))
200 pieces of red pigment CI Pigment Red 242 ("NOVOPERM SCARLET 4RF" by Clariant Co., Ltd.), 1400 parts of pulverized sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) to 80 Mix and stir for 6 hours at °C. The mixture was placed in 8000 parts of warm water, heated to about 80 ° C, and stirred in a high-speed stirrer for about 2 hours to form a slurry. The mixture was repeatedly filtered, washed with water to remove sodium chloride and a solvent, and dried at 85 ° C. For 24 hours, 190 red fine pigments (P-4) were obtained. The average primary particle diameter of the obtained pigment was 28.5 nm.
<Preparation method of resin (B) having a cationic group in a side chain>
(Production Example 1: Preparation of Resin B-1 having a cationic group in a side chain)
In a separate flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 75.1 parts of isopropyl alcohol were placed, and the temperature was raised to 75 ° C under a nitrogen stream. In addition, 18.2 parts of ethyl acrylate, 27.3 parts of methyl propyl acrylate, 27.3 parts of methyl 2-ethylhexyl acrylate, 15.0 parts of methyl hydroxyethyl acrylate, and dimethyl methacrylate methacrylate were uniformly mixed. 12.2 parts of ammonium chloride and 7.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 23.4 parts of methyl ethyl ketone, placed in a dropping funnel, and installed in 4 The separated flask was dripped over 2 hours. Two hours after the completion of the dropwise addition, the polymerization yield was confirmed to be 98% or more from the solid content, and the weight average molecular weight (Mw) was 7,330, and was cooled to 50 °C. Thereafter, 14.3 parts of methanol was added to obtain a resin B-1 having a cationic group at 40% by weight of the resin component and a Tg of 32 °C. The obtained ammonium salt value of the resin was 32 mgKOH/g.
Here, the weight average molecular weight (Mw) of the resin having a cationic group in the side chain is determined by a gel permeation chromatography (GPC) using polystyrene as a standard substance. Further, the ammonium salt value of the resin (B) having a cationic group in the side chain is determined by titration with a 0.1 N aqueous solution of silver nitrate, and is converted into the equivalent value of potassium hydroxide, which indicates the ammonium salt value of the solid component. .
(Production Example 2 to Production Example 17, Production Example 19 to Production Example 24: Preparation of Resins B-2 to 17 and B-19 to 24 having a cationic group in a side chain)
In the same manner as in Production Example 1, except that the monomer, the polymerization initiator, and the reaction temperature were changed to the compositions shown in Table 1, the resins B-2 to 17 and B-19 to having a cationic group in the side chain were obtained. twenty four.
(Production Example 18: Preparation of Resin B-18 having a cationic group in a side chain)
The resin B-18 having a cationic group in the side chain was synthesized in the same manner as in Production Example 1 except that a monomer other than GMA (glycidyl methacrylate) shown in Table 1 was used. The carboxyl group is reacted with a glycidyl group of GMA, whereby a resin B-18 having a cationic group in a side chain having a thermally bridged group (methacryl fluorenyl group) is obtained. The program is shown below.
