JP5948865B2 - Resin for liquid crystal display device member, pigment dispersion, colored resin composition, color filter, liquid crystal display device and organic EL display device - Google Patents

Description

  The present invention resides in a resin for liquid crystal display device members, a pigment dispersion, a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display device.

A color filter used in a liquid crystal display device generally has a transparent substrate and a colored layer formed on the transparent substrate and composed of colored patterns of three primary colors of red, green, and blue.
As a method for forming such a colored layer, a photolithography method using a resist ink containing a pigment is used.
However, resist inks used for photolithography are required to improve the pigment concentration for thinning the colored layer and to make the pigment finer for high brightness and high contrast. Such an increase in pigment concentration and a finer pigment cause an increase in the pigment dispersant in the colored resin composition, resulting in a problem that developability is lowered.

As a result, there is a problem in that the use of a strong developer and an increase in development time are caused, and film roughness occurs in the formed colored layer.
Furthermore, there has been a problem that conditions and facilities different from conventional ones are required, such as changing the developer.
In order to solve the problem of such a decrease in developability, for example, Patent Document 1 discloses a method for improving developability by using a specific resin for the colored resin composition.

JP 2011-127092 A

However, even the method described in Patent Document 1 has a problem that developability becomes insufficient when the pigment concentration is improved or when a fine pigment is used.
Furthermore, the production yield due to the thickening of the colored resin composition over time has also been a problem.
The present invention has been made in view of the above problems, and provides a resin for a liquid crystal display device member that can be used as a pigment dispersion having high solubility in a developing solution of a coating film and having excellent viscosity stability. Let it be an issue.

  The present invention also provides a pigment dispersion having excellent viscosity stability, a colored resin composition having high solubility in a developing solution of the coating film obtained, a color filter having pixels formed using the colored resin composition, and the color It is an object to provide a liquid crystal display device and an organic EL display device having a filter.

As a result of intensive studies by the present inventors, it has been found that the above-mentioned problems can be solved by using a specific polymer for the dispersion resin, and the present invention has been completed.
That is, the present invention is a polymer for a liquid crystal display member characterized by being a polymer having a repeating unit represented by the following formula (I) (hereinafter sometimes simply referred to as “specific resin of the present invention”). ), A pigment dispersion containing the specific resin, a colored resin composition, a liquid crystal display device and an organic EL display device.

(In said formula, R < ¹ > -R < ³ > represents a hydrogen atom or a methyl group each independently.
m represents an integer of 2 to 4,
n represents an integer of 1 to 20. )

The present invention has been made in view of the above problems, and provides a resin for a liquid crystal display device member that can be used as a colored resin composition having high solubility in a developer and a pigment dispersion having excellent viscosity stability and a coating film obtained. It becomes possible to do.
The present invention also provides a pigment dispersion having excellent viscosity stability, a colored resin composition having high solubility in a developing solution of the coating film obtained, a color filter having pixels formed using the colored resin composition, and the color It is possible to provide a liquid crystal display device and an organic EL display device having a filter.

It is a section schematic diagram showing an example of an organic EL device which has a color filter of the present invention.

Embodiments of the present invention will be described in detail below, but the following description is an example of embodiments of the present invention, and the present invention is 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) acrylic acid” "Means" acrylic acid and / or methacrylic acid ".

Further, “total solid content” means all components of the colored resin composition of the present invention other than the solvent components described later.
Furthermore, “aromatic ring” means both “aromatic hydrocarbon ring” and “aromatic heterocycle”.
Moreover, terms such as “CI Pigment Green” mean a color index (CI).
The pigment dispersion of the present invention contains (A) a pigment, (B) a solvent, (D) a dispersant and the specific resin of the present invention.
First, the specific resin of the present invention will be described in detail.

<Specific resin of the present invention>
The specific resin of the present invention is a polymer having a repeating unit represented by the following formula (I) (hereinafter referred to as “repeating unit (I)”).

(In said formula, R < ¹ > -R < ³ > represents a hydrogen atom or a methyl group each independently.
m represents an integer of 2 to 4,
n represents an integer of 1 to 20. )
(For ^R 1 to R ³⁾
R ^{1 to} R ³ each independently represents a hydrogen atom or a methyl group. R ² and R ³ are preferably hydrogen atoms in terms of easy production.

