JP2013077035A - Coloring composition for color filter, color filter, and liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition for color filters which realizes both high contrast and dispersion stability, and has excellent developability when a brominated zinc phthalocyanine green pigment is used.SOLUTION: A coloring composition for color filters and usage of the same are provided. The coloring composition for the color filters contains: pigment dispersion liquid containing pigment, a solvent and a dispersion agent, and binder resin. The pigment is a pigment containing brominated zinc phthalocyanine, and the binder resin is resin obtained by adding unsaturated monobasic acid to at least part of epoxy groups which a copolymer of an epoxy group containing (meth)acrylate and another radical polymerizable monomer has or alkali-soluble resin obtained by adding polybasic acid anhydride to at least part of hydroxyl groups produced by this addition reaction.

Description

  The present invention relates to a coloring composition for a color filter, a color filter, and a liquid crystal display device. More specifically, a pigment dispersion in which a green pigment containing brominated zinc phthalocyanine is dispersed using a solvent and a dispersant, a coloring composition for a color filter containing a specific binder resin, and a pixel using this coloring composition The present invention relates to a formed color filter and a liquid crystal display device including the color filter.

Conventionally, pigment dispersion methods, dyeing methods, electrodeposition methods, and printing methods are known as methods for producing color filters used in liquid crystal display devices and the like. Among these, from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, etc., a pigment dispersion method having excellent characteristics on average is most widely adopted.
In recent years, the trend of technological innovation is rapid, and color filters are required to have higher transmission, higher contrast, and higher density. As the color material that determines the color of the color filter, pigments are generally used from the viewpoint of heat resistance, light resistance, etc., but as a pigment type, the intrinsic transmission absorption spectrum matches the phosphor spectrum of the backlight in the visible light region. Are preferably used. For example, as a green pigment, a copper halide phthalocyanine green pigment has long been put into practical use in combination with various yellow pigments.

  On the other hand, in order to increase the contrast, it is important to suppress light scattering in the color filter layer to the minimum, and the organic pigment is reduced to a size of several tens of nanometers as a primary particle diameter by a solvent salt milling method, a dry milling method, or the like. In general, it is used after atomization. However, since the surface area increases as the particle size decreases, the amount of adsorption of the polymer dispersant or the like is insufficient and reaggregation is likely to occur, and the dispersion system tends to become unstable. Therefore, in recent years, it has become an extremely important technical issue how to stably make an organic pigment atomized in order to increase contrast exist as a dispersion.

  Under these circumstances, in recent years, a new phthalocyanine green pigment having a specific hue as described in Patent Documents 1 and 2 has been proposed for increasing the brightness of green pixels, and is differentiated from conventional copper halide phthalocyanine green pigments. Was realized. However, when the new green pigment is refined to increase the contrast, the dispersion stability is extremely lowered, and the effect of light scattering by the secondary aggregates causes the contrast to be insufficient for television. was there.

In order to solve such problems, for example, Patent Document 2 discloses (meth) acrylic acid-based (co) polymer polyflow No. 75, No. 90, No. 95 as a dispersant for preparing a pigment dispersion. (Manufactured by Kyoeisha Yushi Chemical Co., Ltd.), Megafuck F171, F172, F173 (manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (manufactured by Sumitomo 3M), Solsparse 13240, 20000, 24000, 26000, 28000, etc. Dispersants (manufactured by Avicia), Dispersic 111, 161, 162, 163, 164, 182, 2000, 2001, etc.
It has been shown that polymer dispersants such as Ajispar PB711, PB411, PB111, PB821, and PB822 are used as polymer dispersants such as Ajinomoto Fine-Techno Co., Ltd. The system dispersant “BYK-2001” is exemplified. However, according to the verification by the present inventors, even when these polymer dispersants are used, they are insufficient to maintain the dispersion stability of the above-mentioned finely atomized new phthalocyanine green pigment. There were problems such as viscosity and contrast reduction due to aggregation over time.

Furthermore, it turned out that the coloring composition for color filters using the new atomized phthalocyanine green pigment dispersion has poor solubility in a developer and it is difficult to produce a substantial color filter.
Usually, even if a slight increase in viscosity is observed in the color pigment dispersion, the viscosity stability is often improved by adding a binder resin, a solvent, and the like to the final color composition for color filter. This new phthalocyanine green pigment dispersion increased rather vigorously, and it was found that viscosity stability was difficult to ensure. In addition, it has also been found that foreign matters are likely to be generated over time during storage as a coloring composition for a color filter, and the contrast is also lowered over time.

JP 2004-70342 A JP 2004-70343 A

The present invention has been made in view of the above-mentioned problems, and its object is as follows.
(A) When a brominated zinc phthalocyanine green pigment is used for the purpose of increasing the brightness of a green pixel, (1) dissolution time in the developer, (2) increase in viscosity over time, (3) contrast over time (4) To provide a coloring composition for a color filter having improved high contrast, excellent dispersion stability and good developability, with improved foreign matter generation over time, and the like.
(B) To provide a high-quality color filter using the coloring composition for a color filter.
(C) To provide a high-quality liquid crystal display device using the color filter substrate.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a dispersion containing a brominated zinc phthalocyanine green pigment in combination with a certain binder resin, thereby providing a sufficiently high contrast for a liquid crystal television. It has been found that sufficient dispersion stability, developability, etc. can be realized even with pigments atomized to be in the region. Furthermore, using a new phthalocyanine green pigment dispersion that maintains dispersion stability, it is very important to use a resin having a specific structure in combination in order to construct a color filter coloring composition that solves the above problems. I found it effective. The present invention has been accomplished based on these findings.

  That is, the present invention comprises a plurality of related inventions, and the gist of each invention is as follows.

  (1) A coloring composition for a color filter containing a pigment dispersion containing a pigment, a solvent and a dispersant and a binder resin, wherein the pigment is a pigment containing brominated zinc phthalocyanine, and the binder resin Is obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group of the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer. A coloring composition for a color filter, which is an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of a resin or a hydroxyl group generated by the addition reaction.

  (2) The epoxy group-containing (meth) acrylate constituting the binder resin is glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate and 4- The coloring composition according to (1), which is at least one compound selected from the group consisting of hydroxybutyl (meth) acrylate glycidyl ether.

(3) Another radical polymerizable monomer constituting the binder resin is represented by the following general formula (2).
[In the formula (2), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents the following general formula (1)
In formula (1), R ^{1 to} R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, but R ⁷ and R ⁸ may be linked to each other to form a ring. . (1) or (2), which is either or both of a mono (meth) acrylate represented by the following formula: and at least one compound selected from the group consisting of styrene, benzyl (meth) acrylate, and monomaleimide. The coloring composition as described.

  (4) The colored composition according to any one of (1) to (3), wherein the unsaturated monobasic acid constituting the binder resin is an unsaturated carboxylic acid having an ethylenic double bond.

  (5) The polybasic acid anhydride constituting the binder resin is maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, trimellitic anhydride, The colored composition according to any one of (1) to (4), which is at least one compound selected from the group consisting of pyromellitic anhydride, benzophenonetetracarboxylic anhydride, and biphenyltetracarboxylic anhydride.

  (6) The colored composition according to any one of (1) to (5), further containing a photopolymerizable monomer.

  (7) The photopolymerizable monomer is an addition-polymerizable compound having at least one ethylenic double bond, and the compound has a molecular weight of 650 or less and a double bond equivalent of 150 or less. (6) The coloring composition as described in.

  (8) The dispersant is a block copolymer comprising an A block having solvophilicity and a B block having a functional group containing a nitrogen atom, and the amine value thereof is 80 mgKOH / g or more and 150 mgKOH / g or less (effective solid The colored composition according to any one of (1) to (7), which is a dispersant containing a block copolymer in terms of a fraction.

  (9) The colored composition according to any one of (1) to (8), wherein an average primary particle size of the pigment is 0.04 μm or less.

  (10) A coloring composition for a color filter containing a pigment dispersion containing a pigment, a solvent and a dispersant, a binder resin, and a photopolymerizable monomer, wherein the pigment contains a brominated zinc phthalocyanine The photopolymerizable monomer is an addition-polymerizable compound having at least one ethylenic double bond, the compound having a molecular weight of 650 or less and a double bond equivalent of 150 or less. A coloring composition for a color filter.

  (11) The colored composition according to any one of (1) to (10), further containing a photopolymerization initiator.

  (12) A color filter comprising pixels formed using the colored composition according to any one of (1) to (11).

  (13) A liquid crystal display device comprising the color filter according to (12) and a liquid crystal driving substrate facing each other, and liquid crystal sealed therein.

The present invention has the following effects.
(A) When a brominated zinc phthalocyanine green pigment is used for the purpose of increasing the brightness of a green pixel, (1) the development time is short, (2) there is little increase in viscosity over time, and (3) the contrast is good over time. It is possible to provide a coloring composition for a color filter that is difficult to decrease, (4) less likely to generate foreign matter over time, and (5) can form pixels with less “over” and excellent linearity.
(B) A high-quality color filter can be provided using the coloring composition for a color filter.
(C) A high-quality liquid crystal display device using the color filter can be provided.

The constituent requirements and the like of the present invention will be described in detail below, but these are examples of embodiments of the present invention and are not limited to these contents.
“(Meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) acrylic acid” is “ It means “acrylic acid and / or methacrylic acid”. Further, “total solid content” means all components other than the solvent components described later, which are contained in the pigment dispersion or the colored composition.

In the present invention, the weight average molecular weight refers to a polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
In the present invention, the “amine value” means an amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the weight of KOH equivalent to the amount of base per 1 g of the solid content of the dispersant. . The measuring method will be described later.

[1] Pigment dispersion First, each component of the pigment dispersion according to the present invention will be described. The pigment dispersion according to the present invention contains a pigment, a solvent, and a dispersant as essential components, and if necessary, may contain other additives other than the above components.
Hereinafter, each component will be described.

[1-1] Pigment As a pigment used in the pigment dispersant according to the present invention, a brominated zinc phthalocyanine pigment is essential.
Ordinary zinc phthalocyanine has 16 hydrogen atoms in one molecule, and the brominated zinc phthalocyanine pigment used in the present invention is one obtained by substituting these hydrogen atoms with bromine or chlorine atoms. Of these, brominated zinc phthalocyanine containing an average of 13 or more bromine atoms in one molecule is preferable because it exhibits extremely high transmittance and is suitable for forming a green pixel of a color filter. Furthermore, brominated zinc phthalocyanine having 13 to 16 bromine atoms in one molecule and not containing chlorine or having an average of 3 or less in one molecule is preferable, and in particular, an average of 14 bromine atoms in one molecule is 14 Brominated zinc phthalocyanine having ˜16 and not containing chlorine atoms in one molecule or having an average of 2 or less is preferred.

  Such a brominated zinc phthalocyanine pigment can be produced by a known production method disclosed in JP-A-50-130816. For example, a method of synthesizing a pigment using phthalic acid or phthalonitrile in which some or all of the hydrogen atoms of the aromatic ring are substituted with a halogen atom such as chlorine in addition to bromine as an appropriate starting material. In this case, a catalyst such as ammonium molybdate may be used as necessary.