In a separate flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 75.1 parts of isopropyl alcohol were placed, and the temperature was raised to 75 ° C under a nitrogen stream. In addition, 18.2 parts of methyl acrylate, 27.3 parts of methyl propyl acrylate, 27.3 parts of methyl 2-ethylhexyl acrylate, 15.0 parts of methacrylic acid, and dimethyl chloride ethyl methyl methacrylate were uniformly mixed. 12.2 parts of ammonium and 7.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 23.4 parts of methyl ethyl ketone were placed in a dropping funnel and attached to 4 separate types. The flask was dripped over 2 hours. Two hours after the completion of the dropwise addition, the polymerization yield was confirmed to be 98% or more from the solid content, and a resin B-18' having a cationic group and a Tg of 40 ° C was obtained as an intermediate. Next, after adding 107.1 parts of butyl races, the mixture was heated to 80 ° C or higher, and isopropyl alcohol and methyl ethyl ketone were azeotroped with butyl sedum, and isopropyl alcohol and methyl ethyl ketone were distilled off. When the internal temperature reached 100 ° C, 1 g of the sample was sampled, and the mixture was dried by heating at 180 ° C for 20 minutes to measure a nonvolatile component, and it was confirmed that the nonvolatile content of the resin solution was 50%. Thereafter, 24.8 parts of methyl glycidyl acrylate, 1.0 part of dimethylbenzylamine, and 0.2 part of hydroquinone were placed, and oxygen was sprayed at 100 ml/min. Thereafter, the temperature was raised to 100 ° C and stirred for 6 hours. After 6 hours, 1 g of the sample was sampled, and the mixture was dried by heating at 180 ° C for 20 minutes, and the nonvolatile matter was measured. The reaction rate was confirmed to be 90% or more, and the mixture was cooled to 50 ° C to obtain a resin B-18 having a cationic group in the side chain. The obtained ammonium salt value of the resin was 26.4 mgKOH/g.

The single system in Table 1 uses the following. It is indicated together with the glass transition temperature.
MMA: methyl methacrylate (105 ° C)
n-BMA: methyl n-butyl acrylate (20 ° C)
2-EHMA: methyl 2-ethylhexyl acrylate (-10 ° C)
2-EHA: 2-ethylhexyl acrylate (-85 ° C)
CHMA: cyclohexyl methacrylate (66 ° C)
i-BuMA: isobutyl methacrylate (48 ° C)
HEMA: methyl hydroxyethyl acrylate (55 ° C)
HEA: Hydroxyethyl acrylate (-15 ° C)
4HBA: 4-hydroxybutyl acrylate (-80 ° C)
MAA: methacrylic acid (130 ° C)
AA: Acrylic (106 ° C)
OXMA: 3-(methacrylofluorenyloxymethyl) 3-ethyloxetane (ETERNACOLL OXMA) (105 ° C)
t-BuMA: tertiary butyl methacrylate (107 ° C)
DMC78: dimethylamine ethyl methyl ammonium methacrylate (propylene acrylate DMC (manufactured by Mitsubishi Rayon)) (58 ° C)
MOI-BM: 2-[O-(1'-methylpropylene)carboxylamine methacrylate] (Karenz MOI-BM (manufactured by Showa Denko)) (60 ° C)
GMA: glycidyl acrylate (BLEMMER G (made by Nippon Oil & Fats))
The Tg value of Table 1 is a value calculated by the above formula, wherein the glass transition temperature value of MOI-BM of Production Example 17 is replaced with the value of 2-isocyanate ethyl methacrylate. Further, Production Example 18 is a value of the resin B-18' before the modification of glycidyl acrylate methyl ester.
<Method of Manufacturing Halide (D)>
(Manufacturing Example 25: Modulation of Halide D-1)
A halide (D-1) composed of CI Acid Red 289 and a resin B-1 having a cationic group in its side chain was produced by the following procedure.
Resin B-1 having a cationic group in its side chain was added to the water 2000, and the mixture was sufficiently stirred and stirred, and heated to 60 ° C. Further, an aqueous solution of 10 CI Acid Red 289 dissolved in 90 parts of water was prepared, and the previous resin solution was successively dropped. After dropping, the mixture was stirred at 60 ° C for 120 minutes to sufficiently carry out the reaction. The confirmation of the end point of the reaction is the dropping of the reaction liquid on the filter paper, and the end point is not bleed, and it is judged that the halide is obtained. After cooling to room temperature with stirring, the salt consisting of a counter anion of a resin having a cationic group in the side chain and a counter cation of CI acid red 289 is removed by suction filtration and washing with water, and then dried in a dryer. The halide on the filter paper was dehydrated and dried to obtain 32 parts of CI red 289 and a halide D-1 of a resin B-1 having a cationic group in the side chain.
(Production Examples 29 to 41, 43 to 47, and 49 to 59: Preparation of Halides D-5 to 17, 19 to 23, and 25 to 35)
In the same manner as in Production Example 25 except that the resin having a cationic group in the side chain and the dye were changed to those shown in Table 2, halides D-5 to 17, 19 to 23, and 25 to 35 were produced.
