JP2010044243A - Pigment-dispersed liquid, colored composition for color filter, color filter, liquid crystal display and organic electroluminescent display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment-dispersed liquid from which a thin-film pixel high in luminance and contrast can be formed and to provide a colored composition for a color filter, the high-quality color filter formed by using the pigment-dispersed liquid and the colored composition and use of the color filter. <P>SOLUTION: The pigment-dispersed liquid for the color filter contains a pigment, a solvent and a dispersant at the least. C.I. (color index) pigment yellow 215 having ≤30 nm average primary particle size is used as the pigment. The colored composition for the color filter and use of the color filter are also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a pigment dispersion, a color filter coloring composition, a color filter formed using the same, a liquid crystal display device, and an organic EL display. More specifically, the present invention relates to a pigment dispersion containing a yellow pigment having high luminance, contrast, and coloring power, a coloring composition for a color filter, and uses thereof.

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 higher light transmittance, higher contrast, and higher color density are required for color filters.

  By the way, the coloring composition used for forming the red pixel and the green pixel of the color filter often uses a yellow pigment as a color material for toning in addition to the red pigment and the green pigment. For example, Patent Document 1 discloses C.I. I. (Color index; the same applies hereinafter) A green coloring composition is disclosed in which Pigment Green 36 and a yellow pigment of a specific nickel or copper complex are used in combination. By using this, a green color excellent in chromaticity and transmittance is disclosed. It is described that a color filter can be obtained. However, since the yellow pigment has a weak coloring power, an attempt to increase the color density in a composition containing the yellow pigment results in a significant increase in the pigment density, and developability when used in a photosensitive coloring composition. There was a tendency to decrease. Further improvement is also required for the contrast.

Examples of yellow pigments having high coloring power include C.I. I. Pigment Yellow 139 or the like is also used (see Patent Document 2). However, since the dye has a luminance and contrast that are not so high, there are cases in which the luminance and contrast of the resulting pixel are lowered when used together.
In addition, as seen in Patent Document 2, it is generally described that a wide variety of yellow pigments can be used in the color filter coloring composition. However, in reality, there are many inadequate coloring power and contrast, and among those skilled in the art, the azo nickel complex yellow pigment described in Patent Document 1 and C.I. I. The actual situation is that, except for a very limited yellow pigment such as CI Pigment Yellow 139, it is rarely used.
JP-A-9-269410 JP 2002-303718 A

  The present invention provides a pigment dispersion that can form thin film pixels with high brightness and contrast, and a coloring composition for a color filter, and also provides a high-quality color filter using these and a use thereof.

As a result of intensive studies, the present inventors have heretofore used yellow pigments that have been generally used by sufficiently atomizing specific yellow pigments that have not been used for color filters in general and have strong coloring power. The present inventors have found that brightness and contrast equivalent to or higher than those obtained when using can be achieved with a thin film to solve the above problems.
That is, the gist of the present invention is as follows.
[1] It contains at least a pigment, a solvent, and a dispersant, and the pigment has a C.I. I. (Color Index) Pigment Yellow 215, A pigment dispersion for a color filter.
[2] The color according to [1], wherein the dispersant contains a dispersant which is a block copolymer composed of an A-block having solvophilicity and a B-block having a functional group containing a nitrogen atom. Pigment dispersion for filters.
[3] The pigment dispersion for a color filter according to [1] or [2], further including a binder resin.
[4] A color filter coloring composition comprising a pigment dispersion and a polymerizable monomer in any one of the above [1] to [3].
[5] It contains at least a pigment, a solvent, a dispersant, and a polymerizable monomer, and the pigment has a C.I. I. (Color index) A coloring composition for a color filter, comprising Pigment Yellow 215.
[6] The color according to [5], wherein the dispersant contains a dispersant which is a block copolymer composed of an A-block having solvophilicity and a B-block having a functional group containing a nitrogen atom. Coloring composition for filters.
[7] The colored composition for a color filter according to the above [5] or [6], further comprising a binder resin.
[8] The pigment further contains C.I. I. (Color Index) Pigment Green 7, C.I. I. Pigment green 36, and C.I. I. The colored composition for a color filter according to any one of [4] to [7], comprising at least one selected from the group consisting of CI Pigment Green 58.
[9] The pigment further contains C.I. I. (Color Index) Pigment Red 254 and / or C.I. I. The coloring composition for a color filter according to any one of the above [4] to [7], comprising Pigment Red 177.
[10] A color filter having pixels formed using the color filter coloring composition according to any one of [4] to [9].
[11] A liquid crystal display device, wherein the color filter according to [10] and a liquid crystal driving substrate are opposed to each other, and liquid crystal is sealed therebetween.
[12] An organic EL display comprising the color filter according to [10].

  The pigment dispersion of the present invention and the coloring composition for color filter contain a specific yellow pigment that is sufficiently atomized, so that the image forming ability such as curability of the coloring composition for color filter does not deteriorate. A color filter with high brightness, high contrast, and low film thickness can be manufactured. By using such a color filter, an excellent liquid crystal display device or organic EL display with high brightness and high contrast can be obtained.

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.
In the present invention, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) acryl” "Acid" shall mean "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 this invention, a weight average molecular weight shall mean the polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
In the present invention, “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the weight of the base and the equivalent weight of KOH per 1 g of the solid content of the dispersant. is there. The measuring method will be described later.

[1] Pigment dispersion [1-1] Pigment The pigment used in the present invention has an average primary particle size of 30 nm or less. I. (Color index; the same applies hereinafter) Pigment Yellow 215 is contained as an essential component. By atomizing the pigment in this way, the brightness and contrast of the pigment itself are increased, and the brightness and contrast of pixels formed using a coloring composition for color filters such as red and green containing the pigment. Is also preferable. In addition, since the pigment has a high coloring power, it is not necessary to increase the pigment concentration so as to achieve a desired chromaticity in a pixel formed using the pigment, and as a result, a pixel having a thin film thickness is formed. This is also preferable.

  As the atomization method, a known method is used without particular limitation. For example, a commercially available pigment pigmented to a general-purpose pigment level is ground with a grinder such as a ball mill or a kneader. Among these, from the viewpoint of dispersion stability of the pigment, a pigment composition containing a pigment and a pigment derivative as a crystal growth inhibitor or a crystal transition inhibitor added as necessary, a water-soluble inorganic salt, a water-soluble organic solvent, A so-called solvent salt milling method in which a mixture is mixed and wet ground is preferable, and a kneader or a continuous kneader is mainly used in these methods.

  In the present invention, the average primary particle size is 30 nm or less. I. Pigment Yellow 215 (hereinafter sometimes referred to as “PY215 atomized pigment”) is manufactured by using a pigment pigmented to a general-purpose pigment level (a base pigment, ie, a pigment before atomization treatment) as it is. However, it is preferable to use those whose particle size is 50 nm to 200 nm by pretreatment (relatively gentle grinding) or the like.

  By wet-grinding a mixture prepared by premixing 25 to 2000 parts by weight of a water-soluble inorganic salt and 100 to 350 parts by weight of an organic solvent per 100 parts by weight of the base pigment, using a pressure or open kneader or continuous kneader. In the method for producing atomized pigments, the type of water-soluble inorganic salt to be used is not particularly limited, and sodium chloride (salt) is mainly used in the present invention, but sodium sulfate (bow glass) or the like is also used. be able to. If the amount of the inorganic salt used is too small, the atomization of the pigment becomes insufficient. On the other hand, if the amount of the inorganic salt used is too large, it is uneconomical. Further, if the amount of the organic solvent used is too small, the mechanical load becomes large and grinding is difficult. On the other hand, if the amount of the organic solvent used is too large, the load is hardly applied and the atomization is insufficient. It is.

  As the inorganic salt, sodium chloride (average salt) having an average particle size of 400 μm to 450 μm is usually used by dry grinding to have an average particle size of 50 μm to 60 μm. In the case of sodium chloride, in order to obtain a pigment having a primary particle size of 50 nm or less, it is necessary to devise such as considerably increasing the amount of sodium chloride relative to the pigment. Therefore, in the present invention, it is particularly preferable to use sodium chloride having an average particle size of about 1 to 30 μm.

As the water-soluble organic solvent used in the atomization step, monohydric alcohols, polyhydric alcohols and polyhydric alcohol derivatives can be used. For example, alcohol solvents such as propyl alcohol, 2-butyl alcohol, tert-butyl alcohol, alkylene glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and the like Glycol monoether solvents such as ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, Glycerin such as glycerin and polyglycerin System solvents, and water-soluble organic solvents such as glycerol ether derivatives thereof can be mentioned. The alcohol is not limited to the above.

Next, the method for producing the atomized pigment of the present invention will be described more specifically.
In the present invention, even when wet-grinding with a pressure type or open kneader, continuous kneader, so-called solvent salt milling is performed for a certain period of time while controlling the temperature of the pigment together with sodium chloride and diethylene glycol, The atomized pigment can be obtained by atomizing to the target particle size and repeating washing with demineralized water, filtration and drying.

  The time required for the grinding treatment varies depending on the pressure and temperature during the treatment, the treatment method, the type and particle size of the inorganic salt used, the primary particle size of the target pigment, the blade rotation speed, etc. 1 to 20 hours, preferably about 3 to 12 hours. The grinding treatment may be carried out continuously during the treatment time described above, or may be carried out in several steps, while adding a solvent, sodium chloride or the like as necessary.

The PY215 atomized pigment of the present invention thus obtained has an average primary particle size of 30 nm or less, and is preferably 20 nm or less from the viewpoint of further improving brightness and contrast.
The average primary particle size of the pigment can be determined by the following method. That is, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). From this image, in the case of organic pigments, the particle diameter of each pigment particle is set to a circle equivalent diameter converted to the diameter of a circle having the same area, and each of a plurality (usually 200 to 300) of pigment particles is divided into particles. After obtaining the diameter, the number average value is calculated according to the following formula to obtain the average particle diameter.

The particle diameter of each pigment _{particle: X 1, X 2, X} 3, X 4, ····, X i, ······ X m
Average particle size = ΣX _i / m
The pigment dispersion of the present invention only needs to contain the above-mentioned PY215 atomized pigment, but further contains a red pigment or a green pigment, and is generally used as a material for forming red or green pixels of a color filter. May be.

  Examples of red pigments that can be used in combination with PY215 atomized pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Among these, C.I. PY215 is preferably made from C.I. from the viewpoint that the effect of the finely divided pigment appears remarkably and the luminance and contrast of the obtained pixel are high. I. Pigment red 166, 177, 209, 224, 242, 254, etc., more preferably C.I. I. Pigment red 177, 254 and the like. These red pigments may be used alone or in combination of two or more.

  Examples of green pigments that can be used in combination include C.I. I. CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, and the like. . Among these, C.I. PY215 is preferably made from C.I. from the viewpoint that the effect of the finely divided pigment appears remarkably and the luminance and contrast of the obtained pixel are high. I. Pigment green 7, 36, 58, etc., more preferably C.I. I. And CI Pigment Green 36 and 58. These green pigments may be used alone or in combination of two or more.

The pigment dispersion of the present invention may contain a pigment other than the red pigment and the green pigment described above as long as the effects of the present invention are not impaired.
The average primary particle size of the pigment used in combination with the PY215 atomized pigment is not particularly limited as long as the performance of the PY215 atomized pigment is not impaired, but is usually 100 nm or less, preferably 40 nm or less, more preferably 30 nm or less, and still more preferably. It is 20 nm or less, and is usually 0.005 μm or more.

The pigment content in the pigment dispersion of the present invention is usually 90% by weight or less, preferably 85% by weight or less, more preferably 80% by weight or less, and usually 20% by weight or more, preferably based on the total solid content. Is 30% by weight or more, more preferably 40% by weight or more.
If the amount of the pigment is too large, it is difficult to maintain the dispersed state of the pigment, and aggregation and sedimentation may occur, resulting in problems such as thickening, luminance and a decrease in contrast. There is a possibility of a problem that it is thin and does not sufficiently function as a color filter.

As described above, when the pigment dispersion of the present invention contains a PY215 atomized pigment and other pigments, the ratio of the PY215 atomized pigment to the total amount of the pigment may be appropriately adjusted according to the desired chromaticity. . Specifically, a ratio similar to the ratio described later in the section “[2] Colored composition for color filter” is preferable.
The pigment dispersion of the present invention particularly preferably contains only PY215 atomized pigment as the pigment.

[1-2] Solvent In the pigment dispersion according to the present invention and the color filter coloring composition to be described later, the solvent dissolves or disperses the pigment, the dispersant, and other components blended in some cases, thereby increasing the viscosity. Has the ability to adjust.
As such a solvent, the following are mentioned, for example.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol Monomechi Ether, triethylene glycol monoethyl ether, glycol monoalkyl ethers such as 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, dipropylene glycol dimethyl ether.
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate.

Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diacetate.
Alkyl acetates such as cyclohexanol acetate.
Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether.

Like 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, methoxymethyl pentanone Ketones.
Monovalent or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol glycerin, and benzyl alcohol.

Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene and dodecane.
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and 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, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Chain or cyclic esters such as butyl and 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.
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.
The solvent in the pigment dispersion of the present invention has a good balance of coating properties, surface tension, etc. in the above-mentioned various solvents, and the solubility of the components of the pigment dispersion and the color filter coloring composition described later is relatively high. Glycol alkyl ether acetates are preferred, with propylene glycol monomethyl ether acetate being particularly preferred.