  As another method, a method of brominating zinc phthalocyanine with bromine gas in a melt of about 110 to 170 ° C. composed of a mixture of aluminum chloride, sodium chloride, sodium bromide and the like can be mentioned. In this method, the ratio of various brominated zinc phthalocyanines with different bromine contents can be adjusted by adjusting the ratio of chloride and bromide in the molten salt, or by changing the amount of chlorine gas introduced and the reaction time. Can be controlled arbitrarily.

When the obtained mixture is put into an acidic aqueous solution such as hydrochloric acid after the reaction is completed, the produced brominated zinc phthalocyanine is precipitated. Thereafter, post-treatment such as filtration, washing and drying is performed to obtain brominated zinc phthalocyanine.
The brominated zinc phthalocyanine pigment thus obtained is dry-ground in a pulverizer such as an attritor, ball mill, vibration mill, vibration ball mill or the like as necessary, and then pigmented by a solvent salt milling method or a solvent boiling method. Thus, a brominated zinc phthalocyanine pigment that develops a green color with high transmittance and contrast can be obtained. The pigmentation method is not particularly limited, but it is preferable to employ a solvent salt milling treatment from the viewpoint that crystal growth can be easily suppressed and pigment particles having a large specific surface area can be obtained.

  Solvent salt milling means kneading and grinding a crude pigment immediately after synthesis, an inorganic salt, and an organic solvent. Specifically, a crude pigment, an inorganic salt, and an organic solvent that does not dissolve it are charged into a kneader, and kneading and grinding are performed therein. The kneading machine at this time has, for example, a kneader, a mix muller, or a pulverizing space in which a gap portion of a rotating disk concentric with an annular fixed disk as described in JP-A-2006-77062 is formed. A continuous kneader or the like is preferably used.

  As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used. Further, the particle diameter of these inorganic salts is more preferably 0.5 to 50 μm. Such an inorganic salt can be easily obtained by pulverizing a normal inorganic salt.

  The brominated zinc phthalocyanine thus obtained may be used alone, but the brominated zinc phthalocyanine having a different bromination rate or chlorination rate or other metals as long as the effect of the present invention is not impaired. It can be used by mixing with brominated phthalocyanine substituted with metal. By changing the chlorination rate and bromination rate, or by changing the central metal, it is expected that the color tone of the pigment will change and that variations in the reproducible hue will increase. In addition, C.I. I. You may mix with halogenated copper phthalocyanines, such as pigment green (PG) 36 or 7.

The average primary particle size of the green pigment containing brominated zinc phthalocyanine is usually 0.1 μm or less, preferably 0.04 μm or less, more preferably 0.03 μm or less, and usually 0.005 μm or more. If the average primary particle size is too large, the depolarization characteristics will deteriorate and the contrast will be insufficient, and if it is bad, the transmittance will be lowered. , Production problems such as a decrease in the yield of color filters due to protrusion foreign matter and the cause of blockage of the process filter may occur.On the other hand, if it is too small, the dispersion stability is poor due to an increase in specific surface area, Problems such as deterioration of heat resistance and light resistance due to the pigment approaching the molecular state may occur.

  The average primary particle size of the pigment is determined by ultrasonically dispersing the pigment to be measured in chloroform, dropping it on a collodion film-attached mesh, drying it, and observing it with a transmission electron microscope (TEM). From this image, the primary particle size was measured to determine the average particle size.

In addition, the hue can be combined with at least one yellow pigment. Examples of yellow pigments include C.I. I. Pigment Yellow (P.Y.) 1, 1: 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 1
73, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 199, 200, 202, 203, 204, 205, 206, 207, 208 and the like. Y. 83, 138, 139, 150, 180, 185 are preferred. Y. 138, 150 and 185 are preferred. These can be used alone or in combination of two or more.
The average primary particle diameter of these yellow pigments is usually 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.04 μm or less. When the pigment is atomized, a technique such as the solvent salt milling described above is preferably used.

[1-2] Solvent
The solvent has a function of adjusting the viscosity by dissolving or dispersing components other than those described above in addition to the pigment and the dispersant in the pigment dispersion according to the present invention and the coloring composition described later.
Any solvent can be used as long as it can dissolve or disperse each component, and a solvent having a boiling point in the range of 100 to 200 ° C. is preferably selected. More preferably, it has a boiling point of 120-170 ° C.

Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl. Glycol monoalkyl ethers such as ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycol alkyl ether acetates such as ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;

Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;

Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as propyl, butyl 3-methoxypropionate, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Examples thereof include nitriles such as acetonitrile and benzonitrile.

Examples of commercially available solvents corresponding to the above include mineral spirit, Valsol # 2, Apco # 18 solvent, Apco thinner, and Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like.
These solvents may be used alone or in combination of two or more.

Glycol alkyl ether acetates are preferred from the viewpoints of good balance between the solvent, applicability, surface tension, etc., and relatively high solubility of the components in the composition.
In addition, glycol alkyl ether acetates may be used alone or in combination with other solvents. As the solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. In addition, glycol monoalkyl ethers are highly polar,
If the amount added is too large, the pigment tends to aggregate, and the storage stability tends to decrease, for example, the viscosity of the colored composition obtained later increases. Therefore, the proportion of glycol monoalkyl ethers in the solvent is 5% by weight. % To 30% by weight is preferable, and 5% to 20% by weight is more preferable.

It is also preferable to use a solvent having a boiling point of 150 ° C. or higher in combination. When such a high boiling point solvent is used in combination, the colored composition becomes difficult to dry, but it has the effect of making it difficult for the pigment dispersion to break down due to rapid drying. The content of the high boiling point solvent is preferably 3% by weight to 50% by weight, more preferably 5% by weight to 40% by weight, and particularly preferably 5% by weight to 30% by weight with respect to the solvent. If the amount of the high-boiling solvent is too small, for example, coloring material components may precipitate and solidify at the tip of the slit nozzle to cause a foreign matter defect. There is a concern that it may cause problems such as tact defects in the vacuum drying process and pre-baked pin marks in the color filter manufacturing process.
The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be separately contained.

  Although there is no restriction | limiting in particular in content of the solvent which occupies for the whole coloring composition of this invention, The upper limit shall be 99 weight% or less normally. When the solvent exceeds 99% by weight, the amount of the pigment, the dispersant, etc. becomes too small, which is inappropriate for forming a coating film. On the other hand, the lower limit of the solvent content is usually 75% by weight or more, preferably 80% by weight or more, and more preferably 82% by weight or more in consideration of viscosity suitable for coating.

[1-3] Dispersant The dispersant used in the pigment dispersion according to the present invention is not particularly limited as long as it is a dispersant that can be usually used in a pigment dispersion or a color composition for a color filter. A block copolymer comprising a solvophilic A block and a B block having a functional group containing a nitrogen atom, the amine value of which is 80 mg KOH / g or more and 150 mg KOH / g or less (in terms of effective solid content) Polymers are particularly preferred.

Among these, a (meth) acrylic block copolymer is preferable. Hereinafter, the dispersant will be described by taking a case of a (meth) acrylic block copolymer as an example.
The B block has a functional group containing a nitrogen atom, and the functional group is preferably a primary to tertiary amino group. The content ratio of the primary to tertiary amino groups is preferably 20 mol% or more, more preferably 50 mol% or more of the entire nitrogen atom-containing functional group. As the primary to tertiary amino group, preferably —NR ⁴¹ R ⁴² (wherein R ⁴¹ and R ⁴² are each independently a cyclic or chain alkyl group or substituent which may have a substituent). An aryl group which may have a substituent, or an aralkyl group which may have a substituent is preferable. The

(However, R ⁴¹ and R ⁴² have the same meanings as R ⁴¹ and R ⁴² described above, R ⁴³ represents an alkylene group having 1 or more carbon atoms, and R ⁴⁴ represents a hydrogen atom or a methyl group.)
Among them, R ⁴¹ and R ⁴² are preferably a methyl group, R ⁴³ is preferably a methylene group or an ethylene group, and R ⁴⁴ is preferably a hydrogen atom or a methyl group. As such a partial structure, a structure derived from dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate represented by the following formula is particularly preferably used.

(Wherein R ⁴⁴ has the same meaning as described above.)
Two or more kinds of the partial structure containing an amino group as described above may be contained in one B block. In that case, two or more amino group-containing partial structures may be contained in the B block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain an amino group may be partially contained in the B block, and examples of such a partial structure include a partial structure derived from a (meth) acrylic acid ester monomer. The content of such a partial structure not containing an amino group in the B block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably it is not included.
On the other hand, the solvophilic A block that constitutes the block copolymer of the dispersant does not have a nitrogen atom-containing functional group such as the amino group described above, and can copolymerize with the monomer that constitutes the B block described above. If it consists of a monomer, there will be no restriction | limiting in particular.

  Examples of the solvophilic A block include styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, isopropyl (meth) acrylate, Butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, polyethylene glycol ( (Meth) acrylate monomers such as (meth) acrylate and polypropylene glycol (meth) acrylate; (meth) acrylate monomers such as (meth) acrylic chloride; vinyl acetate monomers; allyl glycidyl ether Polymer structure where the copolymerized comonomers such glycidyl ether monomers such as crotonic acid glycidyl ether.

  Among them, the A block includes a polyalkylene glycol (meth) acrylate such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate as a copolymerization component (that is, a partial structure derived from polyalkylene glycol (meth) acrylate). In particular, an A block having a partial structure represented by the following formula (VIII) is preferable.

(In the formula, n represents an integer of 1 to 5, and R ₁ represents a hydrogen atom or a methyl group.)
The partial structure represented by the above formula (VIII) is particularly preferably contained in the A block in an amount of 5 to 40 mol%.
Although the detailed mechanism of action is unknown, it has a partial structure derived from polyalkylene glycol (meth) acrylate, in particular a partial structure represented by the above formula, so that it is possible to increase hydrogen bonding properties, It is thought that the affinity for the dispersion improves and the stability of the dispersion increases.

The (meth) acrylic dispersant used in the present invention is an AB block or ABA block copolymeric polymer compound composed of such an A block and a B block. Of these, AB block copolymers are preferred. Such a block copolymer is prepared, for example, by the living polymerization method shown below.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method.
In the anion living polymerization method, the polymerization active species is an anion, and is represented by the following scheme, for example.

  In the radical living polymerization method (nitroxyl method, ATRP method), the polymerization active species is a radical, and is represented by the following scheme, for example.

  In synthesizing such a (meth) acrylic block copolymer, JP-A-60-89452, JP-A-9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12 , 79 (1984), BC Anderson, GD Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), K. Hatada, K Ute, et al, Polym. J.18, 1037 (1986), Koichi Right-hand, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers, 46, 189 ( 1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al. , Macromolecules, 20, 1473 (1987), K. Matyaszewski et al, Chem. Rev. 2001, 101, 2921-2990, etc., can be used.

The amine value in 1 g of the solid content of the AB block copolymer and the ABA block copolymer according to the present invention is preferably 90 to 150 mgKOH / g, more preferably 100 to 140 mgKOH / g.
If the amine value is too low, the adsorptive power to the pigment surface becomes insufficient, and sufficient dispersion stability cannot be obtained. On the other hand, when the amine value is too high, it means that the molecular weight of the A block is insufficient, and thus the dispersion stability is poor. In other words, the amine value for expressing the optimum dispersibility is in the above range.