(Manufacturing Example 26: Modulation of Halide D-2)
The halide D-2 was produced in the same manner as in Production Example 25 except that the resin B-2 having a cationic group was used for 24 side chains.
(Manufacturing Example 27: Modulation of Halide D-3)
The halide D-3 was produced in the same manner as in Production Example 25 except that the resin B-3 having a cationic group in the side chain was used.
(Manufacturing Example 28: Modulation of Halide D-4)
The halide D-4 was produced in the same manner as in Production Example 25 except that the resin B-4 having a cationic group was used in 10 side chains.
(Manufacturing Example 42: Modulation of Halide D-18)
The halide D-18 was produced in the same manner as in Production Example 25 except that the resin B-18 having a cationic group of 64 side chains was used.
(Manufacturing Example 48: Modulation of Halide D-24)
The halide D-24 was produced in the same manner as in Production Example 25 except that the resin B-3 having a cationic group of 17 side chains and the 10 acid red 52 were used.
(halide (H-1))
The halide (H-1) consisting of CI Acid Red 289 and distearyl dimethyl ammonium chloride (QUARTAMIN D86P) was prepared by the following procedure.
11.5 QUARTAMIN D86P was added to 2000 parts of a 10% sodium hydroxide aqueous solution, and the mixture was thoroughly stirred and heated to 60 ° C. In addition, an aqueous solution of 10 CI Acid Red 289 dissolved in 90 parts of water was prepared, and the previous solution was successively dropped. After dropping, the mixture was stirred at 60 ° C for 120 minutes to sufficiently carry out the reaction. The confirmation of the end point of the reaction is the dropping of the reaction liquid on the filter paper, and the end point is not bleed, and it is judged that the halide is obtained. After being allowed to cool to room temperature while stirring, suction filtration was carried out, and after washing with water, the halide remaining on the filter paper was removed by a dryer and dried to obtain 17 CI Acid Red 289 and QUARTAMIN D86P halide (H-1). ).
(halide (H-2))
The halide (H-2) consisting of CI Acid Red 52 and monolauryltrimethylammonium chloride (QUARTAMIN 24P) was prepared by the following procedure.
8.1 QUARTAMIN 24P was added to 2000 parts of a 7% sodium hydroxide aqueous solution, and the mixture was thoroughly stirred and heated to 50 ° C. In addition, 90 aqueous solutions of 10 acid red 52 were dissolved in 90 parts of water, and the previous solution was successively dropped. After the dropwise addition, the mixture was stirred at 50 ° C for 120 minutes to sufficiently carry out the reaction. The confirmation of the end point of the reaction is the dropping of the reaction liquid on the filter paper, and the end point is not bleed, and it is judged that the halide is obtained. After being cooled to room temperature while stirring, the mixture was suction filtered, and after washing with water, the halide remaining on the filter paper was removed by a dryer and dried to obtain 16 CI Acid Red 52 and QUARTAMIN 24P halide (H-2). ).

[Examples 1 to 49, Comparative Examples 1 to 11]
[Example 1]
(production of blue coloring composition (DB-1))
The mixture was stirred and mixed uniformly, and then zirconia beads having a diameter of 0.5 mm were used and dispersed by an IGER mill ("Mini Model M-250 MKII" manufactured by Iger Japan Co., Ltd.) for 5 hours, and then 5.0. The filter was filtered to prepare a pigment dispersion (DB-1).
Halide (D-1) 4.0 minifine pigment (P-1) 7.0 resin binder solution 1 40.0 cyclohexanone 10.0 propylene glycol monomethyl ether acetate (PGMAB) 38.0 resin type dispersant (Chiba Japan Company system "EFKA4300") 1.0
[Examples 2 to 49, Comparative Examples 1 to 9]
(Blue coloring composition (DB-2 to 31, DB-50 to 52), purple coloring composition (DB-32, 33, DB-53, 54), red coloring composition (DB-34 to 49, DB) -55～58))
A colored composition (DB-2 to 58) was produced in the same manner as in Example 1 except that the halide and the fine pigment were changed to the compositions shown in Table 3.