(About m)
When m is an integer of 2 to 4, the raw material is easily available and the production is easy.
(About n)
n represents an integer of 1 to 20.
When n is too small, the main chain becomes an obstacle, so that the penetration of the alkali developer becomes small. When n is too large, the hydrophilicity of the side chain becomes high, and adhesion failure during development tends to occur. 4-10 are preferred.

[Repeating unit represented by formula (II)]
The specific resin of the present invention has a repeating hydroxyl group represented by the following formula (II) (hereinafter referred to as the following formula (II)) because it has a hydrophilic hydroxyl group at the end of a long side chain, and the solubility in a developer is easily improved. It is preferable to include “repeating unit (II)”.

(In said formula, R < ¹¹ > -R < ¹³ > represents a hydrogen atom or a methyl group each independently.
p represents an integer of 2 to 4,
q represents the integer of 1-20. )
(About R ^{11 to} R ¹³ )
R < ¹¹ > -R < ¹³ > is synonymous with R < ¹ > -R < ³ > of said Formula (I) respectively. The preferred embodiment is also the same.

(About p and q)
p is the same as m in the formula (I), and q is the same as n in the formula (I). The preferred embodiment is also the same.

[Other structural units]
Any other structural unit may be used as long as it can be combined with the repeating unit (I) to form a copolymer. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) Acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, benzyl (meth) acrylate, ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrene, α-methylstyrene, cyclohexyl (meth) Acry , Dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-vinyl The thing which consists of pyrrolidone etc. can be mentioned.

[Content ratio]
In the specific resin of the present invention, the content of the repeating unit (I) in one polymer chain is usually 0.1 mol% or more, preferably 1.0 mol% or more, and usually 100 mol% or less.
The total content of the repeating unit (I) and the repeating unit (II) in one polymer chain is usually 0.1 mol% or more, preferably 5 mol% or more, and usually 100 mol% or less.
Within the above range, it is preferable in that the effect of the present invention can be obtained satisfactorily.

[Molecular weight]
The weight average molecular weight in terms of polystyrene measured by GPC of the specific resin of the present invention is usually 2000 or more, preferably 4000 or more, more preferably 5000 or more, and usually 100,000 or less, preferably 50000 or less, more preferably 30000 or less. .
It is from the point of compatibility with the component etc. which are contained in a colored resin composition as it is in the said range.

[Acid value]
The acid value of the specific resin of the present invention is usually 10 to 200 mg-KOH / g, preferably 15 to 150 mg-KOH / g, and more preferably 25 to 120 mg-KOH / g.
Within the above range, the solubility in a developer is good, and film roughness is less likely to occur, which is preferable.

[Specific resin production method]
Although the specific resin of this invention can be manufactured by a well-known method, it can synthesize | combine according to the method as described in Unexamined-Japanese-Patent No. 2011-127092 or Unexamined-Japanese-Patent No. 2007-271938, for example.
<Pigment dispersion>
The pigment dispersion of the present invention contains (A) a pigment, (B) a solvent, (D) a dispersant and the specific resin of the present invention. Furthermore, you may contain other additives other than these components.
Hereinafter, each component will be described.

[(A) Pigment]
The pigment dispersion of the present invention contains (A) a pigment.
(A) As a pigment, pigments of various colors such as a red pigment, a green pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment can be usually used.
Examples of the chemical structure of various pigments include organic pigments such as azo, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. In addition to these, various inorganic pigments can also be used.
Specific examples of pigments that can be used in the present invention are shown below by pigment numbers, but are not limited to these examples.

First, as a red pigment, 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. is preferred because it has a high affinity with the specific resin of the present invention and the effects of the present invention can be more easily obtained. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc., more preferably C.I. I. Pigment red 177, 209, 224, 242, 254, etc., particularly preferably C.I. I. Pigment red 177 and 254.

Examples of green pigments include C.I. I. 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. Of these, C.I. I. Pigment green 7, 36, 58, and the like.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 17 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203 , 204, 205, 206, 207, 208, and pigments described in JP-A-2005-325350 and JP-A-2007-25687.

Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, and the pigments described in the above-mentioned two publications, and more preferably C.I. I. Pigment yellow 83, 138, 139, 180, and the pigments described in the above-mentioned 2 publications.
Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Of these, C.I. I. Pigment violet 19, 23, etc., more preferably C.I. I. Pigment violet 23 and the like.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and the like. Of these, Pigment Orange 38 and 71 are preferable.