  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 from the viewpoint of high solubility of the constituents of the pigment dispersion and the color filter coloring composition described later. 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 have high polarity, and if the amount added is too large, the pigment tends to aggregate, and the storage stability such as an increase in the viscosity of the colored composition obtained later tends to decrease. The proportion of glycol monoalkyl ethers is preferably 5 to 30% by weight, more preferably 5 to 20% by weight.

[1-3] Dispersant The dispersant used in the present invention is not particularly limited, and is appropriately selected from those commonly used in pigment dispersions and color filter coloring compositions as long as the effects of the present invention are not impaired. For example, (E-1) a graft copolymer containing a nitrogen atom, (E-2) an acrylic block copolymer containing a nitrogen atom, and (E-3) a urethane resin dispersant, It is preferable to contain one or more selected dispersants.

In any of these (E-1) to (E-3), the nitrogen atom contained therein has an affinity for the pigment surface, and the portion other than the nitrogen atom increases the affinity for the medium as a whole. It is estimated that it contributes to the improvement of dispersion stability.
The performance of the dispersant is greatly influenced by its adsorption behavior on the solid surface. Regarding the relationship between the molecular architecture and the adsorption behavior, it is known that when the same unit is used, the adsorption behavior is excellent in the order of random copolymerization <graft copolymer <block copolymer ( For example, Jones and Richards, "Polymers at Surfaces and Interfaces" p281
).

Although the detailed mechanism is unknown, the following can be inferred.
That is, in the case of a normal random copolymer, the monomer constituting the copolymer has a high probability of being stably arranged in the copolymer sterically and / or electrically during the formation of the polymer. . The portion (molecule) in which the monomer is stably arranged is sterically and / or electrically stable, and thus may be an obstacle when adsorbed to the pigment. In contrast, for resins with a controlled molecular arrangement, such as graft copolymers or block copolymers, the part that prevents the adsorption of the dispersant should be placed at a position away from the adsorption part of the pigment and the dispersant. Can do. That is, an optimum portion for adsorption can be arranged in the adsorption portion between the pigment and the dispersant, and a portion suitable for it can be arranged in the portion requiring solvent affinity. In particular, for the dispersion of pigments having a small crystallite size, it is presumed that this molecular arrangement affects good dispersibility.

(E-1) Graft copolymer containing nitrogen atom
(E-1) A graft copolymer containing a nitrogen atom (hereinafter sometimes referred to as “dispersing agent (E-1)”) is preferable in that the pigment can be dispersed extremely efficiently. The reason is not clear, but it has a structure that can positively eliminate the part (molecule) that obstructs the adsorption of the pigment and the dispersant around the adsorption part to the pigment. It is guessed. As the graft copolymer containing a nitrogen atom, those having a repeating unit containing a nitrogen atom in the main chain are preferred. Especially, it is preferable to have a repeating unit represented by the following general formula (I) or / and a repeating unit represented by the following general formula (II).

(In the general formula (I), R ⁵¹ represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or a group represented by any one of general formulas (III) to (V) described later. )

(In the general formula (II), R ⁵¹ and A have the same meanings as in the general formula (I).)
In the general formulas (I) and (II), R ⁵¹ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, or a propylene group, preferably 2 to 3 carbon atoms. And more preferably an ethylene group.

A represents a hydrogen atom or any one of the following general formulas (III) to (V), and preferably has a structure represented by the following formula (III).

(In the above general formula (III), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms. Among them, an alkylene group having 4 to 7 carbon atoms such as a butylene group, a pentylene group and a hexylene group is preferable. (P represents an integer of 1 to 20, preferably an integer of 5 to 10.)

(In the general formula (IV), Y ₁ represents a divalent linking group, and in particular, an alkylene group having 1 to 4 carbon atoms such as an ethylene group or a propylene group, or a carbon number 1 such as an ethyleneoxy group or a propyleneoxy group. Is preferably an alkyleneoxy group having ˜4, W ₂ represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene group, propylene group, butylene group, etc. Among them, carbon number such as ethylene group, propylene group, etc. Preferred is an alkylene group having _{2 to 3.} Y ₂ represents a hydrogen atom or —CO—R ⁵² (wherein R ⁵² represents an alkyl group having 1 to 10 carbon atoms such as an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group). Among them, an alkyl group having 2 to 5 carbon atoms such as an ethyl group, a propyl group, a butyl group, and a pentyl group is preferable.) Q represents an integer of 1 to 20, and preferably an integer of 5 to 10. .

(In the above general formula (V), W ₃ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms having 1 to 5 hydroxyl groups, among which stearyl and other carbon atoms having 10 to 20 carbon atoms. A C10-20 hydroxyalkyl group having 1-2 hydroxyl groups such as an alkyl group and monohydroxystearyl is preferred.)
The content of the repeating unit represented by the general formula (I) or the general formula (II) in the dispersant (E-1) is preferably higher, and is usually 50 mol% or more, preferably 70 mol% or more. is there. The repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) may both be present, and the content ratio is not particularly limited, but the general formula (I) It is preferable to contain a large number of repeating units. The total number of repeating units represented by general formula (I) or general formula (II) is usually 1 to 100, preferably 10 to 70, and more preferably 20 to 50 in one molecule.

Further, the dispersant (E-1) may contain a repeating unit other than the general formula (I) and the general formula (II), and examples of the other repeating unit include an alkylene group and an alkyleneoxy group. .
(E-1) graft copolymer, the end -NH ₂ or ^-R 51 -NH ₂ (where ^{R 51} is the formula (the same meaning as ^{R 51} in I)) is preferable in.

In addition, as long as the dispersing agent (E-1) is a graft copolymer, the main chain may be linear or branched.
The amine value of a dispersing agent (E-1) is 5-100 mgKOH / g normally, Preferably it is 10-70 mgKOH / g, More preferably, it is 15-40 mgKOH / g or less. If the amine value is too low, the dispersion stability may decrease and the viscosity may become unstable. Conversely, if the amine value is too high, the residue may increase or the electrical characteristics after the liquid crystal panel is formed may deteriorate.

The amine value of the dispersant 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.
In a 100 mL beaker, 0.5-1.5 g of the dispersant sample is precisely weighed and dissolved in 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 polystyrene-reduced weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) of the dispersant (E-1) is preferably from 3,000 to 100,000, particularly preferably from 5,000 to 50,000. When the weight average molecular weight is less than 3,000, the aggregation of the pigment cannot be prevented and the viscosity or gelation may occur. When the weight average molecular weight exceeds 100000, the viscosity itself becomes high and the solubility in an organic solvent is increased. May be insufficient.

As a method for synthesizing the dispersant (E-1), a known method can be adopted, and for example, a method described in JP-B-63-30057 can be used.
In the present invention, as the dispersant (E-1), a commercially available graft copolymer having the same structure as that described above can also be applied.
(E-2) Acrylic block copolymer
(E-2) An acrylic block copolymer (hereinafter sometimes referred to as “dispersing agent (E-2)”) is preferable in that (A) the pigment can be dispersed extremely efficiently. The reason is not clear, but it is presumed that because the molecular arrangement is controlled, there are few structures that obstruct the dispersing agent when adsorbed on the pigment.

As the acrylic block copolymer of the dispersant (E-2), a block copolymer composed of an A-block having solvophilicity and a B-block having a functional group containing a nitrogen atom is preferable.
Specifically, the B-block includes a B-block having a quaternary ammonium base and / or amino group in the side chain as a nitrogen atom-containing functional group, and the solvophilic A-block includes a quaternary ammonium. A-blocks having no base and / or amino group are mentioned. These A-block and B-block, AB block copolymer and / or A
A -BA block copolymer is preferred. Hereinafter, these will be described in detail with reference to examples.

The quaternary ammonium base in the B-block is preferably —N ⁺ R ³¹ R ³² R ³³ · Z ⁻ (wherein R ³¹ R ³² and R ³³ are each independently a hydrogen atom or optionally substituted. Represents a cyclic or chain hydrocarbon group, or two or more of R ³¹ , R ³² and R ³³ may be bonded to each other to form a cyclic structure, and Z ⁻ represents a counter anion. .) Is a quaternary ammonium base. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

As the cyclic structure formed by combining two or more of R ³¹ , R ^32, and R ³³ in —N ⁺ R ³¹ R ³² R ³³ · Z ^— , for example, a 5- to 7-membered nitrogen-containing heterocyclic ring Examples thereof include a single ring or a condensed ring formed by condensing two of these. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following.

(In the above formula, R represents any group of R ³¹ , R ³² and R ^33. These cyclic structures may further have a substituent.)
More preferred as ^{R 31, R 32} and ^{R 33} in ^{-N + R 31 R 32 R 33} , each independently, optionally substituted alkyl group having 1 to 3 carbon atoms, or a substituent It is a phenyl group which may have, or a benzyl group which may have a substituent.

  As the B-block having a quaternary ammonium base, those containing a partial structure represented by the following general formula (VI) are preferable.

(In the general formula (VI), R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, R ³¹ , R ³² And two or more of R ³³ may be bonded to each other to form a cyclic structure, R ³⁴ represents a hydrogen atom or a methyl group, X ¹ represents a divalent linking group, and Z ⁻ Represents a counter anion.)
In the general formula (VI), the hydrocarbon groups of R ³¹ , R ³² and R ³³ are each independently a substituent having an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 20 carbon atoms. preferable. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, and a phenyl group. Of these, a methyl group, an ethyl group, a propyl group, and a benzyl group are preferable.

In the general formula (VI), examples of the divalent linking group X ¹ include an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R ³⁵ —, —COO—R ³⁶ — (provided that R ³⁵ and R ³⁶ is each independently a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R ³⁷ —O—R ³⁸ —: R ³⁷ and R ³⁸ are each independently Represents an alkylene group), and the like, and is preferably —COO—R ³⁶ —.

Further, Z ⁻ of the counter anion includes Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ^{− and the} like.
When the B-block has an amino group, the amino group is preferably a tertiary amino group. Specifically, —NR ⁴¹ R ⁴² (provided that R ⁴¹ and R ⁴² each independently have a substituent). A cyclic or chain alkyl group which may be substituted, an allyl group which may have a substituent, or an aralkyl group which may have a substituent. Examples of the repeating unit having such a structure include structures represented by the following general formula.

^{(However, R 41} and ^{R 42} is synonymous with ^{R 41} and ^{R 42} as described ^{above, R 43} is 1 or more alkylene groups having a carbon ^{number, 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 methyl group. Examples of such repeating units include structures represented by the following structural formula.

Two or more kinds of partial structures containing a specific quaternary ammonium base and / or amino group as described above may be contained in one B-block. In that case, two or more quaternary ammonium bases and / or 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 this quaternary ammonium base and / or amino group may be contained in the B-block, and examples of the partial structure are derived from the (meth) acrylic acid ester monomer described later. And the like. The content of the partial structure containing no quaternary ammonium base and / or amino group in the B-block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably, the base and / or amino group-free partial structure is not contained in the B-block.

  On the other hand, as the A-block constituting the acrylic block copolymer of the dispersant (E-2), for example, styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, (meth) acrylic Ethyl acetate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) (Meth) acrylic ester monomers such as acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate; (meth) acrylic such as (meth) acrylic acid chloride Acid salt Mar; vinyl acetate monomers; allyl glycidyl ether, polymer structure obtained by copolymerizing comonomers including glycidyl ether monomers such as crotonic acid glycidyl ether.

  Among them, as an A-block, polyalkylene glycol (meth) acrylate such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate is included as a copolymerization component (that is, a partial structure derived from polyalkylene glycol (meth) acrylate). (Including) a partial structure is preferable because an appropriate anti-aggregation effect is recognized and contributes to the stabilization of the dispersion, and an A-block having a partial structure represented by the following formula (VII) is particularly preferable.

(In the formula, g represents an integer of 1 to 5, and R ⁶⁰ represents a hydrogen atom or a methyl group.)
The partial structure represented by the above formula (VII) is particularly preferably contained in the A-block in an amount of 5 to 40 mol%.
In addition, the A-block is a (meth) acrylic acid ester-based compound represented by the following general formula (VIII), particularly in terms of improving the familiarity with the nonpolar portion of the solvent by imparting appropriate hydrophobicity. It preferably contains a partial structure derived from a monomer.

(In the general formula (VIII), R ³⁹ represents a hydrogen atom or a methyl group. R ⁴⁰ may have a cyclic or chain alkyl group which may have a substituent, or a substituent. Represents a good allyl group or an aralkyl group which may have a substituent.)
R ⁴⁰ is preferably a cyclic group from the viewpoint of high affinity with the pigment and good compatibility.

  Two or more types of partial structures derived from the (meth) acrylic acid ester monomer may be contained in one A-block. Of course, the A-block may further contain a partial structure other than these. When a partial structure derived from two or more monomers is present in an A-block that does not contain a quaternary ammonium base, each partial structure is contained in the A-block in any form of random copolymerization or block copolymerization. May be. When the A-block contains a partial structure other than the partial structure derived from the (meth) acrylate monomer, the content in the A-block of the partial structure other than the (meth) acrylate monomer is , Preferably 0 to 99% by weight, more preferably 0 to 85% by weight.

The acrylic dispersant of the dispersant (E-2) is an AB block or ABA block copolymer type polymer compound composed of such an A-block and a B-block. Such a block copolymer is prepared by a living polymerization method such as an anion living polymerization method, a cation living polymerization method, or a radical living polymerization method.
The amine value of 1 g of the solid content of the dispersant (E-2) is usually about 1 to 300 mgKOH / g, but the preferred range is when the B-block has a quaternary ammonium base and when it does not. Different.