[Comparative Example 10]
(production of blue coloring composition (DB-59))
A colored composition (DB-59) was produced in the same manner as in Example 1 except that the three-part halide H1 and the eight-part fine pigment P1 were used.
[Comparative Example 11]
(production of blue coloring composition (DB-60))
A colored composition (DB-60) was produced in the same manner as in Example 1 except that the five-part halide H1 and the six-part fine pigment P1 were used.
With respect to the obtained coloring compositions (DB-1 to 60), the heat resistance evaluation of the coating film, the foreign matter test, and the test for the storage stability of the colored composition were carried out by the following methods. The test results are shown in Table 3.
(Evaluation of heat resistance of coating film) The coloring composition (DB-1 to 60) was applied onto a glass substrate of 100 mm × 100 mm and a thickness of 1.1 mm by a spin coater, followed by drying at 70 ° C for 20 minutes, followed by 220 ° C. The film was heated for 30 minutes and allowed to cool to form a coated substrate. Adjusting the coating rotation number of the spin coater so that the film thickness of the coated substrate after heat treatment at 220 ° C will become 2.0 . The chromaticity of the obtained coating film under a C light source was measured by a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optics Co., Ltd.) ([L*(1), a*(1), b*(1)] ). Thereafter, as a heat resistance test, the film was heated at 230 ° C for 1 hour, and the chromaticity under the C light source ([L*(2), a*(2), b*(2)))) was measured by the following calculation. The color difference ΔEab* is calculated by the equation.

When ΔEab* is less than 3, there is no practical problem as a color filter, and if Δ Eab* is 1.5 or less, it is more preferable, and 1.0 or less is most preferable.
(Test for stability over time) On a glass substrate of 100 mm × 100 mm and a thickness of 1.1 mm, a coloring composition (DB-1 to 60) stored for half a year under a cold-keeping condition of 10 ° C was applied by a spin coater. Subsequently, the film was dried at 70 ° C for 20 minutes, then heated at 220 ° C for 30 minutes, and allowed to cool to form a coated substrate, and the coated substrate was observed at 500 magnifications by an optical microscope.
<Evaluation Benchmark>
◎: No foreign matter was detected. ○: Foreign matter was confirmed, but the allowable range was ×: Many foreign matter was generated, outside the allowable range.
(Test method for foreign matter in coating film)
A test substrate was prepared from the newly prepared color composition (DB-1 to 60), and the number of particles was counted and evaluated. First, on a transparent glass substrate of 100 mm × 100 mm and a thickness of 1.1 mm, the film thickness after drying using a spin coater becomes about 2.0. The test substrate was obtained by heating in an oven at 230 ° C for 20 minutes. Then, the surface observation (magnification: 500 times) was carried out using a metal microscope "BX60" manufactured by Olympus System Co., Ltd., and the number of particles which can be observed in any five fields due to penetration was calculated, and the following criteria were evaluated. Among the evaluation results, ◎ and ○ are small in number of foreign matter, and there are many Δ-type foreign matter, but they are not used in the problem-level gradation; × is unevenly coated due to foreign matter (plaque), which is equivalent to an unusable state. .
◎: ~ less than 5 ○: 5 or more, less than 20 Δ: 20 or more, less than 100 ×: 100 or more





AR289: CI Acid Red 289
AR52: CI Acid Red 52


In the examples 1 to 49, since the halide (D) obtained by reacting the resin (B) having a cationic group in the side chain with the anionic dye (C), the resin having a cationic group contains 4-grade ammonium. The salt is at least an acrylic resin containing at least one of a thermal bridging functional group or a Tg of 50 ° C or more, and therefore has good heat resistance and a ΔEab of 3.0 or less. Moreover, the storage stability was good, and the foreign matter of the coating film was also used as a color filter, and the result was good.