The amine value of the dispersant (in terms of effective solid content) is represented by the weight of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method. Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S)
(W: represents the amount of the dispersant sample weighed [g], V: represents the titration amount at the end of titration [mL], and S represents the solid content concentration [wt%] of the dispersant sample.)
The acid value of the block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but generally it is preferably lower, usually 50 mgKOH / g or less, preferably 40 or less, more preferably 30 or less.
In the present invention, a commercially available (meth) acrylic block copolymer having the same structure as described above can also be applied.

  The pigment dispersion according to the present invention is, for example, an AB block copolymer or an ABA block copolymer comprising an A block having a solvophilic property and a B block having a functional group containing a nitrogen atom as a dispersant. It is preferable to use one having a value of 80 mgKOH / g (in terms of effective solid content) or more. By using such a block copolymer as a dispersant, it is possible to satisfy both strong polymer adsorption on the pigment surface and high solvent affinity at the same time, so that high dispersion stability can be expressed. Further, by increasing the amine value, the adsorptive power on the surface of the pigment that has been particularly acid-treated is increased, so that the dispersion stability is further improved.

In particular, it is preferable that at least 20 mol% or more of the functional group components containing nitrogen atoms in the B block are primary to tertiary amino groups. If it is less than this, even if the amine value is 80 mgKOH / g or more, sufficient adsorption power cannot be obtained, and high dispersion stability may not be obtained.
When the average primary particle size of the pigment is small, the specific surface area increases, so that the amount of dispersant adsorbed per unit area decreases. In such a case, the above-described dispersant composed of the AB block copolymer or ABA block copolymer is particularly preferably used because the difference in the effect is very remarkable as compared with the dispersant having another structure. Is.

  The pigment dispersion and the coloring composition according to the present invention may contain a dispersant other than the dispersant composed of the block copolymer described above. Examples of such dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyesters. And the like, and the like. Specific examples of such a dispersant include trade names of EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Geneca), Examples thereof include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (manufactured by Ajinomoto Co., Inc.) and the like. These dispersants may be used alone, or two or more dispersants including the above-described dispersant composed of a block copolymer may be mixed and used in any combination and ratio. .

[1-4] Dispersion aid
In the pigment dispersion according to the present invention, a pigment derivative or the like may be added as a dispersion aid for improving the dispersibility of the pigment and improving the dispersion stability. As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolo Derivatives such as pyrrole and dioxazine pigments may be mentioned. Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, preferably a sulfonamide group and a quaternary salt thereof, and a sulfonic acid group, and more preferably a sulfonic acid group. In addition, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions. Specific examples of pigment derivatives include azo pigment sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, isoindoline pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, quinacridone pigment sulfonic acid derivatives, Examples thereof include sulfonic acid derivatives of diketopyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments.

Among these, a pigment derivative having little interference with the hue of the green pigment dispersion is preferable, and a sulfonic acid derivative of Pigment Yellow 138, a sulfonic acid derivative of Pigment Yellow 139, and a sulfonic acid derivative of Pigment Blue 15 are more preferable.
The addition amount of the pigment derivative is usually 0.1% by weight or more, usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less based on the pigment. is there. This is because if the addition amount is small, the effect tends to be hardly exhibited, and conversely if the addition amount is too large, the dispersibility and dispersion stability may be deteriorated.

[1-5] Dispersing resin
The pigment dispersion according to the present invention may contain a part or all of a resin selected from binder resins that can be used in the colored composition. Specifically, in the dispersion treatment step in the preparation of the pigment dispersion described later, by including a binder resin together with the above-described dispersant, the binder resin contributes to dispersion stability through a synergistic effect with the dispersant, As a result, the amount of dispersant added may be reduced, which is preferable. As described above, the resin used in the dispersion treatment step may be referred to as a dispersion resin.

[2] Coloring composition
The colored composition of the present invention comprises at least the above-described pigment dispersion and a binder resin “copolymer with respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer. A resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group possessed by, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction] [ 2-1-1]. Furthermore, the colored composition of the present invention may contain other binder resin, for example, “(meth) acrylic resin” [2-1-2] or the like as long as the effects of the present invention are not impaired.

The other components constituting the coloring composition can be used without particular limitation as long as they can be used as a color filter forming material. For example, a thermosetting resin composition used in a so-called lift-off type color filter manufacturing process described in JP-A-60-184202 and the like, and an inkjet-type color filter manufacturing described in JP-A-2004-220036 Any type of resin composition may be used such as a thermosetting resin composition used in the process and a photopolymerizable resin composition described later. When the coloring composition is a photopolymerizable composition, a photopolymerization initiator system is an essential component.
Hereinafter, the case where the coloring composition of the present invention is a photopolymerizable resin composition will be described in detail, but the present invention is not limited thereto.

[2-1] Binder resin
Hereinafter, the binder resin used in the present invention will be described in detail.

  [2-1-1] Unsaturated monobasic acid in at least part of the epoxy group of the copolymer with respect to the copolymer of epoxy group-containing (meth) acrylate and other radical polymerizable monomer Or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction

As one particularly preferable resin, “the copolymer has 5 to 90 mol% of an epoxy group-containing (meth) acrylate and 10 to 95 mol% of another radical polymerizable monomer. Resin obtained by adding unsaturated monobasic acid to 10 to 100 mol% of epoxy group, or alkali-soluble resin obtained by adding polybasic acid anhydride to 10 to 100 mol% of hydroxyl group generated by the addition reaction ".

  Examples of the “epoxy group-containing (meth) acrylate” constituting the binder resin of [2-1-1] include, for example, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4- Examples thereof include epoxycyclohexyl) methyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

  As the “other radical polymerizable monomer” copolymerized with the epoxy group-containing (meth) acrylate, mono (meth) acrylate having a structure represented by the following general formula (1) is preferable.

In formula (1), R ^{1 to} R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, but R ⁷ and R ⁸ may be linked to each other to form a ring. .
In the formula (1), the ring formed by connecting R ⁷ and R ⁸ to each other is preferably an aliphatic ring, which may be saturated or unsaturated, and has 5 to 6 carbon atoms. Is preferred.

Especially, as a structure represented by General formula (1), the structure represented by following formula (1a), (1b), or (1c) is preferable. By introducing these structures into the binder resin, when the colored composition of the present invention is used for a color filter or a liquid crystal display element, the heat resistance of the colored composition is improved and formed using the colored composition. It is possible to increase the intensity of the processed pixels.
In addition, the mono (meth) acrylate which has a structure represented by General formula (1) may be used individually by 1 type, and may use 2 or more types together.

  As the mono (meth) acrylate having the structure represented by the general formula (1), various known ones can be used as long as the structure has the structure, and those represented by the following general formula (2) are particularly preferable. .

In the formula (2), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents the structure of the general formula (1).
In the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer, the repeating unit derived from the mono (meth) acrylate having the structure represented by the general formula (1) is: Among repeating units derived from “other radical polymerizable monomers”, those containing 5 to 90 mol% are preferable, those containing 10 to 70 mol% are more preferable, and those containing 15 to 50 mol% are particularly preferable. preferable.

The “other radical polymerizable monomer” other than the mono (meth) acrylate having the structure represented by the general formula (1) is not particularly limited. Specifically, for example, vinyl aromatics such as styrene, styrene α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives; butadiene, 2,3-dimethylbutadiene, isoprene, Dienes such as chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid-n-butyl, (Meth) acrylic acid-sec-butyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid pentyl, (meth) acrylic acid neopentyl, (meth) acrylic acid isoamyl, (meth) acrylic acid hexyl, (meta ) -2-ethylhexyl acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic Cyclopentyl acid, cyclohexyl (meth) acrylate, (meth) acrylate-2-methylcyclohexyl, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, propargyl (meth) acrylate, ( (Meth) acrylic acid phenyl, (meth) acrylic acid naphthyl, (meth) acrylic acid anthracenyl, (meth) acrylic acid anthraninonyl, (meth) acrylic acid piperonyl, (meth) acrylic acid salicylate, (meth) acrylic acid furyl, (Meth) acrylic acid furfuryl, (meth) acrylic acid tetrahydrofuryl, (meth) acrylic acid pyranyl, (meth) acrylic acid benzyl, (meth) acrylic acid phenethyl, (meth) acrylic acid cresyl, (meth) acrylic acid-1 , 1,1-trifluoroe Chill, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as cumyl, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate; (Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, (Meth) acrylic acid amides such as N-di-iso-propylamide and (meth) acrylic acid anthracenylamide; Vinyl compounds such as anilic silylate, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate; diethyl citraconic acid, diethyl maleate, Unsaturated dicarboxylic acid diesters such as diethyl fumarate and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; N- (meta ) Acrylyl phthalimide and the like.

  Among these “other radical polymerizable monomers”, in order to impart excellent heat resistance and strength to the colored composition, at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide is used. It is effective to use. In particular, in the repeating unit derived from “another radical polymerizable monomer”, the content of the repeating unit derived from at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide is 1 to 70 mol. %, Preferably 3 to 50 mol%.

  A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.

  Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; Propylene glycol monoalkyl ether acetates; Acetic esters such as dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, butyl carbitol; Triethylene glycol dialkyl Ethers; propylene glycol dialkyl Ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane and decane Petroleum petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate; dimethylformamide, N-methylpyrrolidone and the like. These solvents may be used alone or in combination of two or more.

The amount of these solvents used is usually 30 to 1000 parts by weight, preferably 50 to 800 parts by weight, with respect to 100 parts by weight of the resulting copolymer. When the amount of the solvent used is outside this range, it becomes difficult to control the molecular weight of the copolymer.

  The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound catalyst should be used. Can do. Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.

Specific examples thereof include, for example, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, and t-butyl peroxy-2. -Ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5 -Bis (t-butylperoxy) hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) ) Peroxydicarbonate, diiso Propyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1 -Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane and the like.
Examples of the azo compound catalyst include azobisisobutyronitrile and azobiscarbonamide.

  Among these, one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature. The usage-amount of a radical polymerization initiator is 0.5-20 weight part with respect to a total of 100 weight part of the monomer used for a copolymerization reaction, Preferably it is 1-10 weight part.

  The copolymerization reaction may be carried out by dissolving the monomer and radical polymerization initiator used in the copolymerization reaction in a solvent and raising the temperature while stirring, or by adding the monomer to which the radical polymerization initiator has been added. Alternatively, the reaction may be performed dropwise in a solvent that has been heated and stirred. Further, the monomer may be added dropwise while the temperature is raised by adding a radical polymerization initiator to the solvent. The reaction conditions can be freely changed according to the target molecular weight.

  In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Is preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter. What consists of 70 mol% and the latter 70-30 mol% is especially preferable.

If the amount of the epoxy group-containing (meth) acrylate is too small, the addition amount of the polymerizable component and the alkali-soluble component described later may be insufficient, while the amount of the epoxy group-containing (meth) acrylate is too large and other radicals. When there are too few polymerizable monomers, heat resistance and intensity | strength may become inadequate.
Subsequently, an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali) are added to the epoxy group portion of the copolymer of the epoxy resin-containing (meth) acrylate and another radical polymerizable monomer. A soluble component).

As the unsaturated monobasic acid to be added to the epoxy group, known ones can be used, and examples thereof include unsaturated carboxylic acids having an ethylenic double bond.
Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These 1 type may be used independently and may use 2 or more types together.