  That is, when the B block of the AB block copolymer and the ABA block copolymer of the dispersant (E-2) has a quaternary ammonium base, the quaternary in 1 g of the copolymer. The amount of ammonium base is preferably 0.1 to 10 mmol. Outside this range, it may not be possible to combine good heat resistance and dispersibility. In such a block copolymer, an amino group generated in the production process may be contained, and its amine value is usually about 1 to 100 mgKOH / g, preferably 1 to 50 mgKOH per 1 g of the copolymer. / G, more preferably 1 to 30 mg KOH / g.

When the quaternary ammonium base is not contained in the B-block, the amine value of the copolymer is usually about 50 to 300 mgKOH / g, preferably 50 to 200 mgKOH / g per gram. The method for measuring the amine value is as described above.
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 is generally preferably lower, usually 100 mgKOH / g or less, and its molecular weight is GPC. The measured polystyrene average weight average molecular weight (Mw) is usually in the range of 1000 or more and 100,000 or less. When the molecular weight of the block copolymer is too small, the dispersion stability is lowered, and when it is too large, the developability and the resolution tend to be lowered.

In the present invention, a commercially available acrylic block copolymer having the same structure as that described above can also be applied as the dispersant (E-2).
(E-3) Urethane resin dispersant
(E-3) As a urethane resin dispersant (hereinafter sometimes referred to as “dispersant (E-3)”), a polyisocyanate compound, a compound having one or two hydroxyl groups in the same molecule, A urethane resin obtained by reacting an active hydrogen with a compound having a tertiary amino group in the same molecule is particularly preferred.

  Examples of the polyisocyanate compounds include aromatics such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω ' -Alicyclic diisocyanates such as diisocyanate dimethylcyclohexane; xylylene diisocyanate, α, α, α ', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as xylylene diisocyanate; lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate And triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane) and tris (isocyanatephenyl) thiophosphate; and their trimers, water adducts, and polyol adducts thereof.

Preferred as the polyisocyanate is a trimer of an organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate, which may be used alone or in combination of two or more. .
As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

Examples of the compound having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, or one terminal hydroxyl group of these compounds is an alkyl group having 1 to 25 carbon atoms and alkoxy. Or a mixture of two or more of these.
Examples of the polyether glycol include polyether diol, polyether ester diol, or a mixture of two or more of these.

  As the polyether diol, those obtained by homopolymerizing or copolymerizing alkylene oxide, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, Or the mixture of 2 or more types of those is mentioned.

Examples of the polyether ester diol include those obtained by reacting a mixture of an ether group-containing diol or other glycol with a dicarboxylic acid or an anhydride thereof, or by reacting polyester glycol with an alkylene oxide. And oxytetramethylene) adipate.
Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Examples of the polyester glycol include dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, and phthalic acid, or anhydrides thereof, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene. Glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neo Pentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentane Diol, 1,6-hexanediol, 2-methyl-2 4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene Aliphatic glycols such as glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol; alicyclic glycols such as bishydroxymethylcyclohexane; aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene Obtained by polycondensation with a diol such as N-alkyldialkanolamine such as N-methyldiethanolamine, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, or the like; The diols The polylactone diol or polylactone monool obtained by using a monohydric alcohol having 1 to 25 carbon atoms as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone, or mixture of two or more thereof. Most preferred as the polyester glycol is a polycaprolactone glycol or polycaprolactone starting from an alcohol having 1 to 25 carbon atoms, more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to a monool. is there.

Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate.
Examples of the polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol.
Of these compounds having one or two hydroxyl groups in the same molecule, polyether glycol and polyester glycol are particularly preferred.

In addition, the number average molecular weight of the compound which has one or two hydroxyl groups in the same molecule is 300-10,000 normally, Preferably it is 500-6,000, More preferably, it is 1,000-4,000.
In the compound having an active hydrogen and a tertiary amino group in the same molecule, the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom includes a hydroxyl group, an amino group, a thiol group, etc. Among these, a hydrogen atom in the functional group is mentioned, and an amino group, particularly a primary amino group hydrogen atom is preferable. As the tertiary amino group, for example, a dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, isopropyl, n-butyl, or the like, and the dialkylamino group are linked to form a heterocyclic structure. More specifically, an imidazole ring or a triazole ring can be mentioned. Among them, a dimethylamino group and an imidazole ring are preferable because of excellent dispersion stability.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  In addition, the tertiary amino group is a nitrogen-containing heterocycle, such as pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include nitrogen-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring; nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline ring. Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. It is done.

  Further, specific examples of the compound having a triazole ring and a primary amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H. -1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino Examples include -1,4-diphenyl-1,2,3-triazole and 3-amino-1-benzyl-1H-2,4-triazole.

Among these, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1
2,4-triazole and the like are preferable.
The preferred use ratio of the raw materials for these (E-3) dispersants is usually 10 to 200 parts by weight, preferably 10 to 200 parts by weight of a compound having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. 20 to 190 parts by weight, more preferably 30 to 180 parts by weight, and the compound having an active hydrogen and a tertiary amino group in the same molecule is usually 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight. is there.

If the content of a compound having one or more hydroxyl groups in the same molecule is more than the above range, the synthesis may be difficult, such as gelation due to too many reaction points during compound synthesis, If the amount is less than the above range, the so-called tail portion of the dispersant is shortened, which may result in insufficient dispersibility.
In addition, if the content of the compound having active hydrogen and amino group in the same molecule is more than the above range, the number of free adsorbing groups that do not adsorb to the pigment increases, and it is considered that these become reaction points in the colored composition. , Storage stability may be adversely affected. When the amount is less than the above range, the dispersant is difficult to be adsorbed to the pigment and may not function sufficiently as a dispersant.

  The dispersant (E-3) is produced according to a known method for producing a urethane resin. Solvents used in the production are usually ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone; esters such as ethyl acetate, butyl acetate and cellosolve; benzene, toluene, xylene and hexane Hydrocarbons such as diacetone alcohol, some alcohols such as isopropanol, sec-butanol and tert-butanol; halogenated hydrocarbons such as methylene chloride and chloroform; ethers such as tetrahydrofuran and diethyl ether; dimethylformamide An aprotic polar solvent such as N-methylpyrrolidone or dimethyl sulfoxide is used. Moreover, as a catalyst at the time of manufacture, a normal urethanization reaction catalyst is used. For example, tin systems such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stanas octoate; iron systems such as iron acetylacetonate and ferric chloride; tertiary amine systems such as triethylamine and triethylenediamine Can be mentioned.

  The amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g by the amine value of the dispersant (E-3) obtained by the reaction, More preferably, it is the range of 5-80 mgKOH / g, More preferably, it is the range of 10-60 mgKOH / g. When the amine value is less than the above range, the dispersing ability tends to decrease, and when it exceeds the above range, the developability tends to decrease. In addition, when an isocyanate group remains in the dispersant (E-3) obtained by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the stability of the dispersant molecule with time increases. .

  The weight average molecular weight (Mw) in terms of polystyrene measured by GPC of the urethane resin dispersant (E-3) is usually 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3, It is in the range of 000 to 50,000. When the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and when it exceeds 200,000, the solubility is lowered, and the dispersibility is inferior and the reaction is difficult to control.

(E-4) Other dispersant
In addition to the various dispersants (E-1) to (E-3) described above, the dispersant used in the pigment dispersion and the coloring composition of the present invention may be other dispersants (hereinafter “dispersant (E-4)”). May be included).
Other dispersants include, for example, polyallylamine dispersants, dispersants composed of monomers and macromonomers having amino groups, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, and polyether phosphates. Examples thereof include a dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

  Specific examples of such a dispersant include EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by Big Chemie), Disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Lubrizol), KP (manufactured by Shinetsu) Chemical products), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and other series names can be mentioned.

The above dispersants (E-1) to (E-4) may be used alone or in combination of two or more.
The pigment dispersion and the coloring composition of the present invention include (E-1) a graft copolymer containing a nitrogen atom and (E-2) an acrylic block copolymer containing a nitrogen atom among the various dispersants described above. It is preferable to include one or more dispersants selected from the coalesced and (E-3) urethane resin dispersants, and it is more preferable to include (E-2) an acrylic block copolymer containing a nitrogen atom. .

  In the pigment dispersion and coloring composition of the present invention, the content of the dispersant is usually 95% by weight or less, preferably 65% by weight or less, more preferably 50% by weight or less, and usually 5% by weight or less. % By weight or more, preferably 7% by weight or more, particularly preferably 10% by weight or more. If the content of the dispersant is too small, adsorption to the pigment is insufficient, aggregation cannot be prevented, and viscosity or gelation may occur, so dispersion stability deteriorates and reaggregation or increase occurs. Problems such as stickiness may occur. On the other hand, if the amount is too large, the ratio of the pigment is relatively reduced, so the coloring power is low, the film thickness is too thick for the color density, and when used in a color filter, the cell gap in the liquid crystal cell forming process. Poor control may occur.

[1-4] Dispersion aid The pigment dispersion according to the present invention may contain a dispersion aid in order to improve the dispersibility and dispersion stability of the pigment. Examples of the dispersion aid include pigment derivatives.
Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketo Examples thereof include derivatives such as pyrrolopyrrole and dioxazine pigments.

  Examples of the substituent of these pigment derivatives include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group. These substituents may be directly bonded to the pigment skeleton, or may be bonded via an alkylene group, an arylene group, a heterocyclic group or the like. Of the substituents, a sulfonamide group and a quaternary salt thereof, and a sulfonic acid group are preferable, and a sulfonic acid group is more preferable.

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 that has little interference with the hue of the pigment dispersion is preferable.
The dispersing aid may not be a derivative of the pigment itself as described above, but may be a compound having a similar chemical structure.
The addition amount of the dispersion aid 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. It is. 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] Dispersion Resin The pigment dispersion of the present invention contains a part or all of a resin selected from binder resins that can be used in the coloring composition for a color filter of the present invention described later. May be. Specifically, in the dispersion treatment step in the preparation of the pigment dispersion described later, the binder resin contributes to the dispersion stability through a synergistic effect with the dispersant by including the binder resin together with the above-described dispersant. As a result, the amount of the dispersant added may be reduced, which is preferable. Further, it is preferable because the developability is improved, the undissolved material does not remain in the non-pixel portion of the substrate, and the adhesion of the pixel to the substrate is improved.

As described above, the binder resin used in the dispersion treatment step may be referred to as a dispersion resin.
The dispersion 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 pigment in the pigment dispersion.
The acid value of the dispersion resin is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, most preferably 50 mgKOH / g or more, more preferably 500 mgKOH / g or less, more preferably 300 mgKOH / g or less, and 200 mgKOH / g or less. Most preferred. 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.

The weight average molecular weight in terms of polystyrene measured by GPC of the dispersion resin is preferably 1000 or more, more preferably 1500 or more, most preferably 2000 or more, more preferably 200000 or less, more preferably 50000 or less, most preferably 30000 or less. 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.
[2] Coloring composition for color filter
The coloring composition for a color filter of the present invention contains at least the pigment, solvent and dispersant described above and a polymerizable monomer.

  In the present invention, the method for preparing the coloring composition is not particularly limited, and a pigment dispersion as described above may be prepared in advance, and various components may be added thereto to prepare a coloring composition for a color filter. Moreover, you may prepare this coloring composition by mix | blending the component which comprises the coloring composition for color filters at once or sequentially. It should be noted that the pigment should be prepared in advance because the pigment can be finely dispersed in the dispersion step described later, and because it is easier to handle when there is no photopolymerization or no photopolymerizable component during the dispersion treatment. A method of adding other components to the pigment dispersion prepared is more preferable.

[2-1] Polymerizable monomer The polymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular compound, but an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred). When the colored composition of the present invention is irradiated with actinic rays, the ethylenic compound is an action of a photopolymerization initiation system described later, or an action of a thermal polymerization initiator described later by heating,
It is a compound having an ethylenic double bond that undergoes addition polymerization and cures. In addition, the monomer in this invention means the concept which opposes what is called a polymeric substance, and means the concept which also includes 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 inferior. 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, dipentaerythritol pentaacrylate, which is 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. Further, the lower limit thereof is not particularly limited, and may be a range that 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.

  In addition, it is preferable to use the ethylenic compound whose molecular weight exceeds 250 from the point of the sensitivity of the coloring composition for color filters obtained. As such a compound, pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are particularly preferable.

  The content of these polymerizable monomers 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 in the total solid content of the colored composition of the present invention. It is preferably 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] Other solids (components)
The colored composition for a color filter of the present invention may further contain a solid content other than the above components as necessary. Examples of such components include binder resins, photopolymerization initiation systems and / or thermal polymerization initiators, surfactants, thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protective agents, adhesion improvers, development improvers, And dyes.

[2-3] Binder resin
It is preferable that the coloring composition for color filters of this invention contains binder resin. The preferred resin for the binder resin varies depending on the means by which the colored composition is cured.
When the coloring composition of the present invention is a photopolymerizable resin composition, examples of the binder resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, Known polymer compounds described in JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, and the like can be used, but preferably [2-3-1 ] A resin obtained by adding an unsaturated monobasic acid to at least a part of an epoxy group of a copolymer of an epoxy group-containing (meth) acrylate and another 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,
[2-3-2] a linear alkali-soluble resin containing a carboxyl group in the main chain;
[2-3-3] A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the “linear alkali-soluble resin containing a carboxyl group in the main chain”;
[2-3-4] (meth) acrylic resin,
[2-3-5] An epoxy (meth) acrylate resin having a carboxyl group and the like can be mentioned. Hereinafter, each of these resins will be described.