In Examples 10 to 15, 26 to 30, 36, 40, 44, and 48, since the heat-bridged functional group contained in the cationic group-containing resin is a hydroxyl group or a carboxyl group, heat resistance is further improved, and ΔEab is 1.5 or less. . In particular, in Examples 12 and 27, an acrylic resin having a glass transition temperature of 50 ° C or higher was used, and therefore the heat resistance was very good, and ΔEab was 1.0 or less.
In the example 5, the thermal bridging functional group contained in the resin having a cationic group is a hydroxyl group, and the acrylic resin having a glass transition temperature of 50 ° C or higher is excellent in heat resistance, and ΔEab is 1.0 or less.

In Comparative Examples 1 to 9, the resin having a cationic group does not contain a thermal bridging functional group, or the glass transition temperature of the resin having a cationic group is less than 50 degrees, so that the heat resistance of each case is not good, and ΔEab exceeds 3.
Further, Comparative Examples 10 and 11 were not only poor in heat resistance, but also poor in storage stability over time, and the results of the coating film foreign matter test were also slightly inferior.
[Example 50]
(Production of blue photosensitive coloring composition (R-1))
The following mixture was stirred and mixed uniformly to 1.0 The filter was filtered to obtain an alkali-developable resist material R-1.
Blue coloring composition (DB-1) 60 parts of resin binder solution 1 11.0 trimethylolpropane triacrylate 4.2
("Nippon Nakamura Chemical Co., Ltd.""NK ester ATMPT")
Photopolymerization initiator (IRGACURE 907, manufactured by Chiba Corporation, Japan) 1.2 sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 Cyclohexanone 5.2 propylene glycol monomethyl ether ethyl ester (PGMAC) 18.0 unit
[Examples 51 to 101 and Comparative Examples 12 to 22]
(Blue photosensitive coloring composition (DB-2 to 34, R-53 to 55, R-62, 63), violet photosensitive coloring composition (R-35 to 36, R-56 to 57), red photosensitive Production of sexual coloring composition (R-37-52, R-58-61)
An alkali-developing photosensitive coloring composition (R-2 to 63) was produced in the same manner as in Example 50 except that the coloring composition and the resin binder solution were changed to the coloring compositions shown in Table 4.
(Evaluation of photosensitive coloring composition)
The photosensitive coloring composition (R-1 to 63) obtained is subjected to a heat resistance evaluation of a coating film, a foreign matter test, a storage stability over time, a test for adhesion to a transparent substrate such as glass, and a solvent resistance. Sex test, alkali developability test. The foreign matter test, the adhesion test with a transparent substrate such as glass, the solvent resistance test, and the alkali developability test were carried out by the following methods. Other evaluations and test methods were carried out in the same manner as those described in Examples 1 to 49 and Comparative Examples 1 to 11.
(Test method for foreign matter in coating film)
A test substrate was prepared using the photosensitive coloring composition (R-1 to 63) which was just prepared, and the number of particles was calculated. First, a photosensitive coloring composition was applied to a transparent glass substrate of 100 mm × 100 mm and a thickness of 1.1 mm by a spin coater to have a dry film thickness of about 2.0. , drying at 70 ° C for 20 minutes, mediation width 100 The mask of the stripe-shaped opening portion was exposed to ultraviolet light having a total amount of light of 150 mJ/cm ² using an ultrahigh pressure mercury lamp, and the unexposed portion was washed with a 0.05% aqueous sodium hydroxide solution containing a surfactant to develop. Next, it was placed in a hot air oven at 230 ° C for 20 minutes to form a width of 100 on the substrate. A striped pattern was obtained to obtain a test substrate. Then, the surface observation (magnification: 500 times) was carried out using a metal microscope "BX60" manufactured by Olympus System Co., Ltd., and the number of observable particles was counted in any five fields by penetration, and the following reference needles were evaluated. Among the evaluation results, ◎ and ○ are small in number of foreign matter, and there are many Δ-type foreign matter, but they are not used in the problem-level gradation; × is unevenly coated due to foreign matter (plaque), which is equivalent to an unusable state. .