By adding such components, polymerizability can be imparted to the binder resin used in the present invention.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. If the addition ratio of the unsaturated monobasic acid is too small, there is a concern that the residual epoxy group may adversely affect the aging stability of the coloring composition. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a copolymer.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferable. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

By adding such a component, alkali solubility can be imparted to the binder resin used in the present invention.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%. When the addition ratio is too large, the remaining film ratio at the time of development may decrease, and when it is too small, the solubility may be insufficient. In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.

Furthermore, in order to improve photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be.
Moreover, in order to improve developability, you may add the glycidyl ether compound which does not have a polymerizable unsaturated group to some produced | generated carboxyl groups.
Both of these may be added.

  Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group. As commercial products, for example, trade names “Denacol EX-111”, “Denacol EX-121”, “Denacol EX-141”, “Denacol EX-145”, “Denacol EX-146”, “Denacol EX-146” manufactured by Nagase Chemical Industries, Ltd. Denacol EX-171 "," Denacol EX-192 "and the like.

The structure of such a resin is described in, for example, JP-A-8-297366 and JP-A-2001-89533, and is already known.
Weight average molecular weight (Mw) of the above-mentioned binder resin in terms of polystyrene measured by GPC.
) Is preferably from 3,000 to 100,000, particularly preferably from 5,000 to 50,000. If the molecular weight is less than 3000, heat resistance and film strength may be inferior, and if it exceeds 100,000, the solubility in a developer tends to be insufficient. Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

[2-1-2] (Meth) acrylic resin
The (meth) acrylic resin refers to a polymer obtained by polymerizing (meth) acrylic acid and / or (meth) acrylic ester as monomer components. Preferred examples of the (meth) acrylic resin include a polymer [2-1-2a] obtained by polymerizing a monomer component containing (meth) acrylic acid and benzyl (meth) acrylate, and the following general formula (4). And / or a polymer obtained by polymerizing a monomer component essentially comprising the compound represented by (5) [2-1-
2b].

In formula (4), R ^1a and R ^2a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In formula (5), R ^1b represents a hydrogen atom or an alkyl group which may have a substituent, L ³ represents a divalent linking group or a direct bond, and X is represented by the following formula (6). Or an adamantyl group which may be substituted. L ³ may be bonded to R ^3b or R ^4b in the following formula (6) to form a ring.

In formula (6), R ^2b , R ^3b and R ^4b each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an amino group, or an organic group, and L ¹ and L ² represent a divalent linking group. 2 or more of L ¹ , L ² and L ³ in the above formula (5) may be bonded to each other to form a ring.

[2-1-2a] Polymer obtained by polymerizing monomer components containing (meth) acrylic acid and benzyl (meth) acrylate Polymerizing monomer components containing (meth) acrylic acid and benzyl (meth) acrylate The polymer is preferably used in that it has a high affinity with the pigment.

  The ratio of the (meth) acrylic acid and benzyl (meth) acrylate in the monomer component is not particularly limited, but (meth) acrylic acid in the total monomer component is usually 10 to 90% by weight, preferably 15%. -80% by weight, more preferably 20-70% by weight. Moreover, benzyl (meth) acrylate is 5 to 90 weight% normally in all the monomer components, Preferably it is 15 to 80 weight%, More preferably, it is 20 to 70 weight%. If the amount of (meth) acrylic acid is too large, the surface of the coating film tends to be roughened during development, and if it is too small, development may be impossible. Further, if the amount of benzyl (meth) acrylate is too much or too little, dispersion tends to be difficult.

[2-1-2b] A polymer obtained by polymerizing a monomer component essentially comprising the compound represented by the general formula (4) and / or (5)
First, the compound of General formula (4) is demonstrated.
In the ether dimer represented by the general formula (4), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ^1a and R ^2a is not particularly limited. Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance. R ^1a and R ^2a may be the same type of substituent or different substituents.

Specific examples of the ether dimer include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 '-[Oxybis (methylene)] bis-2-propenoate,
And di (2-methyl-2-adamantyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate.

Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred.
These ether dimers may be used alone or in combination of two or more.

  The proportion of the ether dimer in the monomer component in obtaining the acrylic resin is not particularly limited, but is usually 2 to 60% by weight, preferably 5 to 55% by weight, based on the total monomer components, Preferably it is 5 to 50 weight%. If the amount of the ether dimer is too large, it may be difficult to obtain a low molecular weight product during polymerization, or may be easily gelled. On the other hand, if the amount is too small, the transparency, heat resistance, etc. The coating film performance may be insufficient.

Then, the compound of General formula (5) is demonstrated.
In general formula (5), R ^1b preferably represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.
In the general formula (6), the organic groups represented by R ^2b , R ^3b , and R ^4b are each independently, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, or an acyl group. Group, carboxyl group, acyloxy group and the like, preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a cyclohexane having 3 to 18 carbon atoms. An alkenyl group, an alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon atom, or an acyloxy group having 1 to 15 carbon atoms, Preferably, it is a C1-C10 alkyl group or a C3-C15 cycloalkyl group.

Preferred substituents among R ^2b , R ^3b and R ^4b are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
L ¹ and L ² are divalent linking groups, L ³ is not particularly limited as long as it is a divalent linking group or a direct bond, but at least either L ¹ or L ² is a linking group having 1 or more carbon atoms. Is preferred. L ¹ , L ² and L ³ are each independently a direct bond, alkylene having 1 to 15 carbon atoms, —O
-, -S-, -C (= O)-, alkenylene having 1 to 15 carbon atoms, phenylene, or a combination thereof is preferable.

As a preferable combination of L ¹ , L ² and L ³ , L ³ is a direct bond, alkylene having 1 to 5 carbon atoms, or a ring formed by combining with R ^3b or R ^4b, and L ¹ and L ² are C1-C5 alkylene.
Moreover, as a preferable thing of General formula (6), the compound represented by following General formula (7) can be mentioned.

In formula (7), R ^2b , R ^3b , R ^4b , L ¹ and L ² have the same meanings as in formula (6), and R ^5b and R ^6b each independently represent a hydrogen atom, a hydroxyl group, a halogen atom An atom, an amino group, or an organic group is shown.
In the general formula (7), the organic groups represented by R ^5b and R ^6b are each independently, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an acyl group, a carboxyl group, Or an acyloxy group and the like, preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, and a carbon number An alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon atom, or an acyloxy group having 1 to 15 carbon atoms, and more preferably a carbon number. It is a 1-10 alkyl group or a C3-C15 cycloalkyl group.

Preferred substituents among R ^5b and R ^6b are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
In addition, the alkyl group of R ^1b , each organic group of R ^2b , R ^3b and R ^4b , the divalent linking group of L ¹ , L ² and L ³ , and the adamantyl group of X are each independently a substituent. Specific examples thereof include the following substituents.

Halogen atom; hydroxyl group; nitro group; cyano group; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, amyl group, t-amyl group, n-hexyl group A linear or branched alkyl group having 1 to 18 carbon atoms such as n-heptyl group, n-octyl group and t-octyl group; carbon number such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and adamantyl group A cycloalkyl group having 3 to 18 carbon atoms; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group and a hexenyl group; a cycloalkenyl group having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, amyl A linear or branched alkoxy group having 1 to 18 carbon atoms such as a xyl group, t-amyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, t-octyloxy group; methylthio group, Ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, s-butylthio group, t-butylthio group, amylthio group, t-amylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, a linear or branched alkylthio group having 1 to 18 carbon atoms such as t-octylthio group; an aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group and mesityl group; carbon such as benzyl group and phenethyl group Aralkyl group having 7 to 18 carbon atoms; straight chain or branched chain having 2 to 18 carbon atoms such as vinyloxy group, propenyloxy group, hexenyloxy group Alkenyloxy group; represented by -OCOR ^18; carboxyl group; an acyl group represented by -COR ^17; vinylthio group, propenylthio group, alkenylthio group linear or branched 2 to 18 carbon atoms such as hexenyl thio group An acyloxy group represented by —NR ¹⁹ R ²⁰ ; an acylamino group represented by —NHCOR ²¹ ; a carbamate group represented by —NHCOOR ²² ; a carbamoyl group represented by —CONR ²³ R ²⁴ ; Carboxylic acid ester group represented by ²⁵ ; sulfamoyl group represented by —SO ₃ NR ²⁶ R ²⁷ ; sulfonic acid ester group represented by —SO ₃ R ²⁸ ; 2-thienyl group, 2-pyridyl group, furyl group , Oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group, tetrahydrothiophene dioxide A saturated or unsaturated heterocyclic group such as a side group; a trialkylsilyl group such as a trimethylsilyl group;

R ^{17 to} R ²⁸ each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. An aryl group or an aralkyl group which may have a substituent is shown.
Moreover, the positional relationship of the said substituent is not specifically limited, When it has a some substituent, it may be same or different.
Specific examples of the compound represented by the general formula (5) include the following.

  In the monomer component constituting the polymer of [2-1-2b] according to the present invention, the ratio of the general formula (5) is not particularly limited, but is usually 0.5 to 60 wt. %, Preferably 1 to 55% by weight, more preferably 5 to 50% by weight. If the amount is too large, the dispersion stability of the dispersion may be lowered when used as a dispersant. On the other hand, if the amount is too small, the soil stain aptitude may be lowered.

[2-1-2] (meth) acrylic resins in the present invention are [2-1-2a] and [2
It is preferable that all have an acid group including the polymer of -1-2b]. By having an acid group, the resulting colored composition can be cured by a crosslinking reaction in which an acid group and an epoxy group react to form an ester bond (hereinafter abbreviated as acid-epoxy curing), Or it can be set as the composition which can visualize an uncured part with an alkali developing solution. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group.
These acid groups may be used alone or in combination of two or more.

  In order to introduce an acid group into the (meth) acrylic resin, for example, a monomer having an acid group and / or a “monomer capable of imparting an acid group after polymerization” (hereinafter, “monomer for introducing an acid group”) May be used as a monomer component. In addition, when using "monomer which can provide an acid group after superposition | polymerization" as a monomer component, the process for providing an acid group as mentioned later is required after superposition | polymerization.

Examples of the monomer having an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; maleic anhydride and itaconic anhydride. Although the monomer etc. which have a carboxylic anhydride group are mentioned, Especially, (meth) acrylic acid is preferable among these.
Examples of the monomer capable of adding an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; monomers having an epoxy group such as glycidyl (meth) acrylate; 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate.
These monomers for introducing an acid group may be only one type or two or more types.

When the monomer component for obtaining the (meth) acrylic resin also includes the monomer for introducing the acid group, the content ratio is not particularly limited, but usually 5% of all the monomer components. It is -70 weight%, Preferably it is 10-60 weight%.
Moreover, the (meth) acrylic resin of [2-1-2] may have a radical polymerizable double bond.

  In order to introduce a radical polymerizable double bond into the (meth) acrylic resin, for example, “a monomer capable of imparting a radical polymerizable double bond after polymerization” (hereinafter referred to as “for introducing a radical polymerizable double bond”). May be referred to as a “monomer”.) Is polymerized as a monomer component, and then a treatment for imparting a radical polymerizable double bond as described later may be performed.

  Examples of the monomer capable of imparting a radical polymerizable double bond after polymerization include, for example, a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid; a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride Monomers: Monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. The monomer for introducing these radical polymerizable double bonds may be only one kind or two or more kinds.