[2-3-1] 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 of particularly preferred resins, “epoxy group-containing (meth) acrylate” And a resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group of the copolymer with respect to a copolymer with the other radical polymerizable monomer or the addition reaction. And “an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group” (hereinafter sometimes referred to as “[2-3-1] resin”). More specifically, with respect to a copolymer of 5 to 90 mol% of an epoxy group-containing (meth) acrylate and 10 to 95 mol% of another radical polymerizable monomer, Resins obtained by adding unsaturated monobasic acid to 10 to 100 mol%, or alkali-soluble resins obtained by adding polybasic acid anhydrides to 10 to 100 mol% of hydroxyl groups generated by the addition reaction ” It is done.

  [2-3-1] Examples of the “epoxy group-containing (meth) acrylate” constituting the resin include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and (3,4-epoxycyclohexyl). Examples thereof include 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. Good.
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 rilates, (meth) acryloylnitriles, 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, the content of the repeating unit derived from at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide in the repeating unit derived from “another radical polymerizable monomer” 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, and 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 the like Are preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably 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 ethylenically unsaturated 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.
[2-3-1] The polystyrene-reduced weight average molecular weight (Mw) of the resin as 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.

[2-3-2] Linear alkali-soluble resin containing a carboxyl group in the main chain
The linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter sometimes referred to as “[2-3-2] resin”) is not particularly limited as long as it has a carboxyl group. It is obtained by polymerizing a polymerizable monomer containing a carboxyl group.
Examples of the carboxyl group-containing polymerizable monomer include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl. Adipic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2 -(Meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyl Oxybutyl succinic acid, 2- (meta Vinyl monomers such as acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid; Monomers obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone; hydroxyalkyl (meth) acrylate to succinic acid, maleic acid, phthalic acid, or Examples thereof include monomers added with acids or anhydrides such as anhydrides thereof. A plurality of these may be used.

Among these, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is more preferable.
The linear alkali-soluble resin containing a carboxyl group in the main chain may be copolymerized with the above-mentioned polymerizable monomer having no carboxyl group to the carboxyl group-containing polymerizable monomer. .

Other polymerizable monomers include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate , Benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxy (Meth) acrylic esters such as ethyl (meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate; vinyl aromatics such as styrene and its derivatives Vinyl compounds such as N-vinylpyrrolidone; N-substituted maleimides such as N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide; polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly-2-hydroxyethyl Examples thereof include macromonomers such as (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, and polycaprolactone macromonomer. These may be used in combination.

  Particularly preferred are styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, They are butyl (meth) acrylate, isobutyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, and N-phenylmaleimide.

  [2-3-2] The resin may further have a hydroxyl group. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and the like. Is mentioned. By copolymerizing these with the above-mentioned various monomers, a resin having a carboxyl group and a hydroxyl group can be obtained.

  [2-3-2] Specifically, for example, (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl ( Polymeric monomers that do not contain hydroxyl groups such as (meth) acrylate and cyclohexylmaleimide, and hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate (Meth) acrylic acid and (meth) acrylic acid esters such as methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl methacrylate, etc. With (meth) a copolymer Copolymers of acrylic acid and styrene; a copolymer of (meth) acrylic acid and styrene and α- methylstyrene; a copolymer of (meth) acrylic acid and cyclohexyl maleimide.

From the viewpoint of excellent pigment dispersibility, a copolymer resin containing benzyl (meth) acrylate and / or cyclohexyl (meth) acrylate is particularly preferable.
[2-3-2] The acid value of the resin is usually 30 to 500 mgKOH / g, preferably 40 to 350 mgKOH / g, more preferably 50 to 300 mgKOH / g.
Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-20000 normally, Preferably it is 3000-50000, More preferably, it is 4000-30000. If the weight average molecular weight is too small, the stability of the colored composition tends to be inferior. If it is too large, the solubility in a developer tends to deteriorate when used in a color filter or a liquid crystal display device described later.
[2-3-3] Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the “linear alkali-soluble resin containing a carboxyl group in the main chain” The “contains a carboxyl group in the main chain” Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the linear alkali-soluble resin (ie, [2-3-3] resin) (hereinafter referred to as [2-3-3] resin) Are also particularly preferred.

The epoxy group-containing unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule.
For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, 4- Acyclic epoxy group-containing unsaturated compounds such as hydroxybutyl (meth) acrylate glycidyl ether can also be mentioned, but from the viewpoints of heat resistance and dispersibility of the pigment described later, alicyclic epoxy group-containing unsaturated compounds are used. preferable.

  Here, as the alicyclic epoxy group-containing unsaturated compound, as the alicyclic epoxy group, for example, 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 7,8-epoxy [tricyclo [5 .2.1.0] dec-2-yl] group and the like. Further, the ethylenically unsaturated group is preferably derived from a (meth) acryloyl group, and suitable alicyclic epoxy group-containing unsaturated compounds are represented by the following general formulas (3a) to (3m). And the compounds represented.

In formulas (3a) to (3m), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents an alkylene group, R ¹³ represents a divalent hydrocarbon group, and n is an integer of 1 to 10.
In general formulas (3a) to (3m), the alkylene group for R ¹² preferably has 1 to 10 carbon atoms. Specific examples include a methylene group, an ethylene group, a propylene group, and a butylene group, and a methylene group, an ethylene group, and a propylene group are preferable. As the hydrocarbon group R ^13, preferably has 1 to 10 carbon atoms, alkylene group, a phenylene group, and the like.

These alicyclic epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.
Among these, a compound represented by the general formula (3c) is preferable, and 3,4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable.
A known method can be used to add the epoxy group-containing unsaturated compound to the carboxyl group portion of the [2-3-2] resin. For example, a carboxyl group-containing resin and an epoxy group-containing unsaturated compound are converted into a tertiary amine such as triethylamine or benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride A quaternary ammonium salt such as pyridine, triphenylphosphine, etc. in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours. Saturated compounds can be introduced.

[2-3-3] The acid value of the resin is usually 10 to 200 mgKOH / g, preferably 20 to 150 mgKOH / g, more preferably 30 to 150 mgKOH / g.
Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-100000 normally, Preferably it is 4000-50000, More preferably, it is 5000-30000.

[2-3-4] (Meth) acrylic resin
(Meth) acrylic resin (hereinafter sometimes referred to as “[2-3-4] resin”) includes (meth) acrylic acid and / or (meth) acrylic acid ester as monomer components. Refers to a polymer obtained by polymerizing Preferred (meth) acrylic resins include, for example, a polymer [2-3-4a] obtained by polymerizing monomer components including (meth) acrylic acid and benzyl (meth) acrylate, and the following general formula (4) And / or a polymer [2-3-4b] obtained by polymerizing a monomer component essentially comprising the compound represented by (5).

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.
[2-3-4a] 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.

[2-3-4b] A polymer obtained by polymerizing a monomer component essentially comprising the compound represented by 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 Examples include '-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, and the like.

  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 not particularly limited as long as they are divalent linking groups and L ³ 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 carbons, —O—, —S—, —C (═O) —, or alkenylene having 1 to 15 carbons. , Phenylene, or combinations thereof are preferred.

Preferred combinations of ^{L 1, L 2, L 3} , L 3 is a direct bond, the ring formed by the bonding alkylene of 1 to 5 carbon atoms, or a R ^3b or R ^4b, L ^1, L ² is 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. You may have, specifically,
For example, the following substituents can be mentioned.

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 [2-3-4b] polymer according to the present invention, the ratio of the general formula (5) is not particularly limited, but usually 0.5 to 60% by weight in the total monomer components. The amount is 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 suitability may be lowered.

The [2-3-4] resin in the present invention preferably has an acid group, including the polymers [2-3-4a] and [2-3-4b]. 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.
[2-3-4] In order to introduce an acid group into the resin, for example, a monomer having an acid group and / or a “monomer capable of imparting an acid group after polymerization” (hereinafter referred to as “single amount for introducing an acid group”) May be referred to as “body”) 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.
[2-3-4] When the monomer component in obtaining the resin also includes the monomer for introducing the acid group, the content ratio is not particularly limited, but usually all monomer components The content is 5 to 70% by weight, preferably 10 to 60% by weight.

[2-3-4] The resin may have a radical polymerizable double bond.
[2-3-4] In order to introduce a radical polymerizable double bond into a resin, for example, “a monomer capable of imparting a radical polymerizable double bond after polymerization” (hereinafter referred to as “to introduce a radical polymerizable double bond”). May be referred to as a “monomer”)), and after the polymerization as a monomer component, 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.

[2-3-4] When the monomer component in obtaining the resin also includes a monomer for introducing the radical polymerizable double bond, the content ratio is not particularly limited, It is 5-70 weight% in a monomer component, Preferably it is 10-60 weight%.
When the [2-3-4] resin is a polymer having the compound of the general formula (4) as an essential monomer component described in [2-3-4a], it preferably has an epoxy group. .

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.

[2-3-4] When the monomer component in obtaining the resin also includes a monomer for introducing the epoxy group, the content ratio is not particularly limited, but usually all monomer components The content is 5 to 70% by weight, preferably 10 to 60% by weight.
[2-3-4] The monomer component for obtaining the resin may contain other copolymerizable monomers, if necessary, in addition to the essential monomer component.

  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 [2-3-4] resin is used as a dispersant as will be described later, it is preferable to use benzyl (meth) acrylate, and the content thereof is usually the total single amount. It may be 1 to 70% by weight, preferably 5 to 60% by weight in the body component.

When the monomer component in obtaining the [2-3-4] 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, [2-3-4] resin production method (polymerization method) 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. The polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and 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 acid group is introduced by using the monomer capable of imparting the acid group described above as the monomer component when obtaining the [2-3-4] resin, a treatment for imparting the acid group after polymerization Need to do. 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 radical polymerizable double bond is introduced by using the monomer capable of imparting the radical polymerizable double bond described above as the monomer component when obtaining the [2-3-4] resin, It is necessary to perform a treatment for imparting a radically polymerizable double bond.
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.

  [2-3-4] The weight average molecular weight of the resin is not particularly limited, but the polystyrene equivalent weight average molecular weight measured by GPC is preferably 2,000 to 200,000, more preferably 4,000 to 100,000. 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.

[2-3-4] When the resin has an acid group, a preferable acid value is 30 to 500 mgKOH / g, more preferably 50 to 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 [2-3-4] resins, examples of the polymer having the compound represented by the general formula (4) as an essential monomer component include, for example, JP-A Nos. 2004-300203 and 2004-2004. Listed are compounds described in Japanese Patent No. 300204.

[2-3-5] Epoxy acrylate resin having carboxyl group
The “epoxy acrylate resin having a carboxyl group” (hereinafter sometimes referred to as “[2-3-5] resin”) has an α, β-unsaturated monocarboxylic acid or ester group in the epoxy resin. It is synthesized by adding an α, β-unsaturated monocarboxylic acid ester and further reacting with a polybasic acid anhydride. Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to “acrylate”, but epoxy resin is a raw material, and “acrylate” is a representative example. It is named like this according to common usage.

  As an epoxy resin used as a raw material, for example, bisphenol A type epoxy resin (for example, “Epicoat 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004”, etc., manufactured by Japan Epoxy Resin Co., Ltd.), Epoxy resin obtained by reaction of alcoholic hydroxyl group and epichlorohydrin (for example, “NER-1302” (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin (for example, manufactured by Japan Epoxy Resin Co., Ltd.) "Epicoat 807", "EP-4001", "EP-4002", "EP-4004 etc."), epoxy resins obtained by reaction of alcoholic hydroxyl groups of bisphenol F type epoxy resins with epichlorohydrin (for example, Nippon Kayaku) “NE” -7406 "(epoxy equivalent 350, softening point 66 ° C)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example," YX-4000 "manufactured by Japan Epoxy Resin), phenol novolac type epoxy resin (for example, Nippon Kayaku) “EPPN-201” manufactured by Yakuhin, “EP-152”, “EP-154” manufactured by Japan Epoxy Resin, “DEN-438” manufactured by Dow Chemical Co., Ltd.), (o, m, p-) cresol novolak Type epoxy resin (for example, “EOCN-102S”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, “TEPIC” manufactured by Nissan Chemical Co., Ltd.), trisphenol Methane type epoxy resin (for example, “EPPN-501”, “EP” manufactured by Nippon Kayaku Co., Ltd.) -502 "," EPPN-503 "), fluorene epoxy resin (for example, cardo epoxy resin" ESF-300 "manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin (" Celoxide 2021P "manufactured by Daicel Chemical Industries, Ltd.) , “Celoxide EHPE”), dicyclopentadiene type epoxy resin obtained by glycidylation of phenol resin by reaction of dicyclopentadiene and phenol (for example, “XD-1000” manufactured by Nippon Kayaku Co., Ltd., “EXA” manufactured by Dainippon Ink & Chemicals, Inc. -7200 "," NC-3000 "," NC-7300 "manufactured by Nippon Kayaku Co., Ltd.), and an epoxy resin represented by the following structural formula (see JP-A-4-355450), etc. are preferably used. it can.

These may be used alone or in combination of two or more.
Another example of the epoxy resin is a copolymer type epoxy resin. Examples of the copolymerization type epoxy resin include glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, vinylcyclohexene oxide and the like (hereinafter referred to as “first component of copolymerization type epoxy resin”) and one other than these. Functional ethylenically unsaturated group-containing compound (hereinafter referred to as “second component of copolymerization type epoxy resin”), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxy Ethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α-methylstyrene, glycerol mono (meth) acrylate, the following general formula (8 Or a compound represented by One or more selected, reacting the city include a copolymer obtained by.