◎: ~ less than 5 ○: 5 or more, less than 20 Δ: 20 or more, less than 100 ×: 100 or more
(glass adhesion test method)
The test substrate was formed by the same procedure as the above-mentioned coating film foreign matter test, and was evaluated by confirming the chemical resistance. The obtained test substrate was immersed in a 5% aqueous sodium hydroxide solution at 25 ° C for 30 minutes, and the adhesion to the glass before and after the immersion was evaluated in three stages by visual observation.
○: Peeling Δ was not confirmed at all: peeling was confirmed slightly ×: peeling was confirmed
(solvent resistance test)
The test substrate was formed by the same procedure as the above-mentioned coating film foreign matter test, and after being immersed in the N-quinone ketal solution for 30 minutes, it was washed with ion-exchanged water and air-dried for 100 The pattern of the mask portion was observed using an optical microscope and evaluated. The evaluation level is as follows.
◎: No change in appearance and color, good ○: Part of the wrinkles, etc., but the color did not change, good Δ: some color loss occurred ×: peeling or fading occurred
(alkali developability test)
The photosensitive coloring composition (R-1 to 63) was applied to a transparent glass substrate of 100 mm × 100 mm and a thickness of 1.1 mm by a spin coater to have a dry film thickness of about 2.0. , drying at 70 ° C for 20 minutes, mediation width 100 The mask of the stripe-shaped opening was exposed to ultraviolet light having an integrated light amount of 150 mJ/cm ² using an ultrahigh pressure mercury lamp. When the unexposed portion was washed with a 0.05% sodium hydroxide aqueous solution containing a surfactant, development was carried out for an appropriate development time, +10 seconds, and +20 seconds, and a microscopic spectrophotometer (OSP manufactured by Olympus Optical Co., Ltd.) was used. -SP200") The surface of the developed glass was measured, and the alkali developability was judged by the presence or absence of residue.
◎: appropriate development time, no residue ○: appropriate development time + 10 seconds, no residue Δ: appropriate development time + 20 seconds, no residue ×: appropriate development time + 20 seconds, with residue



In the examples 50 to 101, since the halide (D) obtained by reacting the resin (B) having a cationic group in the side chain with the anionic dye (C), the resin having a cationic group contains 4-grade ammonium. The salt is at least an acrylic resin containing at least one of a thermal bridging functional group or a Tg of 50 ° C or more, and therefore has good heat resistance and a ΔEab of 3.0 or less. Further, the storage stability was good, and the foreign matter of the coating film was also used as a color filter, and the glass adhesion, solvent resistance, and alkali developability were also good results.
In Examples 62 to 67, 78 to 82, 88, 92, and 96, since the heat-bridged functional group contained in the cationic group-containing resin is a hydroxyl group and a carboxyl group, heat resistance is further improved, and ΔEab is 1.5 or less. Among them, in particular, Examples 64 and 79 are acrylic resins having a glass transition temperature of 50 ° C or higher, and therefore have excellent heat resistance, and ΔEab is 1.0 or less.
In the example 50, the thermal bridging functional group contained in the resin having a cationic group is a hydroxyl group, and the acrylic resin having a glass transition temperature of 50 ° C or higher is excellent in heat resistance, and ΔEab is 1.0 or less.
In Examples 62 to 67, 78 to 82, 88, 92, and 96, since a hydroxyl group and a carboxyl group were contained as a thermal bridging functional group, a strong film was formed by thermal bridging, and as a result, solvent resistance was very good. Further, since the carboxyl group was contained, no residue remained, and as a result, the alkali developability was very good.
In Comparative Examples 12 to 20, the resin having a cationic group does not contain a thermal bridging functional group, or the glass transition temperature of the resin having a cationic group is less than 50 degrees, so that heat resistance of each case is poor, and ΔEab exceeds 3. Further, as a result, solvent resistance was also poor.