When the monomer component for obtaining the (meth) acrylic resin of [2-1-2] also includes a monomer for introducing the radical polymerizable double bond, the content ratio is particularly limited. However, it is usually 5 to 70% by weight, preferably 10 to 60% by weight, based on all monomer components.
When the (meth) acrylic resin according to the present invention is a polymer having the compound of the general formula (4) described in [2-1-2a] as an essential monomer component, it has an epoxy group. Is preferred.
In order to introduce an epoxy group, for example, a monomer having an epoxy group (hereinafter also referred to as “monomer for introducing an epoxy group”) may be polymerized as a monomer component.

Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These monomers for introducing an epoxy group may be only one type or two or more types.

When the monomer component for obtaining the (meth) acrylic resin of [2-1-2] also includes the monomer for introducing the epoxy group, the content ratio is not particularly limited. Is 5 to 70% by weight, preferably 10 to 60% by weight in the total monomer components.
The monomer component for obtaining the (meth) acrylic resin of [2-1-2] contains, in addition to the above essential monomer component, other copolymerizable monomers as necessary. May be.

  Examples of other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate (Meth) acrylic acid esters such as; aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadienes such as butadiene and isoprene; Substituted butadiene compounds; ethylene, propylene, vinyl chloride , Ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate and the like.

Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.
In particular, when a part or all of the (meth) acrylic resin is used as a dispersant as described later, it is preferable to use benzyl (meth) acrylate, and the content thereof is usually all monomer components. The content is 1 to 70% by weight, preferably 5 to 60% by weight.
When the monomer component in obtaining the (meth) acrylic resin also includes the other copolymerizable monomer, the content ratio is not particularly limited, but is preferably 95% by weight or less, and 85% by weight or less. Is more preferable.

Next, the production method (polymerization method) of the (2-1-2) (meth) acrylic resin will be described.
There is no particular limitation on the method for polymerizing the monomer component, and various conventionally known methods can be adopted, but the solution polymerization method is particularly preferable. The polymerization temperature and polymerization concentration (polymerization concentration = [total weight of monomer components / (total weight of monomer components + solvent weight)] × 100) are the types and ratios of the monomer components used. , Depending on the molecular weight of the target polymer. The polymerization temperature is preferably 40 to 150 ° C, more preferably 60 to 130 ° C. Regarding the polymerization concentration, the polymerization concentration is preferably 5 to 50%, more preferably 10 to 40%.

  Moreover, what is necessary is just to use the solvent used by normal radical polymerization reaction when using a solvent at the time of superposition | polymerization. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; Chloroform; Dimethyl sulfoxide and the like Is mentioned. These solvents may be used alone or in combination of two or more.

  When the monomer component is polymerized, a polymerization initiator may be used as necessary. Although there is no restriction | limiting in particular in a polymerization initiator, For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amyl Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexane Carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) and the like. These polymerization initiators may be used alone or in combination of two or more.

The amount of initiator used may be appropriately set according to the combination of monomers used, reaction conditions, target polymer molecular weight, etc., and is not particularly limited, but the weight average molecular weight without gelation. The amount is usually from 0.1 to 15% by weight, more preferably from 0.5 to 10% by weight, based on the total monomer components, in that thousands to tens of thousands of polymers can be obtained.
Moreover, you may add a chain transfer agent for molecular weight adjustment. Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid and methyl mercaptoacetate, and α-methylstyrene dimer. Preferred are n-dodecyl mercaptan and mercaptoacetic acid, which can be reduced and easily obtained. When a chain transfer agent is used, the amount used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but without gelation It is usually 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on the total monomer components, in that a polymer having a weight average molecular weight of several thousand to several tens of thousands can be obtained.

In addition, when the compound of the general formula (4) is used as an essential monomer component, it is considered that the cyclization reaction of the ether dimer proceeds simultaneously in the polymerization reaction. The conversion rate is not necessarily 100 mol%.
When the acrylic resin is obtained, when the acid group is introduced by using the monomer capable of imparting the acid group described above as the monomer component, it is necessary to perform a treatment for imparting the acid group after polymerization. . The treatment varies depending on the type of monomer used. For example, when a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is used, succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride An acid anhydride such as a product may be added. When a monomer having an epoxy group such as glycidyl (meth) acrylate is used, a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol is added, or first ( An acid such as meth) acrylic acid may be added, and an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride or the like may be added to the resulting hydroxyl group. When a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate is used, for example, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.

When the (meth) acrylic resin of [2-1-2] is obtained, a radical polymerizable double bond is formed by using the monomer capable of imparting the radical polymerizable double bond described above as a monomer component. When introducing, it is necessary to perform a treatment for imparting a radically polymerizable double bond after polymerization.
The treatment varies depending on the type of monomer used. For example, when a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl ( A compound having an epoxy group and a radically polymerizable double bond such as (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether may be added. When a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride is used, a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate is added. Just do it. When a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether is used, ) A compound having an acid group such as acrylic acid and a radical polymerizable double bond may be added.

  The weight average molecular weight of the [2-1-2] (meth) acrylic resin is not particularly limited, but the polystyrene equivalent weight average molecular weight measured by GPC is preferably 2000 to 200000, more preferably 4000 to 100000. It is. When the weight average molecular weight exceeds 200,000, the viscosity may become too high to form a coating film, and when it is less than 2,000, sufficient heat resistance tends to be hardly exhibited.

When the said (meth) acrylic-type resin has an acid group, a preferable acid value is 30-500 mgKOH / g, More preferably, it is 50-400 mgKOH / g. When the acid value is less than 30 mgKOH / g, it may be difficult to apply to alkali development, and when it exceeds 500 mgKOH / g, the viscosity tends to be too high to form a coating film.
Among the (meth) acrylic resin components, the polymer having the compound represented by the general formula (4) as an essential monomer component is a known compound per se, for example, JP-A-2004-300203. Examples thereof include compounds described in JP-A-2004-300204.

  The colored composition of the present invention is used as a binder resin with respect to a copolymer of the above-mentioned [2-1-1] “epoxy group-containing (meth) acrylate and another radical polymerizable monomer. Resin obtained by adding an unsaturated monobasic acid to at least a part of an epoxy group of a polymer, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of a hydroxyl group generated by the addition reaction Is contained as an essential component.

As binder resin in this invention, 1 type may be used independently among binder resins of [2-1-1], and 2 or more types may be used together. Moreover, you may use together 1 type, or 2 or more types of the (meth) acrylic-type resin of [2-1-2] in the range which does not impair the effect of this invention.
The binder resin of [2-1-1] described above can be used alone or particularly in combination with the above-described dispersant, etc., thereby shortening the dissolution time in the developer, suppressing the increase in the viscosity of the coloring composition, and dispersion stability. As a result, the developability is improved. Specifically, for example, the non-dissolved material does not remain in the non-image area on the substrate, and the adhesion with the substrate is excellent. There is an effect that a color pixel can be formed.

Moreover, you may use a part of binder resin for the dispersion processing process mentioned later with the above-mentioned dispersing agent, a dispersing aid, etc. By using it, the amount of dispersant added can be reduced, which is effective in improving developability. At this time, the binder resin is preferably used in an amount of about 5 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of the pigment in the pigment dispersion.
As described above, as the binder resin used in the dispersion treatment step, the above-described various resins can be used, and the (meth) acrylic resin of [2-1-2] is particularly preferable. A polymer obtained by polymerizing a monomer component essentially comprising the compound represented by (4) is most preferable.

When used in a dispersion treatment step together with a dispersant, the acid value of the binder resin is 10 mgK.
OH / g or more is preferable, 30 mgKOH / g or more is more preferable, 50 mgKOH / g or more is most preferable, 500 mgKOH / g or less is preferable, 300 mgKOH / g or less is more preferable, and 200 mgKOH / g or less is most preferable. If the acid value is too high, the viscosity tends to be high and synthesis tends to be difficult, and if it is too low, it may be difficult to apply to alkali development.

  When used in a dispersion treatment step together with a dispersant, the weight average molecular weight in terms of polystyrene measured by GPC of the binder resin is preferably 1000 or more, more preferably 1500 or more, most preferably 2000 or more, and 200000 or less. Is more preferable, 50000 or less is more preferable, and 30000 or less is most preferable. If the molecular weight is too large, it tends to be difficult to apply to alkali development, and if the molecular weight is too small, the dispersion stability may decrease.

  In the colored composition of the present invention, the content ratio of the binder resin is usually 0.1% by weight or more, preferably 1% by weight or more, more preferably 10% by weight or more, and usually 80% by weight in the total solid content. % Or less, preferably 60% by weight or less, more preferably 50% by weight or less. When the content of the binder resin is less than this range, the film becomes fragile and the adhesion to the substrate may be lowered. On the other hand, when the amount is larger than this range, the permeability of the developing solution to the exposed portion increases, and the surface smoothness and sensitivity of the pixel may deteriorate.

  The content of the binder resin other than the resin of [2-1-1] in the binder resin is not particularly limited as long as the effect of the present invention is not impaired, but is usually 25% by weight or less, preferably 20% by weight. % Or less, more preferably 17% by weight or less.

[2-2] Other solid content
The colored composition for a color filter of the present invention may further contain a solid content other than the above components as necessary. Such components include photopolymerizable monomers, photopolymerization initiator systems, organic carboxylic acids, organic carboxylic acid anhydrides, surfactants, thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protection agents, and adhesion improvements. Agents, development improvers, dyes and the like.

[2-2-1] Photopolymerizable monomer
The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but is preferably an addition polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation system described later when the colored composition of the present invention is irradiated with actinic rays. In addition, the monomer in this invention means the concept which opposes what is called a polymeric substance, and means the concept also containing a dimer, a trimer, and an oligomer other than the monomer of a narrow sense.

  Examples of the ethylenic compound include an unsaturated carboxylic acid, an ester thereof with a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, An ester, a polyisocyanate compound and a (meth) acryloyl-containing hydroxy compound obtained by an esterification reaction with a saturated carboxylic acid and a polyvalent carboxylic acid and the polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound or aromatic polyhydroxy compound; And an ethylenic compound having a urethane skeleton obtained by reacting.

Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate. And acrylic esters such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, the acrylic acid part of these acrylates is a methacrylic acid ester replaced with a methacrylic acid part, an itaconic acid ester replaced with an itaconic acid part, a crotonic acid ester replaced with a crotonic acid part, or a maleic acid replaced with a maleic acid part Examples include esters.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Typical examples include, for example, condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol. And condensates of glycerin and the like.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclohexane diisocyanate and isophorone diisocyanate. Alicyclic diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3- (Meth) acryloyl group-containing hydroxy compounds such as hydroxy (1,1,1-trimethacryloyloxymethyl) propane Reaction products thereof.

In addition, as the ethylenic compound used in the present invention, for example, acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are also useful.
The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. The polyfunctional monomer provided is preferred, and particularly preferably in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel tends to be poor. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

In the present invention, the polyfunctional monomer having a more preferred acid group is mainly composed of succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate commercially available as TO1382 manufactured by Toagosei Co., Ltd. Is a mixture. Other polyfunctional monomers can be used in combination with this polyfunctional monomer.

In the present invention, the above-mentioned ethylenic compound has a molecular weight of 650 or less, preferably 550 or less, more preferably 400 or less, and a double bond equivalent of 150 or less, preferably 140 or less, more preferably 110 or less. Is appropriate. In addition, the lower limit thereof is not particularly limited as long as it can take a chemical structure capable of addition polymerization.
Among these, a compound having a relatively small molecular weight and a small double bond equivalent is preferable from the viewpoint that the pixel can be formed with less “over” and more excellent linearity. For example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid having a molecular weight of 400 or less and a double bond equivalent of 110 or less is preferred, and more specifically, for example, pentaerythritol tetra Examples thereof include acrylate and pentaerythritol triacrylate.