In Formula (8), R ⁶¹ represents a hydrogen atom or an ethyl group, R ⁶² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and r is an integer of 2 to 10.
Examples of the compound of the general formula (8) include polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and tetraethylene glycol mono (meth) acrylate; methoxydiethylene glycol mono ( Examples thereof include alkoxy polyethylene glycol (meth) acrylates such as meth) acrylate, methoxytriethylene glycol mono (meth) acrylate, and methoxytetraethylene glycol mono (meth) acrylate.

As for the molecular weight of the said copolymerization type epoxy resin, about 1000-200000 is preferable. The amount of the first component of the copolymerization type epoxy resin used is preferably 10% by weight or more, particularly preferably 20% by weight or more, preferably 70% by weight based on the second component of the copolymerization type epoxy resin. % By weight or less, particularly preferably 50% by weight or less.
As such a copolymer type epoxy resin, specifically, “CP-15”, “CP-30”, “CP-50”, “CP-20SA”, “CP-510SA” manufactured by NOF Corporation, “CP-50S”, “CP-50M”, “CP-20MA” and the like are exemplified.

  The molecular weight of the raw material epoxy resin is usually in the range of 200 to 200,000, preferably 300 to 100,000, as the weight average molecular weight in terms of polystyrene measured by GPC. If the weight average molecular weight is less than the above range, there are many cases where a problem occurs in the film forming property. Conversely, if the resin exceeds the above range, gelation easily occurs during the addition reaction of α, β-unsaturated monocarboxylic acid. May become difficult.

Examples of the α, β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid and the like, preferably acrylic acid and methacrylic acid, and particularly acrylic acid is highly reactive. Therefore, it is preferable.
The α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion includes acrylic acid-2-succinoyloxyethyl, acrylic acid-2-malenoyloxyethyl, acrylic acid-2-phthaloyloxyethyl, Acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid-2-succinoyloxyethyl, methacrylic acid-2-malenoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexahydrophthalo Yloxyethyl, crotonic acid-2-succinoyloxyethyl, and the like. Preferred are acrylic acid-2-malenoyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate, and particularly acrylic acid-2-maleic acid. Noyloxyethyl is preferred. These may be used alone or in combination of two or more.

  The addition reaction of an α, β-unsaturated monocarboxylic acid or ester thereof with an epoxy resin can be carried out by using a known method, for example, by reacting at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. can do. As the esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine; quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.

  The amount of α, β-unsaturated monocarboxylic acid or ester thereof used is preferably in the range of 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1, relative to 1 equivalent of the epoxy group of the raw material epoxy resin. Equivalent range. If the amount of α, β-unsaturated monocarboxylic acid or ester thereof used is small, the amount of unsaturated groups introduced is insufficient, and the subsequent reaction with the polybasic acid anhydride becomes insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, if the amount used is large, α, β-unsaturated monocarboxylic acid or ester thereof remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.

  The polybasic acid anhydride to be further added to the epoxy resin to which the α, β-unsaturated carboxylic acid or ester thereof is added includes maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, biphenyltetra Carboxylic acid dianhydride and the like, preferably maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, Biphenyltetracarboxylic dianhydride Particularly preferred compounds are tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. These may be used alone or in combination of two or more.

A known method can also be used for the addition reaction of polybasic acid anhydride, and it can be carried out by continuing the reaction under the same conditions as the addition reaction of α, β-unsaturated carboxylic acid or ester thereof.
The addition amount of the polybasic acid anhydride is preferably such that the acid value of the produced [2-3-5] resin is in the range of 10 to 150 mgKOH / g, more preferably in the range of 20 to 140 mgKOH / g. . If the acid value of the resin is too small, the alkali developability is poor, and if the acid value of the resin is too large, the curing performance tends to be inferior.

  Other [2-3-5] resins include, for example, naphthalene-containing resins described in JP-A-6-49174; JP-A 2003-89716, JP-A 2003-165830, JP-A 2005-325331, JP Examples include fluorene-containing resins described in JP-A-2001-354735 and the like; resins described in JP-A-2005-126684, JP-A-2005-55814, JP-A-2004-295084, and the like.

Moreover, the commercially available epoxy acrylate resin which has a carboxyl group can also be used, and "ACA-200M" by Daicel Corporation etc. can be mentioned as a commercial item, for example.
As the binder resin, for example, an acrylic binder described in JP-A-2005-154708 can also be used.
As the binder resin in the present invention, among the various binder resins described above, [2
-3-1] “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, or “(meth) acrylic” of [2-3-4]. "Resin" is particularly preferred.

As binder resin in this invention, 1 type may be used independently among the above-mentioned various binder resins, and 2 or more types may be used together.
These various binder resins can also be used as a dispersion resin as described above.
As the binder resin used as the dispersion resin, [2-3-3] resin or [2-3-4] resin is particularly preferable. [2-3-4] Among the resins, a polymer obtained by polymerizing a monomer component essentially containing the compound represented by the general formula (4) is particularly preferable.

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 brittle 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.
[2-4] Photopolymerization initiation system and / or thermal polymerization initiator
The colored composition of the present invention preferably contains a photopolymerization initiation system and / or a thermal polymerization initiator for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.

In particular, when the colored composition of the present invention contains a resin having an ethylenic double bond as the binder resin component, or when it contains an ethylenic compound as the aforementioned polymerizable monomer, it directly absorbs light or It is preferable to contain a photopolymerization initiation system that has a function of generating a polymerization active radical by causing a decomposition reaction or a hydrogen abstraction reaction by sensitization and / or a thermal polymerization initiator that generates a polymerization active radical by heat.
[2-4a] Photopolymerization initiator system The photopolymerization initiator may be used alone, but is usually used as a mixture (photopolymerization initiator system) with an accelerator or the like 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, N- Radical activators such as aryl-α-amino acid esters, α-aminoalkylphenone compounds,
Examples include oxime ester compounds described in JP-A No. 06-36750, JP-A No. 2002-323762, JP-A No. 2000-80068, and the like.

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 -Ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine and other halomethyl-s-triazine derivatives ;
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, diethylaminobenzophenone, 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, 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
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-cyclopentaenyl-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) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Α-aminoalkylphenone compounds such as
1- [9-Ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-oxime-O-acetate, 1- (4-phenylsulfanyl-phenyl) -octane-1,2-dione-2-oxime-O-benzoate, and other oxime ester systems Compound.

  The photopolymerization initiator used in the present invention preferably contains an oxime ester compound as a photopolymerization initiator, and among them, an oxime ester compound represented by the following general formula (I) is particularly preferable. Compounds.

[In the above general formula (I), R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or 4 to 25 carbon atoms. A heteroarylalkyl group, any of which may have a substituent; Alternatively, R ¹ may be bonded to X or Y to form a ring.
R ² is an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 10 carbon atoms. , An aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroaryloyl group having 3 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms, It may have a substituent.

X represents a divalent aromatic hydrocarbon group and / or an aromatic hetero group formed by condensation of two or more rings which may have a substituent.
Y represents an aromatic group which may have a substituent. ]
In the general formula (I), Y-C ( = O) -X moiety forms a light-absorbing portion, the oxime ^{structure: -C (-R 1) = N} -OR 2 moiety is a radical generation site. Absorbing part: Y—C (═O) —X efficiently absorbs light, and the absorbed energy is efficiently transferred to the oxime structure part to achieve high sensitivity. In addition, the light absorption part represented by the YC (= O) -X part, especially when added at a high concentration in the composition, the molecules are associated with each other, and apparently a plurality of molecules are single molecules. It is considered that the absorbance and the absorption efficiency tend to be reduced by behaving as The oxime ester compound (I) according to the present invention is preferable because it can have a high absorbance even when added at a high concentration by making the Y portion a bulky group.

  In addition, it is important that the YC (= O) -X moiety generates high-efficiency triplet energy that can be easily used for radical generation in the oxime structure part, achieving efficient energy transfer within the molecule. Therefore, it is important to make the YC (═O) —X portion and the oxime structure portion spatially close as much as possible.

The compound represented by the general formula (I) contains a benzophenone structure having a high efficiency of state change from a singlet state to a triplet state or a similar structure in the YC (= O) -X moiety. Therefore, the absorbed light can be efficiently converted into triplet energy.
Furthermore, the compound represented by the general formula (I) is a compound in which the benzophenone structure or a similar structure is likely to overlap with the oxime structure portion due to spatial rotation in the molecule. Efficient energy transfer is possible and higher sensitivity can be achieved.

In the general formula (I), X represents a divalent aromatic hydrocarbon group and / or an aromatic heterocyclic group, which may have a substituent and is formed by condensation of two or more rings.
Specific examples of X include a group derived from a condensed ring composed of an aromatic hydrocarbon ring such as a naphthalene ring, anthracene ring, chrysene ring, phenanthrene ring, azulene ring, fluorene ring, acenaphthylene ring, and indene ring; acridine ring And groups derived from condensed rings composed of aromatic hydrocarbon rings such as phenanthridine ring, xanthene ring, carbazole ring, phenazine ring, phenothiazine ring, phenoxazine ring, and benzothiazole ring, and aromatic heterocycle.

Any of these may have an arbitrary substituent. This “optional substituent” will be described later.
Among the compounds represented by the general formula (I), in particular, a compound represented by the following general formula (i), that is, the X group in the general formula (I) is a benzene ring X ¹ in the general formula (i) and A compound having a structure represented by ring X ² to be condensed is preferable.

[Wherein, R ¹ , R ² and Y have the same meanings as in the general formula (I). Ring X ² represents a ring condensed with benzene ring X ¹ , and may be a single ring or a condensed ring composed of two or more rings. Ring X ² may be condensed at any position of benzene ring X ¹ . The benzene ring X ¹ and the ring X ² condensed thereto may further have a substituent. ]
In the compound represented by the general formula (i), the benzene ring X ¹ can form a benzophenone structure or a similar structure together with —C (═O) —Y. This is preferable because the excitation efficiency to the state is high.

The X in the general formula (I) preferably a group containing an aromatic heterocyclic ring, when the ring X ² fused to the benzene ring X ¹ is a heterocyclic particularly preferably the general formula (i).
X is usually a divalent group derived from 2 to 4 condensed rings, and is preferably a divalent group derived from 2 or 3 condensed rings from the viewpoint of relatively low molecular weight, and is used for photocuring of the composition. From the viewpoint of easily adapting to the wavelength of light, a divalent group derived from a tri-fused ring is more preferable.

As the structure formed by X in general formula (I) and benzene ring X ¹ and ring X ² in general formula (i), a group derived from a carbazole ring is particularly preferable. When X is a group derived from a carbazole group, it is preferable because it is a robust skeleton in addition to the compatibility with irradiation light during exposure.

In the general formula (I), R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 2 carbon atoms
25 alkenyl group, C3-C20 heteroaryl group or C4-C25 heteroarylalkyl group, and these alkyl groups, alkenyl groups, heteroaryl groups, and heteroarylalkyl groups are all substituted. You may have. By making R ¹ such a group, the sensitivity to light is higher than that of a compound in which R ¹ is a phenyl group or the like. Moreover, since the synthesis | combination of a compound is also easy, it is preferable also from an industrial viewpoint.

Examples of the alkyl group having 1 to 20 carbon atoms of R ¹ include a methyl group, an ethyl group, a propyl group, and a butyl group, preferably an alkyl group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
Examples of the alkenyl group having 2 to 25 carbon atoms for R ¹ include a vinyl group and a propenyl group, preferably an alkenyl group having 3 to 12 carbon atoms such as a propenyl group, more preferably an alkenyl group having 2 to 5 carbon atoms. .

Examples of the heteroaryl group having 3 to 20 carbon atoms of R ¹ include thionyl group, furyl group, imidazolyl group, benzthiazolyl group, benzoxazolyl group, etc., preferably 3 to 15 carbon atoms, more preferably carbon atoms. 4 to 10 heteroaryl groups.
Examples of the heteroarylalkyl group having 4 to 25 carbon atoms of R ¹ include thionylmethyl group, furfuryl group, imidazolylmethyl group, benzthiazolylmethyl group, benzoxazolylmethyl group, and preferably 4 carbon atoms. -18, more preferably a heteroarylalkyl group having 4 to 10 carbon atoms.

In addition, each group mentioned above may have a substituent. The substituent will be described later.
R ¹ is particularly preferably an alkyl group which may have a substituent. Among these, an unsubstituted alkyl group is preferable from the viewpoint of ease of production. Moreover, when the compound represented by general formula (I) is used for a photopolymerizable composition so that it may mention later, the alkyl group substituted by the substituted amino group from a viewpoint of the adhesiveness to the board | substrate of this composition. And an alkyl group substituted with an N-acetyl-N-acetoxyamino group is most preferable.

In the general formula (I), R ² is an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, or a carbon number. 2-10 alkoxycarbonyl group, C7-20 aryloxycarbonyl group, C2-20 heteroaryl group, C3-20 heteroaryloyl group, C2-20 alkylaminocarbonyl group These alkanoyl group, alkenoyl group, cycloalkanoyl group, aryloyl group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryl group, heteroarylloyl group, and alkylaminocarbonyl group all have a substituent. Also good. By using R ² as such a group, the cleavage of the oxime portion is likely to proceed, and the sensitivity can be easily improved by the generation of radicals.