In Comparative Examples 21 and 22, not only heat resistance was poor, but also stability over time, glass adhesion, and solvent resistance were poor, and the results of the coating film foreign matter test were also slightly inferior.
<Production of Color Filters>
The red photosensitive coloring composition, the blue photosensitive coloring composition, and the green photosensitive coloring composition for producing a color filter are combined with the photosensitive coloring composition of the present invention.
(Production of red photosensitive coloring composition (RR-1))
After the mixture of the following composition was stirred and mixed uniformly, the zirconia beads having a diameter of 0.5 mm were dispersed in an IGER mill ("Mini Model M-250 MKII" manufactured by Iger Japan Co., Ltd.) for 5 hours, and then 5.0. The filter was filtered to produce a red colored composition (DR-1).
Red pigment (CI Pigment Red 254) 9.6 red pigment (CI Pigment Red 177) 2.4 Resin dispersant ("EFKA4300" manufactured by Chiba Japan Co., Ltd.) 1.0 resin binder solution 1 35.0 propylene glycol monomethyl ether acetate 52.0 Next, the mixture of the following composition is stirred and mixed uniformly to 1.0. The filter is filtered to produce a red photosensitive coloring composition (RR-1)
Red coloring composition (DR-1) 42.0 resin binder solution 1 13.2 photopolymerizable monomer (ARONIX M400 manufactured by Toagosei Co., Ltd.) 2.8 photopolymerization initiator (IRGACURE 907, manufactured by Chiba Corporation, Japan) 2.0 sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.4 parts of ethylene glycol monomethyl ether ethyl ester 36.9 parts
(Production of blue photosensitive coloring composition (RB-1))
After the mixture of the following composition was stirred and mixed uniformly, the zirconia beads having a diameter of 0.5 mm were dispersed in an IGER mill ("Mini Model M-250 MKII" manufactured by Iger Japan Co., Ltd.) for 5 hours, and then 5.0. The filter was filtered to produce a blue colored composition (DB-1).
Blue pigment (CI Pigment Blue 15:6) 7.2 purple pigment (CI Pigment Violet 23) 4.8 resin type dispersant ("EFKA4300" manufactured by Chiba Japan Co., Ltd.) 1.0 resin binder solution 1 17.5 propylene glycol monomethyl ether B Acid ester 69.5, next, the mixture of the following composition is stirred and mixed uniformly, to 1.0 The filter is filtered to produce a blue photosensitive coloring composition (RB-1)
Blue coloring composition (DB-1) 34.0 resin binder solution 1 7.6 photopolymerizable monomer (ARONIX M400 manufactured by Toagosei Co., Ltd.) 3.3 Photopolymerization initiator (IRGACURE 907, manufactured by Chiba Corporation, Japan) ) 2.0 sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.4 parts of ethylene glycol monomethyl ether ethyl ester 52.7 parts
(Production of green photosensitive coloring composition (RG-1))
After the mixture of the following composition was stirred and mixed uniformly, the zirconia beads having a diameter of 0.5 mm were dispersed in an IGER mill ("Mini Model M-250 MKII" manufactured by Iger Japan Co., Ltd.) for 5 hours, and then 5.0. The filter was filtered to produce a green coloring composition (DG-1).
Green pigment (CI pigment green 58) 12.0 resin dispersant ("EFKA4300" manufactured by Chiba Japan Co., Ltd.) 1.0 resin binder solution 1 35.0 parts propylene glycol monomethyl ether acetate 52.0 parts Next, a mixture of the following components After mixing and mixing evenly, to 1.0 The filter is filtered to produce a green photosensitive coloring composition (RG-1)
Green coloring composition (DG-1) 34.0 resin binder solution 1 15.2 photopolymerizable monomer (ARONIX M400 manufactured by Toagosei Co., Ltd.) 3.3 Photopolymerization initiator (IRGACURE 907, manufactured by Chiba Corporation, Japan) 2.0 sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.4 part of ethylene glycol monomethyl ether ethyl ester 45.1 on a glass substrate, and patterned the black matrix on the substrate to rotate The coater was applied with a red photosensitive coloring composition (RR-1) and applied to have a film thickness of x=0.640 to form a colored film. In the coating film, an ultraviolet ray of 300 mJ/cm 2 was irradiated with an ultrahigh pressure mercury lamp by interposing a photomask. Next, spray development was carried out by an alkali developing solution composed of a 0.2% by weight aqueous sodium carbonate solution, and the unexposed portion was removed, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C for 20 minutes to form a red filter segment. . By applying the blue photosensitive coloring composition (R-2) of the present invention in the same manner, the film thickness becomes 2.0. On the other hand, a blue color filter segment was formed, and then a green photosensitive coloring composition (RG-1) was used, and a green filter segment was formed to have a film thickness of y=0.600 to obtain a color filter.