  In addition, it is preferable to use the ethylenic compound whose molecular weight exceeds 400 from the point of the sensitivity of the coloring composition for color filters obtained. As such a compound, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are particularly preferable. These are preferable because a well-balanced composition can be obtained by using in combination with the above-described ethylenic compound having a molecular weight of 400 or less and a double bond equivalent of 150 or less (more preferably 110 or less).

  The blending ratio of the ethylenic compound is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and usually 80% by weight or less, preferably in the total solid content of the colored composition of the present invention. Is 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less. The ratio to the colorant is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, particularly preferably 20% by weight or more, and usually 200% by weight or less, preferably 100% by weight. Hereinafter, it is more preferably 80% by weight or less.

[2-2-2] Photopolymerization Initiation System The photopolymerization initiator is usually used as a mixture (photopolymerization initiation system) with an accelerator and an additive such as a sensitizing dye added as necessary. The photopolymerization initiation system is a component that has a function of directly absorbing light or photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.
Examples of the photopolymerization initiator constituting the photopolymerization initiation system component include metallocene compounds including titanocene compounds described in JP-A Nos. 59-152396 and 61-151197, and the like. Hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, and the like described in Kaihei 10-39503 Radical activators such as aryl-α-amino acid esters, α-aminoalkylphenone compounds,
Examples thereof include oxime ester-based initiators described in JP-A-00-80068.

Specific examples of the polymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;

  2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxa Diazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5 monofuryl-1,3 Halomethylated oxadiazole derivatives such as 4-oxadiazole;

  2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- ( 2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5 -Imidazole derivatives such as diphenylimidazole dimer;

Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;

  Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;

  2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1,1,1 An acetophenone derivative such as trichloromethyl- (p-butylphenyl) ketone;

Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;
Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate; Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine; Phenazines such as 9,10-dimethylbenzphenazine Derivatives;

Anthrone derivatives such as benzanthrone;
Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentagenyl-Ti-bis-phenyl, di-cyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl -1 monoyl, di-cyclopentagenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentagenyl-Ti-bis-2,4,6-tri Fluorophen-1-yl, di-cyclopentagenyl-Ti-2,6-dipuruolophen-1-yl, di-cyclopentagenyl-Ti-2,4-di-fluorophen-1-yl, Di-methylcyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentagenyl-Ti-bis-2,6-di-fluoropheny -1 Yl, di - cyclopentadienyl -Ti-2,6-di - fluoro-3- (pill-1-yl) - titanocene derivatives such as 1-yl;

2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl 2-Dimethylamino-1- (4-morpholinophenyl) butane
1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2 , 5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, α-aminoalkylphenone compounds such as 4- (diethylamino) chalcone;

  1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- Oxime ester compounds such as 3-yl]-, 1- (O-acetyloxime).

Examples of the accelerator constituting the photopolymerization initiation system component include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, A mercapto compound having a heterocyclic ring such as 2-mercaptobenzimidazole or an aliphatic polyfunctional mercapto compound is used.
These photopolymerization initiators and accelerators may be used alone or in combination of two or more.

Specific photopolymerization initiation system components include, for example, dialkyl acetophenone series described on pages 16 to 26 of “Fine Chemical” (March 1, 1991, vol. 20, No. 4), In addition to benzoin, thioxanthone derivatives, etc., as described in JP-A-58-403023 and JP-B-45-37777, hexaarylbiimidazole series, S-trihalomethyltriazine series, JP-A-4-221958 Examples include a combination of titanocene and a xanthene dye, an addition-polymerizable ethylenic saturated double bond-containing compound having an amino group or a urethane group described in JP-A-4-219756.

  The blending ratio of the photopolymerization initiation system component is generally 0.1 to 40% by weight, preferably 0.5 to 30% by weight, based on the total solid content of the color filter coloring composition of the present invention. If the blending ratio is extremely low, the sensitivity to the exposure light may be lowered. Conversely, if the blending ratio is extremely high, the solubility of the unexposed portion in the developer is lowered, and development failure may be induced.

  If necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source can be added to the photopolymerization initiation system component for the purpose of increasing the sensitivity. These sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and 3-ketocoumarin compounds described in Kaihei 3-239703 and 5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A 47-2528, 54-155292, JP 45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-6988, JP-A-57-168088. No. 5, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818. Mention may be made of a dye or the like having a skeleton.

Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-diethylamino) Phenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, (p- P such as (dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. -Dialkylaminophenyl group-containing compounds. Of these, 4,4′-dialkylaminobenzophenone is most preferred.
A sensitizing dye may also be used individually by 1 type, and 2 or more types may be mixed and used for it.

  The blending ratio of the sensitizing dye in the colored composition of the present invention is usually 0% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% by weight or more in the total solid content of the colored composition. Moreover, it is usually 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less.

[2-2-3] Organic carboxylic acid, organic carboxylic anhydride
The coloring composition of the present invention may contain an organic carboxylic acid and / or an organic carboxylic acid anhydride having a molecular weight of 1000 or less.

  Specific examples of the organic carboxylic acid compound include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, and methacrylic acid, oxalic acid, malonic acid, succinic acid, Examples thereof include dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, and tricarboxylic acids such as tricarbaryl acid and aconitic acid. Examples of the aromatic carboxylic acid include carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and carboxylic acids in which a carboxyl group is bonded to the phenyl group through a carbon bond. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically maleic acid, malonic acid, succinic acid, and itaconic acid are preferred.

  Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specific examples include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, and tetrahydrophthalic anhydride. Succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. An aliphatic carboxylic acid anhydride is mentioned. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferable.

The addition amount of these organic carboxylic acids and / or organic carboxylic anhydrides is usually 0.01 to 10% by weight, preferably 0.03 to 5% by weight, more preferably 0.05 to 3% in the total solid content.
It is in the range of wt%.
By adding these organic carboxylic acids and / or organic carboxylic acid anhydrides having a molecular weight of 1000 or less, it is possible to further reduce the remaining undissolved coloring composition while maintaining high pattern adhesion.

[2-2-4] Surfactant
Various surfactants such as anionic, cationic, nonionic and amphoteric surfactants can be used as surfactants, but nonionic surfactants are less likely to adversely affect various properties. It is preferable to use an agent. The concentration range of the surfactant is usually 0.001% by weight or more, preferably 0.005% by weight or more, more preferably 0.01% by weight or more, and most preferably 0.03% by weight with respect to the total composition amount. In addition, the range of usually 10% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight or less, and most preferably 0.3% by weight or less is used.

[2-2-5] Thermal polymerization inhibitor
As the thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like are used. The blending amount of the thermal polymerization inhibitor is preferably in the range of 0% by weight to 3% by weight with respect to the total solid content of the composition.

[2-2-6] Plasticizer Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like. Is used. The blending amount of these plasticizers is preferably in the range of usually 10% by weight or less with respect to the total solid content of the composition.

[3] Preparation of coloring composition
Next, a method for preparing the colored composition of the present invention (hereinafter sometimes referred to as “resist”) will be described.

  First, a predetermined amount of each of pigment, solvent and dispersant is weighed, and in the dispersion treatment step, a green pigment containing brominated zinc phthalocyanine is dispersed to prepare a pigment dispersion. In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By performing this dispersion treatment, the coloring material is made fine particles, so that the coating characteristics of the coloring composition are improved, and the transmittance of the pixels in the product color filter substrate is improved.

When dispersing the pigment, as described above, it is preferable to use a dispersion aid or a dispersion resin in combination as appropriate.
Further, as the pigment, it is essential to contain the above-mentioned green pigment containing brominated zinc phthalocyanine, but it may be mixed with other pigments for dispersion and dispersed.
When the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set to 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time varies depending on the composition of the pigment dispersion, the size of the sand grinder apparatus, and the like, and therefore needs to be adjusted appropriately.

The pigment dispersion obtained by the dispersion treatment is mixed with a solvent, a binder resin, and in some cases, a predetermined amount of a photopolymerizable monomer, a photopolymerization initiation system component, a component other than the above, and the like, To do. In each of the dispersion treatment step and the mixing step, fine dust may be mixed. Therefore, the obtained pigment dispersion is preferably filtered with a filter or the like.

[4] Manufacture of color filter substrates
Next, the color filter of the present invention will be described.
The color filter of the present invention is characterized in that pixels are formed on the substrate using the above-described colored composition.

[4-1] Transparent substrate (support)
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Materials include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, polysulfone thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, and poly (meth) acrylic. Examples thereof include thermosetting resin sheets such as a resin, and various glasses. Among these, glass or heat resistant resin is preferable from the viewpoint of heat resistance.

  For transparent substrates and black matrix forming substrates, to improve surface properties such as adhesion, corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents and urethane resins, as necessary May be performed. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01 micrometer or more normally, Preferably it is 0.05 micrometer or more, and is 10 micrometers or less normally, Preferably it is the range of 5 micrometers or less.

[4-2] Black matrix
The color filter according to the present invention can be manufactured by providing a black matrix on the above-described transparent substrate, and forming red, green, and blue pixel images. The colored composition is used as a coating solution for forming a green pixel (resist pattern) among red, green, and blue pixels. Using the green resist, on a resin black matrix forming surface formed on a transparent substrate, or on a metal black matrix forming surface formed using a chromium compound or other light shielding metal material, coating, heat drying, image exposure, Each process of development and thermosetting is performed to form a pixel image.

The black matrix is formed on a transparent substrate using a light-shielding metal thin film or a photosensitive colored resin composition for black matrix. As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide, and chromium nitride, nickel and tungsten alloys, and the like may be used, and these may be laminated in a plurality of layers.
These metal light shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape with a positive photoresist, ceric ammonium nitrate, perchloric acid and / or nitric acid are added to chromium. Other materials are etched using an etchant according to the material, and finally a positive photoresist is stripped with a dedicated stripper to form a black matrix. be able to.

  In this case, first, a thin film of the metal or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, after forming a coating film of the colored composition on the thin film, the coating film is exposed and developed using a photomask having a repetitive pattern such as a stripe, a mosaic, and a triangle to form a resist image. Thereafter, this coating film can be etched to form a black matrix.

  When using the photosensitive coloring resin composition for black matrix, a black matrix is formed using the coloring resin composition containing a black coloring material. For example, black color material such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black or the like, or red, green, blue or the like appropriately selected from inorganic or organic pigments and dyes A black matrix can be formed in the same manner as described below for forming a red, green, and blue pixel image using a colored composition containing a black color material by mixing.

[4-3] Pixel formation
The method for forming the pixel differs depending on the type of the coloring composition to be used. Here, a case where a photopolymerizable composition is used as the coloring composition will be described as an example.
A colored composition of one of red, green, and blue is applied on a transparent substrate provided with a black matrix, dried, a photomask is layered on the coating film, and image exposure and development are performed via this photomask. If necessary, a pixel image is formed by heat curing or photocuring to create a colored layer. A color filter image can be formed by performing this operation for each of the three colored compositions of red, green, and blue.

  The coloring composition for a color filter can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, there is no influence of mist adhering when using the spin coating method, and the generation of foreign matter is further suppressed. It is preferable from a viewpoint.