Examples of the alkanoyl group having 2 to 20 carbon atoms of R ² include an acetyl group, a propanoyl group, a butanoyl group and the like, preferably an alkanoyl group having 2 to 12 carbon atoms such as acetyl, more preferably 2 to 7 carbon atoms. is there.
Examples of the alkenoyl group having 3 to 25 carbon atoms of R ² include a crotonoyl group and an acryloyl group, preferably an alkenoyl group having 3 to 12 carbon atoms, such as crotonoyl, and more preferably 3 to 7 carbon atoms.

Examples of the cycloalkanoyl group having 4 to 8 carbon atoms of R ² include a cyclohexylcarbonyl group,
A methylcyclohexylcarbonyl group, a cyclopentylcarbonyl group, etc. are mentioned, Preferably it is C4-C8, such as cyclohexylcarbonyl, More preferably, it is a C4-C7 cycloalkanoyl group.
Examples of the aryloyl group having 7 to 20 carbon atoms of R ² include a benzoyl group, a methylbenzoyl group, and a naphthoyl group. Preferably, the aryloyl group has 7 to 12 carbon atoms, such as naphthoyl, and more preferably 7 to 10 carbon atoms. It is.

Examples of the alkoxycarbonyl group having 2 to 10 carbon atoms of R ² include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group, preferably 2 to 10 carbon atoms such as a methoxycarbonyl group, more preferably a carbon number. 2 to 8 alkoxycarbonyl groups.
Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms of R ² include phenoxycarbonyl group, p-methylphenoxycarbonyl group, naphthoxycarbonyl group and the like, preferably 7 to 15 carbon atoms such as naphthoxycarbonyl group, More preferred is an aryloxycarbonyl group having 7 to 10 carbon atoms.

Examples of the heteroaryl group having 2 to 20 carbon atoms of R ² include a thiophenyl group, a pyrrolyl group, and a pyridyl group, and preferably a heterocycle having 2 to 12 carbon atoms, such as a thiophenyl group, and more preferably 2 to 7 carbon atoms. An aryl group.
Examples of the hetero aryloyl group having 3 to 20 carbon atoms of R ² include a thiophenecarbonyl group, a pyrrolylcarbonyl group, and a pyridinecarbonyl group, preferably 5 to 15 carbon atoms such as a thiophenecarbonyl group, more preferably carbon. It is a hetero aryloyl group of several 7 to 10.

Examples of the alkylaminocarbonyl group having 2 to 20 carbon atoms of R ² include a morpholinocarbonyl group, a dimethylaminocarbonyl group, and a methylaminocarbonyl group, preferably 2 to 12 carbon atoms such as dimethylaminocarbonyl. An alkylaminocarbonyl group having 2 to 10 carbon atoms is preferred.
Among the groups described above, from the viewpoint of exposure sensitivity, R ² is preferably an akanoyl group, a cycloalkanoyl group, or an aryloyl group, and more preferably an akanoyl group or an aryloyl group.

In addition, although the substituent which each group mentioned above as R < ² > may have is mentioned later, as each group mentioned above, what does not have a substituent is especially preferable.
In the general formula (I), Y represents an aromatic group which may have a substituent, and more specifically, Y is a monovalent group derived from an aromatic hydrocarbon ring or an aromatic heterocyclic ring, All may have a substituent. When Y is a monovalent group derived from an aromatic heterocycle, one or more rings may be formed on a 5- or 6-membered heteroaryl group even if the phenyl group is a group in which one or more rings are condensed. It may be a group formed by condensation.

As described above, the compound represented by the general formula (I) is a benzophenone having a phenyl group or an aromatic heterocyclic part contained in Y via a — (C═O) — group and a part of X. This is preferable because it forms a structure or a similar structure.
In addition, as described above, the compound represented by the general formula (I) is a compound in which the benzophenone structure or a similar structure is likely to overlap with the oxime structure portion due to spatial rotation in the molecule. It is preferable because efficient energy transfer within the molecule is possible and higher sensitivity can be achieved.

  When Y is a condensed ring group formed by condensing one or more rings to a phenyl group, at least one position selected from 2,3-position, 3,4-position and 4,5-position of the phenyl group In addition, a group derived from 2 to 4 condensed rings formed by condensing 1 to 5 5- or 6-membered rings is preferable. Further, the ring condensed with the phenyl group in Y is preferably a hydrocarbon ring, an aromatic hydrocarbon ring and / or an aromatic heterocyclic ring. The ring condensed with the phenyl group in Y is preferably a hydrocarbon ring from the viewpoint of high quantum yield, and is preferably an aromatic ring from the viewpoint of widening the absorption wavelength.

As the ring of Y, a monocyclic ring or a 2-4 condensed ring group is preferable, and a monocyclic ring or a 2-3 condensed ring group is more preferable from the viewpoint that the molecular weight does not become too large. preferable. In addition, when Y is a group derived from a 3-4 condensed ring, it is industrially preferable because the absorption wavelength region becomes relatively long and adapts to an inexpensive light source.
Specific examples of the ring in Y include, for example, a benzene ring; naphthalene ring, anthracene ring, chrysene ring, phenanthrene ring, azulene ring, fluorene ring, acenaphthylene ring, indene ring and other aromatic hydrocarbon rings. Groups derived from aromatic heterocycles that are 5- or 6-membered rings such as thienyl, pyridyl, furyl, oxazolyl and thiazolyl groups; or acridine ring, phenanthridine ring, xanthene ring, carbazole ring, phenazine And a group derived from a condensed ring composed of an aromatic hydrocarbon ring and an aromatic heterocyclic ring such as a ring, a phenothiazine ring, a phenoxazine ring, a benzothiazole ring, and a benzoxazole ring.

As the ring group for Y, a phenyl group, a naphthyl group, a thienyl group, a furyl group, and a 2-pyridyl group are particularly preferable, and a phenyl group, a naphthyl group, and a thienyl group are most preferable from the viewpoint of sensitivity.
Examples of the substituent that the ring group in Y described above may have include, for example, an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, and a propyl group; and 1 to carbon atoms such as a methylthio group and an ethylthio group. 20 alkylthio groups; a sulfonic acid alkyl ester group represented by —SO ₃ R (where R is an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group); a carbon such as a pentyloxy group or a hexyloxy group An alkoxy group having 5 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms such as a cyclopentyl group and a cyclohexyl group; a cycloalkyloxy group having 5 to 20 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group; a morpholino group and a piperidino group A cyclic amino group having 5 to 20 atoms such as pyrrolidinyl group; 4 carbon atoms such as diisopropylamino group and di-t-butylamino group A dialkylamino group which is 20, an aryl group such as a phenyl group or a naphthyl group; a heteroaryl group such as a pyridyl group; an aralkyl group such as a benzyl group or a phenethyl group; a halogen atom such as Cl, Br, I or F; a tetrahydrothienyl oxide Group, and the like.

Among these alkyl groups, alkoxy groups, -SO 3 _R, the cyclic amino group or a dialkylamino group preferably from the viewpoint of further improving sensitivity, particularly preferably a cyclic amino group or a dialkylamino group.
A compound in which X is a group derived from a carbazole ring which may have a substituent, which is a particularly preferable form among the compounds represented by the general formula (I), is represented by the following general formula (III), for example. .

[Wherein, R ¹ , R ² and Y have the same meanings as in the general formula (I). R ^{3 to} R ⁹ each independently represent a hydrogen atom or an optional substituent Z described later. ]
Substituents that X in the general formula (I) can have (substituents that the benzene ring X ¹ in general formula (i) and the ring X ² condensed thereto can have), general formulas (I), (i ) And (III) R ¹ and R ² may have a substituent, and R ^{3 to} R ⁹ in the general formula (III) are:
Independently, those selected from the following substituents Z can be mentioned.

[Substituent group Z]
Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; nitro group; cyano group; any organic group.
The arbitrary organic groups include 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, n- C1-C18 linear or branched alkyl groups such as heptyl, n-octyl and t-octyl; C3-C18 such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl A linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group or a hexenyl group; a cycloalkenyl group having 3 to 18 carbon atoms such as a cyclopentenyl group or a cyclohexenyl group; a methoxy group Ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, n-amyloxy group a linear or branched alkoxy group having 1 to 18 carbon atoms such as a 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, n-amylthio group, t-amylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, t A linear or branched alkylthio group having 1 to 18 carbon atoms such as an octylthio group; an aryl group optionally substituted with an alkyl group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, or a mesityl group; Aralkyl groups having 7 to 18 carbon atoms such as benzyl group and phenethyl group; vinyloxy group, propenyloxy group, hexenyloxy group Linear or branched alkenyloxy group having 2 to 18 carbon atoms; represented by -COR ^17; vinylthio group, propenylthio group, alkenylthio group linear or branched 2 to 18 carbon atoms such as hexenyl thio group Carboxyl group; acyloxy group represented by —OCOR ¹⁸ ; amino group represented by —NR ¹⁹ R ²⁰ ; acylamino group represented by —NHCOR ²¹ ; carbamate group represented by —NHCOOR ²² ; A carbamoyl group represented by ²³ R ²⁴ ; a carboxylic acid ester group represented by —COOR ²⁵ ; a sulfamoyl group represented by —SO ₃ NR ²⁶ R ²⁷ ; a sulfonic acid ester group represented by —SO ₃ R ²⁸ ; 2-thienyl, 2-pyridyl, furyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, morpholino, pyrrolidi A trialkylsilyl group such as a saturated or unsaturated aromatic heterocyclic group such as a nyl group or a tetrahydrothiophene dioxide group, or a trimethylsilyl group;

R ^{17 to} R ²⁸ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkanoyl group, an optionally substituted alkylcarbonyloxy group, or a substituted group. An alkenyl group which may be substituted, an aryl group which may be substituted, or an aralkyl group which may be substituted; These positional relationships are not particularly limited, and when they have a plurality of substituents, they may be the same or different.

In the above, a plurality of substituents may be bonded to form a ring, and the formed ring may be a saturated or unsaturated aromatic hydrocarbon ring or aromatic heterocyclic ring, Further, each may have a substituent, and the substituent may further form a ring.
In the general formula (III), R ^{3 to} R ⁹ are each independently selected from a hydrogen atom or the above substituent group Z. Among the substituent groups Z, R ^{3 to} R ⁹ preferably have a substituent. An alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group; an aryl group having 6 to 20 carbon atoms such as a phenyl group which may have a substituent; A C3-C20 heteroaryl group such as a good pyridyl group; a C7-C18 aralkyl group which may have a substituent; a trialkylsilyl group which may have a substituent; Particularly preferred is an alkyl group.

In addition, what is preferable as the substituent which X in the general formula (I) may have (the benzene ring X ¹ in the general formula (i) and the ring X ² condensed thereto) may have the above R ^3. it is the same as those preferred to R ^9.
As the substituent that R ¹ may have, an amino group and an aryl group represented by —NR ¹⁹ R ²⁰ are preferable, and R ¹⁹ and R ²⁰ may be an alkanoyl group that may be substituted, or may be substituted. An alkylcarbonyloxy group is preferred. As described above, an amino group represented by —NR ¹⁹ R ²⁰ such as an N-acetyl-N-acetoxyamino group is particularly preferable because it is effective for improving the adhesion of the composition.

  Of the compounds represented by the general formula (I) of the present invention, the compound represented by the following general formula (II) is most preferable.

[Wherein R ¹ represents an alkyl group having 1 to 3 carbon atoms, or the following formula (IIa)

(Wherein, R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom, a phenyl group or an N-acetyl-N-acetoxyamino group), and R ² represents a carbon number 2-4 alkanoyl group is shown, X shows the bivalent carbazolyl group in which the nitrogen atom may be substituted by the alkyl group of 1-4. Y ^a represents a phenyl group which may be substituted with an alkyl group or a naphthyl group which may be substituted with a morpholino group. ]
The oxime ester compound represented by the general formula (I) can be synthesized according to the methods described in, for example, WO2002 / 100903, WO2005 / 080337, and JP-A-2006-36750.

  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.
Considering the type of radical generated by the photopolymerization initiator, it is particularly preferable to use a plurality of photopolymerization initiators in combination, for example, an oxime ester compound represented by the general formula (I), an acetophenone derivative, A combination with an α-aminoalkylphenone compound or a thioxanthone derivative may be mentioned. In this case, examples of the acetophenone derivative include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, and examples of the α-aminoalkylphenone compound include 2-dimethylamino-2. -(4-Methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone- 1, As the thioxanthone derivative, thioxanthone, 2,4-diethylthioxanthone and the like are preferable.

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

The blending ratio of the photopolymerization initiation system component (that is, the total amount of the photopolymerization initiator and the accelerator) is usually 0.1 to 40% by weight in the total solid content of the color filter coloring composition of the present invention, Preferably it is 0.5-30 weight%. 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 used in combination with 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-di Tilaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, ( p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. P-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, more preferably 10% by weight or less.

[2-4b] Thermal polymerization initiator
Specific examples of the thermal polymerization initiator that may be contained in the colored composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used.
Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexene-1-carbonitrile), 2, 2′-azobis (2,4-dimethylvaleronitrile), 1-[(1-cyano-1-methylethyl) azo] formamide (2- (carbamoylazo) isobutyronitrile), 2,2-azobis {2 -Methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2 '-Azobis [N- (2-propenyl) -2-
Ethyl propionamide], 2,2′-azobis [N-butyl-2-methylpropionamide], 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), 2,2′-azobis (dimethyl- 2-methylpropionamide), 2,2′-azobis (dimethyl-2-methylpropionate), 2,2′-azobis (2,4,4-trimethylpentene), and the like. However, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) and the like are preferable.