Alternatively, the pigment dispersion of the present invention may be used to prepare a colored resin composition as will be described later to form a resin black matrix of a color filter. In that case, a black pigment can be used. . In addition, a black pigment may be used independently and may mix and use pigments, such as red, green, and blue. Further, it may be an inorganic pigment or an organic pigment.
Examples of inorganic pigments that can be used in the present invention include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide.

In addition, the above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, as the (A) pigment, a red pigment and a yellow pigment can be used in combination, or a green pigment and a yellow pigment can be used in combination.
The average primary particle size of the pigment in the present invention is usually 100 nm or less, preferably 80 nm or less, more preferably 10 nm or more and 70 nm or less. Since the present invention is particularly effective in the case of a composition containing a highly atomized pigment, the case of containing a pigment having an average primary particle size of 10 nm or more and 60 nm or less is particularly preferable.

By keeping the average primary particle size of the pigment used in the above range, the depolarization characteristics are kept good, high contrast and transmittance are realized, dispersion stability is good, and heat resistance and light resistance are also improved. An excellent pigment dispersion for a color filter and a colored resin composition can be obtained.
The primary particle diameter of the pigment can be determined by the following method.
First, 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). However, in the case of organic pigments, the particle diameter of each pigment particle is the diameter corresponding to the area circle converted to the diameter of a circle having the same area, and the particle diameter of each of plural (usually about 200 to 300) pigment particles. Ask for. Using the obtained primary particle size value, the number average value is calculated according to the following formula to obtain the average particle size.

The pigment thus obtained may be used alone, but one or two or more pigments can be mixed and used within a range not impairing the effects of the present invention.
In addition, a dye can be used to obtain the color characteristics of the color filter. In general, dyes are more permeable than pigments and can produce high-intensity color filters.
The content of the pigment (A) in the present invention is usually 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, based on the total solid content of the pigment dispersion. It is 1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more.

In the present invention, the content of the pigment (A) is usually 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less, and usually 3% by weight based on the total solid content of the colored resin composition. % By weight or more, preferably 5% by weight or more, more preferably 10% by weight or more.
When the thickness is within the above range, the film thickness with respect to the color density is moderate, without adversely affecting the gap control during liquid crystal cell formation, and sufficient image formability is obtained, and the pigment dispersion state is also maintained. Therefore, it is preferable in that aggregation and sedimentation hardly occur, and as a result, problems such as thickening and lowering of luminance and contrast can be solved.

[(B) Solvent]
(B) In this invention, a solvent has the function to dissolve or disperse | distribute components other than these mix | blended with the case other than the said component, and to adjust a viscosity.
The solvent is not particularly limited as long as it can dissolve or disperse each component. Examples of such solvents include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene Glycol monoalkyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol monomethyl ether;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycol alkyl ether acetates such as ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;

Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, 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:
Commercially available products corresponding to these solvents include mineral spirits, valsol # 2, Apco # 18 solvent, apco thinner, and soak 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.

Of the above solvents, glycol alkyl ether acetates are preferred from the viewpoint of good dispersibility in solvents such as the pigment. Furthermore, propylene glycol monomethyl ether acetate is particularly preferable from the viewpoint of solubility of various components in the colored resin composition.
The content of the solvent in the pigment dispersion of the present invention is not particularly limited, but is usually 99% by weight or less, usually 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more. is there.
Further, the content of the solvent in the entire colored resin composition of the present invention is not particularly limited, but the upper limit is usually 99% by weight or less, preferably 50% by weight in consideration of viscosity suitable for coating. Above, more preferably 60% by weight or more, particularly preferably 70% by weight or more.

[(D) Dispersant]
As the (D) dispersant in the present invention, a known dispersant can be used regardless of the type as long as the pigment can be dispersed and kept stable, and examples thereof include cationic, anionic, nonionic and amphoteric. The dispersant may be a polymer dispersant. Specific examples include block copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate esters of polymer copolymers, and cationic comb graft polymers. Of these dispersants, block copolymers, polyurethanes, and cationic comb graft polymers are preferred. A block copolymer is particularly preferable. Among them, the block copolymer is composed of an A block having a solvophilic property and a B block having a functional group containing a nitrogen atom, and the amine value thereof is 80 mg-KOH / g or more and 150 mg-KOH. / G or less (in terms of effective solid content) is particularly preferable. More preferably 100 mg-KOH / g or more, 140 m
It is g-KOH / g or less.