  If the thickness of the coating film is too large, pattern development becomes difficult and gap adjustment in the liquid crystal cell forming process may be difficult. On the other hand, if it is too small, it is difficult to increase the pigment concentration. Color expression may be impossible. The thickness of the coating film is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm as the film thickness after drying. The range is as follows.

[4-4] Drying of coating film
The coating film after applying the coloring composition to the substrate is preferably dried by a drying method using a hot plate, IR oven, or convection oven. Usually, after preliminary drying, it is heated again and dried. The conditions for the preliminary drying can be appropriately selected according to the type of the solvent component, the performance of the dryer to be used, and the like. The drying temperature and drying time are selected according to the type of the solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature is usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 80 The drying time is usually 15 seconds or longer, preferably 30 seconds or longer, and usually 5 minutes or shorter, preferably 3 minutes or shorter.

  The temperature condition for reheat drying is preferably higher than the pre-drying temperature. Specifically, it is usually 50 ° C. or higher, preferably 70 ° C. or higher, and usually 200 ° C. or lower, preferably 160 ° C. or lower, particularly preferably 130 ° C. It is the range below ℃. Moreover, although it depends on the heating temperature, the drying time is usually 10 seconds or more, preferably 15 seconds or more, and usually 10 minutes or less, preferably 5 minutes. The higher the drying temperature, the better the adhesion to the transparent substrate. However, when the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. In addition, as a drying process of this coating film, you may use the reduced pressure drying method which dries in a reduced pressure chamber, without raising temperature.

[4-5] Exposure process
Image exposure is performed by superimposing a negative matrix pattern on the coating film of the colored composition and irradiating an ultraviolet or visible light source through the mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

[4-6] Development process
The color filter of the present invention uses an organic solvent or an aqueous solution containing a surfactant and an alkaline compound after performing image exposure with the above-described light source on the coating film using the colored composition of the present invention. By performing the development, an image can be formed on the substrate and manufactured. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, phosphorus Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- Or trimethylamine, mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), coli And organic alkaline compounds such as.
These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.
There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, further 40 ° C. or lower. Is preferred. The development method can be any method such as immersion development, spray development, brush development, and ultrasonic development.

[4-7] Thermosetting treatment
The color filter after development is subjected to heat curing. In this case, the thermosetting treatment conditions are such that the temperature is usually 100 ° C. or more, preferably 150 ° C. or more, and usually 280 ° C. or less, preferably 250 ° C. or less, and the time is 5 minutes or more and 60 minutes or less. Selected by range. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.

  In addition to the manufacturing method described above, the color filter of the present invention includes (1) a curable coloring composition containing a solvent, a brominated zinc phthalocyanine pigment as a coloring material, and a polyimide resin as a binder resin. It can also be manufactured by a method of applying and forming a pixel image by an etching method. In addition, (2) a method of forming a pixel image directly on a transparent substrate using a coloring composition containing a brominated zinc phthalocyanine pigment as a coloring ink, and (3) a coloring composition containing a brominated zinc phthalocyanine pigment. A method of depositing a colored film on an ITO electrode having a predetermined pattern by immersing the substrate as an electrodeposition solution and immersing the substrate in the electrodeposition solution may be used. Further, (4) a method in which a film coated with a coloring composition containing a brominated zinc phthalocyanine pigment is attached to a transparent substrate and peeled off, image exposure and development to form a pixel image, and (5) brominated zinc phthalocyanine. Examples thereof include a method of forming a pixel image with an ink jet printer using a coloring composition containing a pigment as a coloring ink. The manufacturing method of a color filter employ | adopts the method suitable for this according to the composition of the coloring composition for color filters.

[4-8] Formation of transparent electrode
The color filter of the present invention forms a transparent electrode such as ITO on the image as it is, and is used as a part of components such as a color display and a liquid crystal display device, but improves surface smoothness and durability. Therefore, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

[5] Liquid crystal display device (panel)
Next, the manufacturing method of the liquid crystal display device (panel) of this invention is demonstrated. In the liquid crystal display device of the present invention, an alignment film is usually formed on the color filter of the present invention, spacers are dispersed on the alignment film, and then bonded to the counter substrate to form a liquid crystal cell. Liquid crystal is injected into the cell and connected to the counter electrode to complete. The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to form a surface state in which the tilt of the liquid crystal can be adjusted.

  As the spacer, a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by a photolithography method, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of vacuum in the liquid crystal cell is usually in the range of 1 × 10 −2 Pa or more, preferably 1 × 10 −3 Pa or more, and usually 1 × 10 −7 Pa or less, preferably 1 × 10 −6 Pa or less. The liquid crystal cell is preferably heated during decompression, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower.
The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. In the liquid crystal cell into which liquid crystal is injected, a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The type of liquid crystal is not particularly limited, and may be any of conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, and may be any of lyotropic liquid crystals, thermotropic liquid crystals, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

Next, although a manufacture example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the following examples, “part” represents “part by weight”.
<Examples 1-7 and Comparative Examples 1-2>
[1] Synthesis of green pigment
[1-1] Synthesis Example 1: Synthesis of brominated zinc phthalocyanine Zinc phthalocyanine was produced using phthalodinitrile and zinc chloride as raw materials. This 1-chloronaphthalene solution had light absorption at 600 to 700 nm. For halogenation, 3.1 parts by weight of sulfuryl chloride, 3.7 parts by weight of anhydrous aluminum chloride, 0.46 parts by weight of sodium chloride and 1 part by weight of zinc phthalocyanine were mixed at 40 ° C., and 4.4 parts by weight of bromine was added dropwise. I went. The mixture was reacted at 80 ° C. for 15 hours, and then the reaction mixture was poured into water to precipitate a brominated zinc phthalocyanine crude pigment. This aqueous slurry was filtered, washed with hot water at 80 ° C., and dried at 90 ° C. to obtain 3.0 parts by weight of a purified brominated zinc phthalocyanine crude pigment.

Next, 12 parts by weight of crushed sodium chloride, 1.8 parts by weight of diethylene glycol, and 0.09 parts by weight of xylene are charged into a double-arm kneader in 1 part by weight of the above brominated zinc phthalocyanine crude pigment and kneaded at 70 ° C. for 10 hours. did. After kneading, it was taken out into 100 parts by weight of water at 80 ° C., stirred for 1 hour, and then filtered, washed with hot water, dried and ground to obtain a brominated zinc phthalocyanine pigment.
The obtained brominated zinc phthalocyanine pigment had an average composition of ZnPcBr14Cl2 (Pc: phthalocyanine) based on a halogen content analysis by mass spectrometry, and contained an average of 14 bromines in one molecule. Moreover, the average value of the primary particle size measured with a transmission electron microscope (H-9000UHR manufactured by Hitachi, Ltd.) was 0.023 μm. The average primary particle diameter of the pigment was ultrasonically dispersed in chloroform, dropped onto a mesh coated with a collodion film, dried, and a primary particle image of the pigment was obtained by observation with a transmission electron microscope (TEM). The primary particle size was measured from the image to determine the average particle size.

[2] Resin synthesis
[2-1] Synthesis Example 1: Synthesis of Dispersing Resin A A separable flask equipped with a cooling tube was prepared as a reaction vessel, charged with 400 parts by weight of propylene glycol monomethyl ether acetate, purged with nitrogen, and then stirred with an oil bath And the temperature of the reaction vessel was raised to 90 ° C.

  Meanwhile, 30 parts by weight of dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, 60 parts by weight of methacrylic acid, 110 parts by weight of cyclohexyl methacrylate, t-butylperoxy-2-ethyl Charge 5.2 parts by weight of hexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate, charge 5.2 parts by weight of n-dodecyl mercaptan and 27 parts by weight of propylene glycol monomethyl ether acetate to the chain transfer agent tank, and temperature of the reaction tank After stabilizing at 90 ° C., dropping was started from the monomer tank and the chain transfer agent tank to initiate polymerization. While maintaining the temperature at 90 ° C., dropping was carried out over 135 minutes each, and 60 minutes after the dropping was finished, the temperature was raised and the reaction vessel was brought to 110 ° C.

After maintaining at 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Next, 39.6 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 parts by weight of triethylamine were charged into the reaction vessel at 110 ° C. as it was. For 9 hours.
After cooling to room temperature, a polymer solution having a weight average molecular weight of 8000 and an acid value of 101 mgKOH / g was obtained.

[2-2] Synthesis Example 2: Synthesis of Resin B 145 parts by weight of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate, and 66 parts by weight of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2.2'-azobis-2-methyl 9.00 parts by weight of butyronitrile was added dropwise over 3 hours, and stirring was further continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 part by weight of trisdimethylaminomethylphenol and 0.12 part by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw measured by GPC of the binder resin thus obtained was about 6000, and the acid value was 90 mgKOH / g.

[2-3] Synthesis Example 3: Synthesis of Resin C 145 parts by weight of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. 30 parts by weight of benzyl methacrylate, 85.2 parts by weight of glycidyl methacrylate and 46 parts by weight of a monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2.2'-azobis-2- 7.47 parts by weight of methylbutyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 part by weight of trisdimethylaminomethylphenol and 0.12 part by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 50.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The binder resin thus obtained had a weight average molecular weight Mw measured by GPC of about 14,000 and an acid value of 80 mgKOH / g.

[2-4] Synthesis Example 4: Synthesis of Resin D Similarly to Resin B, styrene, glycidyl methacrylate, and monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were polymerized, and then the inside of the reaction vessel was Instead of air substitution, 4 parts by weight of acrylic acid was charged with 0.7 parts by weight of trisdimethylaminomethylphenol and 0.12 parts by weight of hydroquinone, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 50.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The binder resin thus obtained had a weight average molecular weight Mw measured by GPC of about 8000 and an acid value of 78 mgKOH / g.

[2-5] Synthesis Example 5: Synthesis of Resin E 145 parts by weight of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. 10 parts by weight of styrene, 115.2 parts by weight of glycidyl methacrylate, and 46 parts by weight of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2.2′-azobis-2-methyl 7.47 parts by weight of butyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 parts by weight of trisdimethylaminomethylphenol and 0.12 parts by weight of hydroquinone were added to 58.3 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 57.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The binder resin thus obtained had a weight average molecular weight Mw measured by GPC of about 8,000 and an acid value of 100 mgKOH / g.

[2-6] Synthesis Example 6: Synthesis of Resin F In the same manner as Resin B, styrene, glycidyl methacrylate, and monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were polymerized. Instead of air substitution, 4 parts by weight of acrylic acid was charged with 0.7 parts by weight of trisdimethylaminomethylphenol and 0.12 parts by weight of hydroquinone, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 30.1 parts by weight of succinic anhydride and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The binder resin thus obtained had a weight average molecular weight Mw measured by GPC of about 9000 and an acid value of 81 mgKOH / g.

[2-7] Synthesis Example 7: Synthesis of Resin G In the same manner as Resin B, styrene, glycidyl methacrylate, and monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were polymerized. Instead of air substitution, 4 parts by weight of acrylic acid was charged with 0.7 parts by weight of trisdimethylaminomethylphenol and 0.12 parts by weight of hydroquinone, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 69.2 parts by weight of trimellitic anhydride and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The binder resin thus obtained had a weight average molecular weight Mw measured by GPC of about 7000 and an acid value of 79 mgKOH / g.