  Examples of the organic peroxide include benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide and the like. Specifically, diisobutyryl peroxide, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3, 3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di (2-ethoxyethyl) peroxy Dicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t -Butyl peroxypivale Di (3,5,5-trimethylhexanoyl) peroxide, di-n-octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2 -Ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, t-butylperoxy-2-ethylhexanoate, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (T-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) Cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (4,4-di (t-butylperoxy) cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate, t- Butyl peroxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) Hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl peroxyacetate, 2,2-di (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-di (t-butylperoxy) valerate, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyltrimethylsilyl peroxide, 2, 3-dimethyl-2,3-diphenylbutane, di (3-methylbenzoyl) peroxy Mixtures of benzoyl (3-methylbenzoyl) peroxide and dibenzoyl peroxide may be mentioned.

Among the photopolymerization initiators described in the section [2-4a], there are those that also function as thermal polymerization initiators, such as α-aminoalkylphenone compounds. Therefore, a compound selected from the examples given as examples of the photopolymerization initiator may be used as the thermal polymerization initiator.
These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.
When the ratio of the thermal polymerization initiator in the coloring composition is too small, the film is not sufficiently cured and the durability as a color filter may be insufficient. If the amount is too large, the degree of thermal shrinkage increases, and cracking and cracking may occur after thermosetting. Moreover, the tendency for storage stability to fall is seen. Therefore, the content of the thermal polymerization initiator is preferably in the range of 0 to 30% by weight, particularly 0 to 20% by weight, based on the total solid content of the colored composition of the present invention.

[2-5] 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.

[2-6] 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.

[2-7] Plasticizer
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 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 pigment dispersion and coloring composition
Next, a method for preparing the pigment dispersion of the present invention and the coloring composition will be described.
As described above, the coloring composition of the present invention may be prepared by mixing other components with a pigment dispersion prepared in advance, or all components may be mixed simultaneously or sequentially. Good. Below, the case where it prepares according to the former method is demonstrated to an example, However, It is not limited to this.

The colored composition of the present invention may be photocurable (photopolymerizable) or heat polymerizable depending on the production process to be applied. Below, although the case where a coloring composition is a photopolymerizable composition (this may be hereafter called a "resist") is demonstrated to an example, this invention is not limited to this.
First, a predetermined amount of each of the pigment, the solvent and the dispersant is weighed, and in the dispersion treatment step, the pigment 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 pigment is made into fine particles, so that the coating characteristics of the colored composition are improved, and the transmittance of the pixels on 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, the pigment is as described above, and may be further dispersed by mixing with various pigments, dyes and the like for toning.
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 appropriate dispersion time varies depending on the composition of the pigment dispersion, the size of the sand grinder apparatus, and the like. Therefore, it is necessary to appropriately adjust the dispersion time so that it is in the vicinity of the optimum point of viscosity and contrast.
The pigment dispersion obtained by the dispersion treatment is mixed with a solvent, a polymerizable monomer, and in some cases, a predetermined amount of a binder resin, a photopolymerization initiation system component, and other components to obtain a uniform dispersion solution. 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 filters
Next, the color filter of the present invention will be described.
The color filter of the present invention has a pixel formed using the above-described coloring composition on a substrate.
[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. Examples of materials include 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, silane coupling agents, thin film formation treatment of various resins such as urethane resins, etc. 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 further forming pixels of red, green and blue. The colored composition of the present invention is used as a coating liquid for forming at least one color pixel (resist pattern) among red, green and blue pixels. Using the colored composition (resist), coating on a resin black matrix forming surface formed on a transparent substrate or a metal black matrix forming surface formed using a chromium compound or other light shielding metal material, heating and drying Then, each process of exposure, development and thermosetting is performed to form a pixel.

The black matrix is formed on a transparent substrate using a light-shielding metal thin film or a photosensitive coloring 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 etching solution according to the material, and finally a positive photoresist is stripped with a special stripping agent 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 pattern. Thereafter, this coating film can be etched to form a black matrix.

  When utilizing the photosensitive coloring composition for black matrices, a black matrix is formed using the coloring 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 pixel forming method varies 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, but the present invention is not limited to this.
On a transparent substrate provided with a black matrix, a coloring composition of one color of red, green, and blue is applied and dried, then a photomask is overlaid on the coating film, and exposure, development, If necessary, pixels are formed by thermal 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 coating film thickness is too large, development becomes difficult and gap adjustment in the liquid crystal cell forming process may be difficult. On the other hand, if the coating film thickness is too small, it is difficult to increase the pigment concentration. 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
The exposure is performed by superposing a negative matrix pattern on the coating film of the colored composition and irradiating with ultraviolet rays or visible rays 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 exposure is not particularly 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
In the color filter of the present invention, the coating film formed using the colored composition of the present invention is exposed to light, and then developed using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. By doing so, the pixel can be formed on the substrate. 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 usually subjected to thermosetting treatment. 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 patterning order of each color is not limited to the order described above.

  In addition to the manufacturing method described above, the color filter of the present invention is obtained by applying (1) a colored composition containing a solvent, a pigment, a dispersant, and a polyimide resin as a binder resin to a substrate, and performing etching. It can also be manufactured by a method of forming a pixel. In addition, (2) a method of forming a pixel directly on a transparent substrate by using a coloring composition containing a solvent, a pigment and a dispersant as a colored ink, and a printing machine, and (3) including a solvent, a pigment and a dispersant. Examples thereof include a method in which a colored composition is used as an electrodeposition solution, and a colored film is deposited on an ITO electrode having a predetermined pattern by immersing the substrate in the electrodeposition solution. Further, (4) a method in which a film coated with a coloring composition containing a solvent, a pigment and a dispersant is attached to a transparent substrate and peeled off, exposed and developed to form a pixel, and (5) a solvent, a pigment and a dispersion. And a method of forming pixels with an ink jet printer using a coloring composition containing an agent 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 an image as it is, and is used as a part of components such as an organic EL display and a liquid crystal display device. In order to enhance, 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. The liquid crystal display device of the present invention is manufactured by making the color filter of the present invention and a liquid crystal driving substrate face each other and encapsulating liquid crystal therebetween. More specifically, 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 a counter substrate for driving a liquid crystal to form a liquid crystal cell. The liquid crystal is injected into the liquid crystal 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. 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.
There are no particular restrictions on the type of liquid crystal, and it is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, 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.

[6] Organic EL Display When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. Is formed using the colored composition of the present invention), and a color filter of the present invention is formed by forming a resin black matrix (not shown) provided between adjacent pixels 20 Then, by laminating the organic light-emitting body 500 on the color filter via the organic protective layer 30 and the inorganic oxide film 40, an organic EL element can be produced.

  As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. A method described in, for example, “Organic EL display” (Ohm, published on August 20, 2004, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) using the organic EL element 100 thus manufactured, etc. Thus, an organic EL display can be produced.

  The color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, unless this invention exceeds the summary, it is not limited to a following example.
[Synthesis Example 1]
114 parts by weight of propylene glycol monomethyl ether acetate was placed in a four-necked flask and heated to 85 ° C. while performing nitrogen bubbling. To this, 114 parts by weight of benzyl methacrylate, 26 parts by weight of methacrylic acid, 2,2′-azobis (isobutyronitrile)
9.9 parts by weight was dissolved in 96 parts by weight of propylene glycol monomethyl ether acetate and added dropwise over 4 hours.

After the dropwise addition, the reaction solution was further stirred for 2 hours while maintaining the temperature at 85 ° C., then, nitrogen bubbling was stopped, the temperature was raised to 100 ° C. and stirred for 1 hour. A solution obtained by adding 0.7 parts by weight of tetraethylammonium chloride to this, stirring and dissolving at 80 ° C., and further mixing 16 parts by weight of 3,4-epoxycyclohexyl-1-methyl acrylate and 24 parts by weight of propylene glycol monomethyl ether acetate was prepared. The solution was added dropwise over 1 hour.
The reaction solution was stirred for 30 hours while maintaining at 80 ° C. to obtain a polymer solution having a weight average molecular weight of 8000 in terms of polystyrene and an acid value of 90 mgKOH / g as measured by GPC.

[Synthesis Example 2]
Prepare a separable flask with a cooling tube as a reaction tank, charge 400 parts by weight of propylene glycol monomethyl ether acetate, purge with nitrogen, and heat in an oil bath while stirring to raise the temperature of the reaction tank to 90 ° C. did.
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.
The mixture was cooled to room temperature to obtain a polymer solution having a weight average molecular weight of 8000 and an acid value of 70 mgKOH / g.

[Synthesis Example 3]
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. 20 parts by weight of styrene, 57 parts by weight of glycidyl methacrylate and 82 parts by weight of a monoacrylate having a tricyclodecane skeleton (“FA-513M” manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and the mixture was further stirred at 120 ° 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 27 parts by weight of acrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Thereafter, 52 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 120 ° C. for 3.5 hours.
The weight average molecular weight Mw in terms of polystyrene measured by GPC of the binder resin F thus obtained was about 15000.

[Synthesis Example 4]
Prepare a separable flask with a cooling tube as a reaction tank, charge 400 parts by weight of propylene glycol monomethyl ether acetate, purge with nitrogen, and heat in an oil bath while stirring to raise the temperature of the reaction tank to 90 ° C. did.
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 in terms of polystyrene measured by GPC and an acid value of 101 mgKOH / g was obtained.
[A] Atomization treatment of PY215 (CI Pigment Yellow 215) pigment Using a pressure kneader or an open kneader with a capacity of 300 mL, each component shown in Table-1 is kneaded under the conditions shown in Table-2. Dating. The obtained wet milled product was dissolved in 10 times the total weight of demineralized water and stirred for 30 minutes. Filter through 5C filter paper.

The filtrated material was dissolved in 5 times by weight of demineralized water and stirred for 30 minutes. The mixture was filtered through 5C filter paper, and this was repeated a total of 3 times to obtain a wet cake.
The obtained wet cake was dried with a hot air dryer at 50 ° C. for 8 hours, and the obtained dried product was pulverized using a pulverizer (“Lab Miller Plus” manufactured by Osaka Organic Chemical Co., Ltd.).
The above steps were repeated until a pigment having a desired average primary particle size was obtained, and three types of PY215 atomized pigments (Pigments 1 to 3) shown in Table 3 were obtained. The crystal shape and average primary particle diameter of the pigment were observed and measured by the following methods.

[Calculation of pigment crystal shape and average primary particle size]
The pigment was ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment was obtained by observation with a transmission electron microscope (TEM). From this image, the crystal shape of the pigment was observed.
In addition, from the primary particle image of the obtained pigment, the particle diameter of each pigment particle is set to an equivalent circle diameter obtained by converting the particle diameter of each pigment particle into the diameter of a circle having the same area. Then, the number average value was calculated according to the following formula to determine the average particle size.

The particle diameter of each pigment _{particle: X 1, X 2, X} 3, X 4, ····, X i, ······ X m
Average particle size = ΣX _i / m

[B] Measurement of chromaticity and contrast (PY215 atomized pigment)
A colored composition for a color filter was prepared using the pigments 1 to 3 obtained in the above [a].
First, each component shown in Table 4 below and zirconia beads (0.5 mm diameter) 2.5 times the total amount of these components are put in a pressure-resistant glass container, sealed, and attached to a paint shaker for dispersion treatment. And pigment dispersions 1 to 3 were obtained. (Pigment dispersion 1 contains pigment 1, pigment dispersion 2 contains pigment 2, and pigment dispersion 3 contains pigment 3.)
The dispersion treatment times were 8 hours (pigment dispersion 1), 24 hours (pigment dispersion 2), and 80 hours (pigment dispersion 3), respectively.

表−４中、ビックケミー社製「Disperbyk- 2000」（アクリル系ブロック共重合体。４
級アンモニウム塩基（ジメチルベンジルアンモニウム塩基）を有するＢ−ブロックと、有さないＡ−ブロックからなるＡ−Ｂブロック共重合体であり、アミン価は１０ｍｇＫＯＨ／ｇ（固形分換算）、酸価は０ｍｇＫＯＨ／ｇ）は、固形分換算での含有量である。

In Table 4, “Disperbyk-2000” (acrylic block copolymer. 4) manufactured by Big Chemie.
It is an AB block copolymer comprising a B-block having a secondary ammonium base (dimethylbenzylammonium base) and an A-block not having an amine value, the amine value is 10 mgKOH / g (in terms of solid content), and the acid value is 0 mgKOH / G) is the content in terms of solid content.

Using each of the obtained pigment dispersions, it was mixed with each component described in Table-5 below, and a solvent was added to prepare colored compositions 1 to 3. (Coloring composition 1 includes pigment dispersion 1, coloring composition 2 includes pigment dispersion 2, and coloring composition 3 includes pigment dispersion 3.)
In addition, the numerical value in Table-5 represents a weight part, and all are the amount of solid content conversion. Further, the solvent to be added is propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), and the solid content concentration of the composition is 18% by weight and is contained in the composition (PGMEA): (PGME) = 9: 1 (weight ratio).

なお、表−５における各成分の略称の意味は、以下の通りである。
「ＤＰＨＡ」：商品名、日本化薬（株）製。ジペンタエリスリトールヘキサアクリレート。
「Ｉｒｇ ＯＸＥ０２」： チバ・スペシャルティ・ケミカルズ社製、商品名「Irgacure OXE02」。下記構造式で表される化合物である。

In addition, the meaning of the abbreviation of each component in Table-5 is as follows.
“DPHA”: trade name, manufactured by Nippon Kayaku Co., Ltd. Dipentaerythritol hexaacrylate.
“Irg OXE02”: Product name “Irgacure OXE02” manufactured by Ciba Specialty Chemicals. It is a compound represented by the following structural formula.