Within the above range, the adsorptive power to the pigment surface is sufficient and the dispersion stability is good.
As the block copolymer, an acrylic block copolymer is preferable. The acrylic block copolymer can disperse the pigment (A) very efficiently. This is presumably because the molecular arrangement is controlled, so that there are few structures that obstruct the dispersant when adsorbing to the pigment.

In the present invention, the acrylic block copolymer is preferably an AB block composed of an A block and a B block and / or an ABA block copolymer.
The B block constituting the acrylic block copolymer preferably has a primary to tertiary amino group as a functional group containing a nitrogen atom, and the amino group is preferably —NR ⁴¹ R ⁴² (provided that R ⁴¹ And R ⁴² are each independently a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. What is preferable as a partial structure containing this is represented by the following formula (1).

^{(However, R 41} and ^{R 42} has the same meaning as above ^{R 41} and ^{R 42, R 43} is one 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 methyl groups, R ⁴³ is preferably a methylene group or an ethylene group, and R ⁴⁴ is preferably a methyl group. Examples of such a compound include a partial structure represented by the following formula.

  Two or more kinds of the partial structure containing an amino group as described above may be contained in one B block. In that case, two or more amino group-containing partial structures may be contained in the B block in any form of random copolymerization or block copolymerization. In addition, a partial structure not containing an amino group may be partially contained in the B block within a range not impairing the effects of the present invention. Examples of such a partial structure include (meth) acrylic acid esters. And a partial structure derived from a monomer.

On the other hand, in the present invention, the A block of the (D) dispersant is not particularly limited as long as it is solvophilic and is composed of a monomer that can be copolymerized with the monomer constituting the B block described above.
Examples of the A block include polymer structures obtained by copolymerizing comonomers such as styrene monomers, (meth) acrylate monomers, (meth) acrylate monomers, vinyl acetate monomers, glycidyl ether monomers, and the like. It is done.

The (D) dispersant contained in the pigment dispersion and colored resin composition of the present invention may contain an AB block or an ABA block copolymer comprising the A block and the B block as described above. Of these, AB block copolymers are preferred. Such a block copolymer is prepared, for example, by a living polymerization method.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Specifically, for example, a method described in JP-A-2007-270147 can be mentioned.

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

Amine value [mg-KOH / g] = (5.61 × 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.)
Further, the acid value of this block copolymer is preferably lower, although it depends on the presence and type of acidic groups that are the basis of the acid value, and is usually 50 mg-KOH / g or less, preferably 40 mg-KOH / g. Hereinafter, it is more preferably 30 mg-KOH / g or less.

When the average primary particle size of the pigment is small, the specific surface area increases and the amount of adsorbing dispersant per unit area decreases. In this case, the dispersant made of the copolymer is preferably used because it is more effective than the other dispersants.
Furthermore, as another dispersing agent, the thing as described in Unexamined-Japanese-Patent No. 2006-343648 is mentioned, for example.

The (D) dispersant in the present invention is preferably 5% by weight or more, more preferably 10% by weight or more, and usually 200% by weight or less, more preferably, based on the total amount of the pigment in the pigment dispersion or colored resin composition. Is used in an amount of 100% by weight or less.
It is preferable that it is in the above-mentioned range particularly in that a balance between pigment dispersion stability and development solubility can be achieved.
In addition, as (D) dispersing agent, 1 type (s) or 2 or more types may be used together, and other dispersing agents other than specific resin may be used. When using other dispersants, the total amount of the dispersant is adjusted to be within the above range.

[Dispersion aid]
The pigment dispersion or colored resin composition of the present invention may further contain a dispersion aid. The dispersion aid here may be a pigment derivative. Examples of the pigment derivative include JP-A Nos. 2001-220520, 2001-271004, 2002-179976, and 2007-. Various compounds described in Japanese Patent Application Publication No. 113000 and Japanese Patent Application Publication No. 2007-186681 can be used.

The content of the dispersion aid in the pigment dispersion or colored resin composition of the present invention is usually 0.1% by weight or more, usually 30% by weight or less, preferably 20% by weight or less, based on the pigment. Preferably it is 10 weight% or less, More preferably, it is 5 weight% or less.
Within the above range, the effect as a dispersion aid is effectively obtained, and this is preferable in terms of good dispersibility and dispersion stability.

[Dispersion resin]
The pigment dispersion and colored resin composition of the present invention may contain other dispersion resins other than the specific resin of the present invention as long as the effects of the present invention are not impaired.
In the present invention, a part or all of a resin selected from (C) binder resin or other binder resin described later may be contained as a dispersion resin.