[2-8] Synthesis Example 8: Synthesis of Resin H 114.0 g of propylene glycol monomethyl ether acetate was added to 500 ml of 4
The flask was placed in a three-necked flask and heated to 85 ° C. while performing nitrogen bubbling. 96.8 g (0.55 mol) of benzyl methacrylate, 33.3 g (0.45 mol) of methacrylic acid, and 4.93 g (0.03 mol) of 2,2′-azobis (isobutyronitrile) were added to propylene glycol 1-monomethyl. It melt | dissolved in 96.45g of ether 2-acetate, and was dripped over 4 hours. After dropping, the reaction solution was further stirred for 2 hours while maintaining the temperature at 85 ° C., and thereafter nitrogen bubbling was stopped, the temperature was raised to 100 ° C., and the mixture was stirred for 1 hour. The obtained binder resin had a weight average molecular weight of 15000 and an acid value of 180 mgKOH / g.

[2-9] Synthesis Example 9: Synthesis of Resin I 114.0 g of propylene glycol monomethyl ether acetate was placed in a 500 ml four-necked flask and heated to 85 ° C. while performing nitrogen bubbling. 96.8 g (0.55 mol) of benzyl methacrylate, 33.3 g (0.45 mol) of methacrylic acid, and 9.85 g (0.06 mol) of 2,2′-azobis (isobutyronitrile) were added to propylene glycol 1-monomethyl. It melt | dissolved in 96.45g of ether 2-acetate, and was dripped over 4 hours. After dropping, the reaction solution was further stirred for 2 hours while maintaining the temperature at 85 ° C., and thereafter nitrogen bubbling was stopped, the temperature was raised to 100 ° C., and the mixture was stirred for 1 hour. The obtained binder resin had a weight average molecular weight of 8,000 and an acid value of 175 mgKOH / g.

[3] Preparation of green pigment dispersion
As a green pigment, 7.1-1 parts by weight of brominated zinc phthalocyanine obtained in [1-1] Synthesis Example 1 and C.I. I. 2.54 parts by weight of Pigment Yellow 150, 60.00 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 1.96 parts by weight of a dispersant “BYK-LPN6919” (a dispersant manufactured by Big Chemie), and a dispersion A stainless steel container was filled with 3.26 parts by weight of resin A in terms of solid content and 225 parts by weight of zirconia beads having a diameter of 0.5 mm, and dispersed in a paint shaker for 6 hours to prepare a green pigment dispersion.

The dispersant “BYK-LPN6919” is a methacrylic AB block copolymer having a solvophilic A block and a B block having a nitrogen atom-containing functional group, the main chain of which is methacrylic acid. Its amine value is about 120 mg KOH / g.

[4] Preparation of coloring composition
Green pigment dispersion prepared in [3], solvent (propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate), binder resin (resin B to resin I), photopolymerizable monomer (dipentaerythritol hexaacrylate, pentaerythritol) Tetraacrylate), photopolymerization initiation system component [2,2 ′-(o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 4,4′-bis-diethylaminobenzophenone, 2-mercaptobenzothiazole 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one] and a surfactant [F-475 (fluorinated surfactant, manufactured by Dainippon Ink & Chemicals, Inc.)] Were mixed at the ratio shown in Table 1 to prepare the colored compositions of Examples 1 to 7 and Examples 8 to 9. . In addition, the numerical value of Table 1 is content (weight part).

[5] Change in viscosity of coloring composition
The viscosity (20 rpm) after one day of preparation of the coloring composition and after standing for 7 days in a constant temperature bath at 35 ° C. was measured using an E-type viscometer “RE-80L” manufactured by Toki Sangyo Co., Ltd. Table 2 shows the viscosities measured for the colored compositions of Examples and Comparative Examples after one day of preparation and seven days after preparation.

  From Table 2, the viscosity after 7 days at 35 ° C. was reduced or changed by 1% or less in the colored compositions of Examples 1 to 7.

[6] Preparation of substrate for contrast measurement The above colored composition of Example 1 composition, Comparative Example 1 and 2 compositions after 1 day of preparation on a glass substrate (Asahi Glass Co., Ltd., AN100) having a 50 mm square and a thickness of 0.7 mm. After applying with a spin coater, it was dried at 80 ° C. for 3 minutes. Next, the entire surface exposure process was performed with a 2 kW high pressure mercury lamp at an exposure amount of 300 mJ / cm 2. Thereafter, development was performed using a 0.04 wt% aqueous potassium hydroxide solution at a developer temperature of 23 ° C. Subsequently, a spray water washing treatment was performed at a water pressure of 3 kg / cm 2 for 30 seconds to prepare a colored composition coated substrate. Then, the thermosetting process for 30 minutes was performed at the temperature of 230 degreeC.

When the transmission spectrum of the coated substrate thus obtained was measured with a spectrophotometer U-3310 manufactured by Hitachi, Ltd., the chromaticity calculated with the C light source was x = 0.280 and y = 0.600.
Similarly, a substrate for contrast measurement was prepared for the colored composition 7 days after adjustment and 12 days after storage at 23 ° C.

[7] Contrast measurement The contrast of the coated substrate (hereinafter referred to as a colored plate) was measured by the method described below. The results are shown in Table 3.
<Contrast measurement of colored composition using colored plate>
FIGS. 1A and 1B are schematic diagrams for explaining a method of measuring the chromaticity of parallel transmitted light and orthogonal transmitted light of a colored plate. First, as shown in FIG. 1A, polarizing plates 33 and 35 are stacked on both sides of a coated substrate (corresponding to a color filter; hereinafter referred to as “colored plate 34”) obtained in [6] above, In a state where the polarization axes of the plates 33 and 35 are parallel to each other, the light 36 of the backlight 37 is applied from the side of one polarizing plate 35, and the luminance Lp of the light transmitted through the other polarizing plate 33 (of the parallel transmitted light). Luminance) was measured using a color luminance meter “BM-5A” 32 manufactured by Topcon Technohouse under the condition of a 2 ° visual field.

Next, as shown in FIG. 1B, with the polarization axes of the polarizing plates 33 and 35 orthogonal to each other, the light 36 of the backlight 37 is applied from one polarizing plate 35 side, and the other polarizing plate 33 is applied. The luminance Lc (the luminance of the orthogonal transmitted light) transmitted through the light was measured with the color luminance meter 32 in the same manner as the above Lp.
The backlight 37 has an emission spectrum as shown in FIG. The spectrum was measured and calculated using a Konica Minolta spectral radiance meter CS-1000A and a filter “ND filter ND4” manufactured by Kenko in order to control the amount of light and facilitate the measurement. The polarizing plates 33 and 35 have the spectral characteristics shown in FIG.

  The above-mentioned contrast of the coloring composition is calculated from the brightness Lp of the parallel transmitted light and the brightness Lc of the orthogonal transmitted light using the formula Lp / Lc, and is a blank value when measured using raw glass instead of the coated substrate. Was 12800.

  From Table 3, the color composition of Example 1 showed no change in contrast over time due to storage after preparation.

[8] Production of Pattern (Pixels) Each of the colored compositions was spin-coated on a glass substrate on which chromium was vapor-deposited, and prebaked on a hot plate at 80 ° C. for 3 minutes. At the time of application, the number of rotations was adjusted so that the color coordinate y = 0.600 after drying.
Next, the sample was exposed at 60 mj / cm 2 through a linear mask pattern having a width of 50 μm and a length of 3 mm with a high-pressure mercury lamp, and then 0.04 wt% potassium hydroxide aqueous solution was used.
Spray development was performed at a developer temperature of 23 ° C. and a pressure of 0.25 MPa. The development time was set to twice the dissolution time of the colored composition measured in advance. The dissolution time measurement will be described later. After development, the substrate was rinsed with sufficient water and then dried with clean air. Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes. The film thickness after drying was about 1.8 μm.

[9] Measurement of dissolution time of colored composition In the same manner as in [8], a colored composition is applied on a glass substrate, dried, exposed, and then developed using a 0.04 wt% aqueous potassium hydroxide solution. When developing at a temperature of 23 ° C. and a pressure of 0.25 MPa, the time during which the unexposed colored composition was completely dissolved in the developer and the substrate was exposed was defined as the dissolution time of the colored composition.

[10] Measurement of application of linear pattern Ten patterns obtained by the method described in [8] were observed 10 times using an optical microscope, and the number of application of the dents on the edge of the line was counted. This was repeated twice to confirm reproducibility. A photomicrograph of a representative example of the pattern (pixel) is shown in FIG.

  Table 4 shows the dissolution time and the number of pieces measured for the compositions of Examples 2 to 9.

  From Table 4, the coloring compositions of Examples 2 to 7 have a short dissolution time of 60 seconds or less. Further, it was found that the colored composition of Example 7 had a particularly small number of linear patterns and a pattern having good linearity was obtained.

From the above results, the following is clear.
(1) The colored composition of the present invention has a short development time, a small increase in viscosity over time, a low contrast, and a pattern (pixel) with less “over” and excellent linearity. It has excellent characteristics, and it is possible to realize both high contrast and dispersion stability, which has been a problem until now when a brominated zinc phthalocyanine green pigment is used for the purpose of increasing the brightness of a green pixel.
(2) The color filter produced using the colored composition of the present invention is of a very high quality with both high brightness and high contrast.

The present invention has the following useful effects, and its industrial utility value is extremely great.
1. The coloring composition of the present invention can realize both high contrast and dispersion stability, which has been a problem until now when a brominated zinc phthalocyanine green pigment is used for the purpose of increasing the brightness of a green pixel.
2. The colored composition can achieve both high brightness, high contrast, and long-term storage stability.
3. A color filter using the colored composition as a green pixel has extremely high color characteristics.
4). Since the liquid crystal display device according to the present invention uses an extremely high-quality color filter having green pixels having both high luminance and high contrast, the liquid crystal display device is extremely high quality.

(A), (b) is a schematic diagram for demonstrating the method to measure the chromaticity of the parallel transmission light and orthogonal transmission light of a colored plate, respectively. It is a figure showing the emission spectrum of the light source used when measuring the chromaticity coordinate (x, y) of an XYZ color system chromaticity diagram about the green pixel formed using the green pigment dispersion liquid. It is a spectrum figure which shows the characteristic of the polarizing plate used for the measurement of an Example and a comparative example. It is a microscope picture of the representative example of the pattern (pixel) used for the measurement. In FIG. 4, (a) is a pattern with no multiplication, (b) is a pattern with 57 multiplications, and (c) is a pattern with 100 or more multiplications.

32 color luminance meter
33, 35 Polarizing plate
34 Colored board
36 light
37 Backlight

Claims (4)

  A coloring composition for a color filter containing a pigment dispersion containing a pigment, a solvent and a dispersant, a binder resin and a photopolymerizable monomer, wherein the pigment is a pigment containing brominated zinc phthalocyanine, A color, wherein the photopolymerizable monomer is an addition-polymerizable compound having at least one ethylenic double bond, the compound having a molecular weight of 650 or less and a double bond equivalent of 150 or less Coloring composition for filters.   Furthermore, the coloring composition of Claim 1 containing a photoinitiator.   It has a pixel created using the coloring composition of Claim 1 or 2, The color filter characterized by the above-mentioned.   4. A liquid crystal display device, wherein the color filter according to claim 3 and a liquid crystal driving substrate are opposed to each other, and liquid crystal is sealed therebetween.