Further, the red photosensitive coloring composition (R-47), the blue photosensitive coloring composition (RB-1), and the green photosensitive coloring composition (RG-1) of the present invention were used in the same manner to obtain a filter region. segment.
By using the photosensitive coloring composition of the present invention, the heat resistance of the color filter, the foreign matter test, the adhesion to a transparent substrate such as glass, the solvent resistance, and the alkali developability are improved, so that it can be suitably used. .

no

Claims (11)

A coloring composition for a color filter, characterized by comprising a coloring agent, a resin binder and an organic solvent;
The coloring agent contains a halide obtained by reacting a resin having a cationic group in a side chain with an anionic dye;
The resin having a cationic group in the side chain includes an acrylic resin having a structural unit represented by the following general formula (1); the acrylic resin is selected from an acrylic resin having a thermal bridging functional group, and has a glass transition temperature of 50 ° C or higher. An acrylic resin, and an acrylic resin having a heat-bridged functional group and having a glass transition temperature of 50 ° C or higher; (In the general formula (1), R ₁ represents a hydrogen atom, or a substituted or unsubstituted alkyl group. R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group which may be substituted, or may be substituted. An alkenyl group or an aryl group which may be substituted, and _{two of} R ₂ , R ₃ and R ₄ may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, -CONH-R ₅ - or -COO-R ₅ -, R ₅ represents an alkylene group. Y ^- represents an inorganic or organic anion.) The coloring composition for a color filter according to the first aspect of the invention, wherein the heat-bridged functional group is selected from the group consisting of a hydroxyl group, a carboxyl group, an oxetanyl group, a tertiary butyl group, an isocyanate group, and a (meth) group. At least one of the group consisting of acryl groups. A coloring composition for a color filter according to the first or second aspect of the invention, wherein the acrylic resin comprising the structural unit represented by the above general formula (1) is a copolymer comprising a structural unit having a thermal bridging functional group. The copolymer is contained in an amount of 100% by weight in total, and includes 10 to 35% by weight of the structural unit having the aforementioned thermally bridged functional group. The coloring composition for a color filter according to any one of claims 1 to 3, wherein the heat-bridged functional group contains a hydroxyl group. The coloring composition for a color filter according to any one of claims 1 to 4, wherein the heat-bridged functional group is a hydroxyl group and a carboxyl group. The colored composition for a color filter according to any one of the items 1 to 5, wherein the ammonium salt of the acrylic resin having the structural unit represented by the above general formula (1) is 10 to 200 mgKOH/g. . The coloring composition for a color filter according to any one of the items 1 to 6, wherein the halide is in an aqueous solution, and a resin having a cationic group and an anionic dye are mixed in the side chain, and the removal is performed by A compound prepared by a side chain having a counter anion of a cationic group resin and a counter cation of an anionic dye. The colored composition for a color filter according to any one of the items 1 to 7, wherein the main component of the organic solvent is Propylene glycol monomethyl ether acetate. The coloring composition for a color filter according to any one of the items 1 to 8, wherein the coloring agent further contains a pigment. The coloring composition for a color filter according to any one of the items 1 to 9, further comprising a photopolymerizable monomer and/or a photopolymerization initiator. A color filter formed by a coloring composition for a color filter according to any one of claims 1 to 10.