The dispersion resin is preferably 10% by weight or more, and usually 200% by weight or less, preferably 100% by weight or less based on the total amount of the pigment in the pigment dispersion and the colored resin composition.
Even when the pigment dispersion and the colored resin composition of the present invention contain other dispersion resins other than the specific resin of the present invention, the total addition amount of the dispersion resins is set within the above range.
In addition, when the pigment dispersion and colored resin composition of this invention contain a dispersion resin, it is preferable to contain only the specific resin of this invention as this dispersion resin.

  When a resin other than the specific resin of the present invention is used as the dispersion resin, the acid value is preferably 0 mg-KOH / g or more, more preferably 1 mg-KOH / g or more, most preferably 5 mg-KOH / g or more, Moreover, 300 mg-KOH / g or less is preferable, 200 mg-KOH / g or less is more preferable, and 150 mg-KOH / g or less is the most preferable. By controlling the acid value within the above range, the alkali developability is improved, and the handling becomes easy in synthesis and the like.

  When a resin other than the specific resin of the present invention is used as the dispersion resin, the polystyrene-equivalent weight average molecular weight measured by GPC of the resin is preferably 1000 or more, more preferably 1500 or more, and most preferably 2000 or more. 200,000 or less is preferable, 50000 or less is more preferable, and 30000 or less is most preferable. By controlling the molecular weight within the above range, the alkali developability can be improved and the dispersion stability can be prevented from being lowered.

<Colored resin composition>
The colored resin composition of the present invention contains at least the above-mentioned (A) pigment, (B) solvent, (D) dispersant, (E) polymerizable monomer, and the specific resin of the present invention. You may contain additives other than these components. Further, it is particularly preferable to contain (C) a binder resin, (F) a photopolymerization initiating component and / or a thermal polymerization initiating component.

The colored resin 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. .
As components other than these essential components, in addition to the various components described in the present specification, any components that can be used as a color filter forming material can be used without particular limitation.

[(C) Binder resin]
The colored resin composition of the present invention is not particularly limited as the binder resin (C) unless the effects of the present invention are impaired. For example, when the colored resin composition of the present invention is a photopolymerizable resin composition, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, etc. Although the high molecular compound described in each gazette etc. can be used, Preferably the resin of the following (C-1)-(C-5) etc. are mentioned especially.

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Resin to be added, or an alkali-soluble resin (hereinafter referred to as “resin (C-1)”) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. .)
(C-2): Carboxyl group-containing linear alkali-soluble resin (C-2) (hereinafter sometimes referred to as “resin (C-2)”)
(C-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter sometimes referred to as “resin (C-3)”).
(C-4): (Meth) acrylic resin (hereinafter sometimes referred to as “resin (C-4)”)
(C-5): Epoxy acrylate resin having a carboxyl group (hereinafter sometimes referred to as “resin (C-5)”)
Of these, the resin (C-1) is particularly preferable, and the resin will be described below.

The resins (C-2) to (C-5) may be anything as long as they are dissolved in an alkaline developer and are soluble to the extent that the desired development processing is performed. It is the same as that described as the same item in 2009-025813. The preferred embodiment is also the same.
(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. As one of particularly preferable resins of the alkali-soluble resin resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction, or an epoxy group, Unsaturated in 10 to 100 mol% of the epoxy group of the copolymer with respect to the copolymer of 5 to 90 mol% of (meth) acrylate and 10 to 95 mol% of other radical polymerizable monomer Examples thereof include a resin obtained by adding a monobasic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of a hydroxyl group generated by the addition reaction.

  Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

  The other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is not particularly limited as long as the effects of the present invention are not impaired. For example, vinyl aromatics, dienes, (meth) Examples include acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, and the like, and in particular, mono (meth) having a structure represented by the following formula (7) Acrylate is preferred.

  The repeating unit derived from the mono (meth) acrylate having the structure represented by the following formula (7) contains 5 to 90 mol% among the repeating units derived from “other radical polymerizable monomers”. The content is preferably 10 to 70 mol%, more preferably 15 to 50 mol%.

In the above formula (7), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the following formula (8).

The formula ^{(8), R} 91 ~R ⁹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ may be connected to each other to form a ring.
The ring formed by connecting R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
Among these, among the structures represented by the formula (8), those represented by the following structural formulas (8a), (8b), or (8c) are particularly preferable.