“Irg 907”: Product name “Irgacure 907” manufactured by Ciba Specialty Chemicals. (2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one)
“F-475”: trade name, manufactured by Dainippon Ink & Chemicals, Inc. Fluorosurfactant Each of the obtained colored compositions 1 to 3 was spin-coated on a glass substrate for a color filter, and prebaked for 3 minutes on an 80 ° C. hot plate. At the time of application, the number of rotations was adjusted so that the film thickness would be a color coordinate x = 0.422 after drying. Subsequently, after exposure at 60 mJ / cm ² with a high-pressure mercury lamp, post-baking was performed in an oven at 230 ° C. for 30 minutes to form a colored resin film having a thickness of about 1.2 μm.

  About each obtained colored resin film, the contrast was measured by the method mentioned later. The results are shown in Table-6.

[Measurement of contrast of colored plate]
2 (a) and 2 (b) show the chromaticity of parallel transmitted light and orthogonal transmitted light of a colored plate (a glass substrate having a colored resin film prepared in the above [b], the same applies hereinafter). It is a schematic diagram for demonstrating the method to measure. First, as shown in FIG. 2A, polarizing plates 33 and 35 are stacked on both sides of the colored plate obtained in the above [b] (hereinafter referred to as “colored plate 34”). With the polarization axes parallel to each other, the light L of the backlight 37 is applied from the side of one polarizing plate 35, and the luminance Lp (the luminance of the parallel transmitted light) transmitted through the other polarizing plate 33 is the color luminance. The measurement was performed under the condition of 2 ° visual field using “BM-5A” 32 manufactured by Topcon Technohouse.

Next, as shown in FIG. 2B, in a state where the polarization axes of the polarizing plates 33 and 35 are 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 of the light transmitted through (the luminance of the orthogonal transmitted light) was measured with the color luminance meter 32 in the same manner as Lp.
Note that the backlight 37 has an emission spectrum as shown in FIG. This 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 contrast of each colored plate obtained in [b] was calculated using the formula Lp / Lc from the luminance Lp of the parallel transmitted light and the luminance Lc of the orthogonal transmitted light. The results are shown in Table-6.
[C] Preparation and evaluation of red composition for color filter [c-1] Preparation of red composition for color filter C.I. I. Pigment red 254 and C.I. I. Pigment Red 177 was used, and each component in the ratio shown in Table 7 below was placed in a stainless steel container together with zirconia beads (0.5 mm diameter) 2.5 times the total amount of these components, and sealed. Then, the dispersion was applied to a paint shaker to obtain a red pigment dispersion. Hereinafter, for each of the obtained red pigment dispersions, C.I. I. Pigment Red 254 containing Pigment Red 254 is referred to as “PR245 Dispersion”, C.I. I. The pigment dispersion containing Pigment Red 177 is referred to as “PR177 dispersion”.

  In addition, a azo nickel complex yellow pigment “E4GN-GT” manufactured by LANXESS, Inc. was used as a pigment, and was similarly subjected to dispersion treatment together with each component described in Table 7 below to obtain a yellow pigment dispersion. Hereinafter, the obtained yellow pigment dispersion is referred to as “PY-AZO dispersion”. In addition, the numerical value in Table-7 represents a weight part, and all are the amount of solid content conversion.

得られた顔料分散液「ＰＲ２５４分散液」、「ＰＲ１７７分散液」及び「ＰＹ−ＡＺＯ分散液」、並びに前記［２］にて得られた顔料分散液３（顔料３、すなわち平均一次粒径１５ｎｍのＣ．Ｉ．ピグメントイエロー２１５、を含有する顔料分散液）を用い、下記表−８に記載の割合で各成分を加え、さらに溶剤を加えて混合し、カラーフィルタ用赤色組成物を得た（実施例１及び比較例１）。

The obtained pigment dispersions “PR254 dispersion”, “PR177 dispersion” and “PY-AZO dispersion”, and the pigment dispersion 3 obtained in the above [2] (pigment 3, ie, average primary particle size 15 nm) CI Pigment Yellow 215) was added to each component in the proportions shown in Table 8 below, and a solvent was added and mixed to obtain a red composition for a color filter. (Example 1 and Comparative Example 1).

The ratio of the pigment in each composition was determined so that the chromaticity coordinates (x, y) = (0.648, 0.330) in the XYZ color system of the colored resin film having a film thickness of 2.2 μm.
In addition, the numerical value in Table-8 represents a weight part, and all are the amount of solid content conversion. Further, the solvent to be added is propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), and the solid content concentration of the composition is 22% by weight, and is contained in the composition (PGMEA): (PGME) = 9: 1 (weight ratio).

なお、表−８における各成分の略称の意味は、以下の通りである。
「ＢＩ」：２，２’−ビス（ｏ−クロロフェニル）−４，５，４’，５’−テトラフェニル−１，２’−ビイミダゾール
「Ｉｒｇ ９０７」：チバ・スペシャルティ・ケミカルズ社製、商品名「Irgacure 907」。（２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン）
「２−ＭＢＴ」：２−メルカプトベンゾチアジール
「ＤＥＴＸ−Ｓ」：日本化薬社製「ＫＡＹＡＣＵＲＥ ＤＥＴＸ−Ｓ」（２，４−ジエチルチオキサントン）
「Ｆ−４７５」：商品名、大日本インキ化学工業社製。フッ素系界面活性剤
［ｃ−２］色度及びコントラストの測定
前記［ｃ−１］にて得られた赤色組成物を用い、前記［ｂ］と同様にガラス基板上に着色樹脂膜を形成し（但し膜厚は２．２μｍとした）、前記［ｂ］の［着色板のコントラスト測定］の項に記載の方法にて、コントラストを測定した。得られたコントラストの値を、Ｙ値及び各組成物の全固形分に対する顔料濃度（重量％）とともに表−９に示す。

In addition, the meaning of the abbreviation of each component in Table-8 is as follows.
“BI”: 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole “Irg 907”: manufactured by Ciba Specialty Chemicals The name “Irgacure 907”. (2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one)
“2-MBT”: 2-mercaptobenzothiazyl “DETX-S”: “KAYACURE DETX-S” (2,4-diethylthioxanthone) manufactured by Nippon Kayaku Co., Ltd.
“F-475”: trade name, manufactured by Dainippon Ink & Chemicals, Inc. Fluorosurfactant [c-2] Measurement of chromaticity and contrast Using the red composition obtained in [c-1], a colored resin film was formed on a glass substrate in the same manner as in [b]. The contrast was measured by the method described in the section [Measurement of contrast of colored plate] in [b] above (however, the film thickness was 2.2 μm). The obtained contrast values are shown in Table 9 together with the Y value and the pigment concentration (% by weight) relative to the total solid content of each composition.

As can be seen from the description in Table-9, the red composition for a color filter of Example 1 has an equivalent Y value at a low pigment concentration and high contrast as compared with the composition of Comparative Example 1. Therefore, it is preferable.
[D] Preparation and evaluation of green composition for color filter [d-1] Preparation of green composition for color filter C.I. I. Pigment green 58 and C.I. I. Using Pigment Green 36, each component in the ratio shown in Table 10 below is placed in a stainless steel container together with zirconia beads (0.5 mm diameter) 2.5 times the total amount of these components, and tightly sealed. Then, it was mounted on a paint shaker and dispersed to obtain a green pigment dispersion.

  Hereinafter, for each of the obtained green pigment dispersions, C.I. I. Pigment Green 58 containing pigment dispersion is referred to as “PG58 Dispersion”, C.I. I. The pigment dispersion containing Pigment Green 36 is referred to as “PG36 dispersion”. In addition, the numerical value in Table-10 represents a weight part, and all are the amount of solid content conversion.

* 3 Dispersant “BYK-LPN 6919” manufactured by Big Chemie:
Methacrylic acid AB block copolymer. The weight average molecular weight Mw is about 9000, the amine value is 121 mgKOH / g, and the acid value is 1 mgKOH / g or less. Of the repeating units having a nitrogen atom-containing functional group contained in the B-block, about 100 mol% is a structure represented by the following formula (i), and is a repeating unit represented by the following formula (ii): The proportion in the A-block is 11 mol%.

* 4 Dispersant “Disprebyk-2001” manufactured by Big Chemie
A mixture of the “Disprebyk-2000” and a phosphoric acid derivative. The amine value is about 63 mg KOH / g (in terms of solid content).
Obtained pigment dispersions “PG58 dispersion”, “PG36 dispersion”, “PY-AZO dispersion” prepared in the section “[c-1] Red composition for color filter”, and [b] Using the pigment dispersion 3 (pigment 3, that is, pigment dispersion containing CI Pigment Yellow 215 having an average primary particle size of 15 nm), the components were mixed at the ratios shown in Table 11 below. In addition, a solvent was further added and mixed to obtain green compositions for color filters (Examples 2-3 and Comparative Examples 2-3).

The ratio of the pigment in each composition was determined so that the chromaticity coordinates (x, y) = (0.290, 0.599) in the XYZ color system of the colored resin film having a film thickness of 2.2 μm.
In addition, the numerical value in Table-11 represents a weight part, and all are the amount of solid content conversion. Further, the solvent to be added is propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), and the solid content concentration of the composition is 22% by weight, and is contained in the composition (PGMEA): (PGME) = 9: 1 (weight ratio).

なお表−１１中の成分の略称の意味は、前記表−５におけると同様である。
［ｄ−２］色度及びコントラストの測定
前記［ｄ−１］にて得られた緑色組成物を用い、前記［ｂ］と同様にガラス基板上に着色樹脂膜を形成し（但し膜厚は２．２μｍとした）、前記［ｂ］の［着色板のコントラスト測定］の項に記載の方法にて、コントラストを測定した。得られたコントラストの値を、各組成物の全固形分に対する顔料濃度（重量％）とともに表−１２に示す。

The meanings of the abbreviations of the components in Table-11 are the same as those in Table-5.
[D-2] Measurement of chromaticity and contrast Using the green composition obtained in [d-1], a colored resin film is formed on a glass substrate in the same manner as in [b] (however, the film thickness is The contrast was measured by the method described in the section [Measurement of contrast of colored plate] in [b]. The obtained contrast values are shown in Table-12 together with the pigment concentration (% by weight) relative to the total solid content of each composition.

表−１２の記載から分かるように、実施例２及び３にて得られたカラーフィルタ用緑色組成物は、それぞれ比較例２及び３にて得られた組成物と比較して、低い顔料濃度で同じ色度が達成でき、かつ高いコントラストを示すため好ましい。

As can be seen from the description in Table-12, the green compositions for color filters obtained in Examples 2 and 3 have a lower pigment concentration than the compositions obtained in Comparative Examples 2 and 3, respectively. It is preferable because the same chromaticity can be achieved and high contrast is exhibited.

  According to the present invention, high brightness, high contrast, and low film thickness can be obtained without reducing image forming ability such as curability of the color filter coloring composition by containing a sufficiently finely atomized specific yellow pigment. The color filter can be manufactured. By using such a color filter, an excellent liquid crystal display device or organic EL display with high brightness and high contrast can be obtained.

It is a cross-sectional schematic diagram which shows an example of the organic EL element provided with the color filter of this invention. (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.

Explanation of symbols

32 color luminance meter
33, 35 Polarizing plate
34 Colored board
36 light
37 Backlight
10 Transparent support substrate
20 pixels
30 Organic protective layer
40 Inorganic oxide film
50 transparent anode
51 Hole injection layer
52 Hole transport layer
53 Light emitting layer
54 Electron injection layer
55 Cathode
100 Organic EL device
500 Organic light emitter

Claims (12)

  C. containing at least a pigment, a solvent and a dispersant, and the pigment has an average primary particle size of 30 nm or less. I. (Color Index) Pigment Yellow 215, A pigment dispersion for a color filter.   The pigment dispersion for a color filter according to claim 1, wherein the dispersant contains a dispersant which is a block copolymer composed of an A-block having solvophilicity and a B-block having a functional group containing a nitrogen atom. liquid.   Furthermore, the pigment dispersion liquid for color filters of Claim 1 or 2 containing binder resin.   A coloring composition for a color filter comprising the pigment dispersion according to any one of claims 1 to 3 and a polymerizable monomer.   C. having at least a pigment, a solvent, a dispersant, and a polymerizable monomer, and having an average primary particle size of 30 nm or less. I. (Color index) A coloring composition for a color filter, comprising Pigment Yellow 215.   The coloring composition for a color filter according to claim 5, wherein the dispersant contains a dispersant which is a block copolymer composed of an A-block having solvophilicity and a B-block having a functional group containing a nitrogen atom. object.   Furthermore, the coloring composition for color filters of Claim 5 or 6 formed by containing binder resin.   The pigment further comprises C.I. I. (Color Index) Pigment Green 7, C.I. I. Pigment green 36, and C.I. I. The colored composition for a color filter according to any one of claims 4 to 7, comprising at least one selected from the group consisting of CI Pigment Green 58.   The pigment further comprises C.I. I. (Color Index) Pigment Red 254 and / or C.I. I. The coloring composition for color filters according to any one of claims 4 to 7, comprising Pigment Red 177.   The color filter which has a pixel formed using the coloring composition for color filters as described in any one of Claims 4 thru | or 9.   A liquid crystal display device comprising: the color filter according to claim 10 and a liquid crystal driving substrate facing each other, and liquid crystal sealed therein.   An organic EL display comprising the color filter according to claim 10.

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