In addition, the mono (meth) acrylate which has a structure represented by the said Formula (8) may be used individually by 1 type, and may use 2 or more types together.
As "other radical polymerizable monomers" other than the mono (meth) acrylate having the structure represented by the formula (8), the heat resistance and strength excellent in the colored resin composition can be improved. , Styrene, (n-butyl) (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate , (Meth) acrylic acid-2-hydroxyethyl, N-phenylmaleimide, N-cyclohexylmaleimide.

The content ratio of repeating units derived from at least one selected from the above monomer group is preferably 1 to 70 mol%, more 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.
In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Is preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter. What consists of 70 mol% and the latter 70-30 mol% is especially preferable.

Within the above range, the addition amount of the polymerizable component and alkali-soluble component described later is sufficient, and the heat resistance and strength are sufficient, which is preferable.
The epoxy group portion of the epoxy group-containing copolymer synthesized as described above is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).
Here, as an unsaturated monobasic acid added to an epoxy group, a well-known thing can be used, For example, unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned.

  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 may be used alone or in combination of two or more.

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%. It is preferable for it to be in the above range since the colored resin composition is excellent in stability over time. 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, succinic anhydride and tetrahydrophthalic anhydride are preferred. 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%.

Within the above range, the remaining film ratio and solubility during development are sufficient, which is preferable.
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. Such a resin structure is described in, for example, Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.

  The polystyrene-reduced weight average molecular weight (Mw) of the above-described binder resin (C-1) measured by GPC (gel permeation chromatography) is preferably 3000 to 100,000, and particularly preferably 5000 to 50000. 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.

In addition, the acid value of binder resin (C-1) is 10-200 mg-KOH / g normally, Preferably it is 15-150 mg-KOH / g, More preferably, it is 25-100 mg-KOH / g.
Within the above range, the solubility in a developer is good and film roughness is not likely to occur, which is preferable.
In addition, the content of the (C) binder resin is preferably 0.1 to 80% by weight, more preferably 1 to 60% by weight in the total solid content of the colored resin composition.
Within the above range, the adhesion to the substrate is good, the permeability of the developer to the exposed area is moderate, and the surface smoothness and sensitivity of the pixels are good.

[(E) Polymerizable monomer]
The colored resin composition of the present invention contains (E) a polymerizable monomer. (E) The polymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but it may be an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred).

The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of the photopolymerization initiation component when the colored resin composition of the present invention is irradiated with actinic rays. In addition, the (E) polymerizable monomer in this invention means the concept opposite to what is called a polymeric substance, and also includes a dimer, a trimer, and an oligomer other than a monomer in a narrow sense.
(E) Examples of the ethylenic compound in the polymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and unsaturated carboxylic acids; Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Esterification of unsaturated carboxylic acids with polyvalent carboxylic acids and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds described above An ester obtained by the reaction; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound;

Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. In addition, the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid portion, a crotonic acid portion replaced with a crotonic acid portion, or a maleic acid ester replaced with a maleic acid portion, etc. Is mentioned.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, 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. Representative examples are condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol A condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  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; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane A reaction product with a group-containing hydroxy compound is exemplified.

In addition, examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .
Among these, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, pentaerythritol or (meth) acrylic acid esters of dipentaerythritol are more preferred, and dipentaerythritol hexa (meth) acrylate is particularly preferred.

  The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having a group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

These monomers may be used alone, but since it is difficult to obtain a single compound in production, a mixture of two or more kinds may be used.
Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as (E) polymeric monomer as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 120 mg-KOH / g, and particularly preferably 5 mg-KOH / g to 90 mg-KOH / g.

When it is within the above range, the development and dissolution characteristics are hardly deteriorated, and the production and handling are easy. Furthermore, it is preferable because the photopolymerization performance is hardly lowered and the curability such as the surface smoothness of the pixel is good.
In the present invention, a more preferred polyfunctional monomer having an acid group is, for example, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, succinic acid ester of dipentaerythritol pentaacrylate, or a mixture mainly composed of phthalic acid ester. is there. It is also possible to use this polyfunctional monomer in combination with another polyfunctional monomer.

In the colored resin composition of the present invention, the content of these (E) polymerizable monomers is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more in the total solid content. Further, it is usually 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less.
The ratio of (E) polymerizable monomer to the total amount of all (A) pigments is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and particularly preferably 20% by weight or more. In addition, it is usually 200% by weight or less, preferably 150% by weight or less, and more preferably 110% by weight or less.
If it is within the above range, photocuring is appropriate, poor adhesion during development is unlikely to occur, the cross-section after development is unlikely to be an inversely tapered shape, and peeling phenomenon and omission failure due to lower solubility are less likely to occur. preferable.

[(F) Photopolymerization initiation component and / or thermal polymerization initiation component]
The colored resin composition of the present invention preferably contains (F) a photopolymerization initiation component and / or a thermal polymerization initiation component 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 resin composition of the present invention includes a resin having an ethylenic double bond as the component (C), or includes an ethylenic compound as the component (E), it directly absorbs light, or It is preferable to contain a photopolymerization initiating component that has a function of generating a polymerization active radical and / or a thermal polymerization initiating component that generates a polymerization active radical by heat. In the present invention, the component (F) as a photopolymerization initiation component refers to a photopolymerization initiator (hereinafter arbitrarily referred to as (F1) component) and a polymerization accelerator (hereinafter arbitrarily referred to as (F2) component). , Means a mixture in which an additive such as a sensitizing dye (hereinafter, arbitrarily referred to as component (F3)) is used in combination.

(Photopolymerization initiation component)
The photopolymerization initiating component that may be contained in the colored resin composition of the present invention is usually (F1) a photopolymerization initiator, and (F2) a polymerization accelerator and (F3) sensitization that are added as necessary. It is a component having a function of generating a polymerization active radical by being used as a mixture with an additive such as a dye and directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of the (F1) photopolymerization initiator constituting the photopolymerization initiating component include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197; JP-A-10-300922 Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl-s -Radical activators such as triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives And oxime ester derivatives described in JP-A No. 2000-80068 and the like.

Specific examples include photopolymerization initiators described in International Publication No. 2009/107734 pamphlet and the like.
Among these photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.

  The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), and a compound represented by the following formula (XI).

(In formula (XI), R ¹⁰¹ represents 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 a heteroaryl group having 4 to 25 carbon atoms. An alkyl group, each of which may have a substituent, or R ¹⁰¹ may be bonded to X or Z to form a ring;
R ¹⁰² represents 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 ring group and / or an aromatic hetero group formed by condensation of two or more rings which may have a substituent.

Z represents an aromatic group which may have a substituent. )
Of the compounds represented by the formula (XI), compounds in which X is a carbazole ring which may have a substituent are preferable. Specifically, compounds represented by the following formula (XII) Among them, the compound represented by the following formula (XIII) is particularly preferable.

(In the formula, R ¹⁰¹ , R ¹⁰² and Z have the same meanings as in formula (XI). R ^{10
3 to} R ¹⁰⁹ each independently represent a hydrogen atom or an arbitrary substituent. )

(In the formula, R ^101a represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following formula (XIIIa).

^{(Wherein, R 103} and ^{R 104} each independently represent a hydrogen atom, a phenyl group or a N- acetyl -N- acetoxy amino group.
* Represents a binding site. )
R ^102a represents an alkanoyl group having 2 to 4 carbon atoms, and X ^a represents a 3,6-carbazolyl group in which the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms. Za represents ^a phenyl group which may be substituted with an alkyl group or a naphthyl group which may be substituted with a morpholino group. )
In addition, benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2,4-diethylthioxanthone, etc. Examples also include thioxanthone derivatives, benzoate derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like.

Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable. In particular, oxime ester derivatives are preferable.
Examples of the (F2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Examples thereof include mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

These (F1) photopolymerization initiators and (F2) polymerization accelerators may be used alone or in combination of two or more.
Further, (F3) sensitizing dye is used for the purpose of increasing the sensitivity as required. As the sensitizing dye, an appropriate one is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; No. 239703, JP-A-5-289335, etc. Coumarin dyes having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes; Pyrromethene dyes described in JP-A-6-19240, etc .; JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-
84183, JP 52-112681, JP 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, Examples thereof include dyes having a dialkylaminobenzene skeleton described in JP-A-5-107761, JP-A-5-210240, JP-A-4-288818, and the like.

(F3) A sensitizing dye may also be used alone or in combination of two or more.
In the colored resin composition of the present invention, the content of these (F) photopolymerization initiating components is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.8% by weight based on the total solid content. It is 5% by weight or more, usually 40% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight or less.
Within the above range, the sensitivity to the exposure light beam is good, the solubility of the unexposed portion in the developer is good, and it is preferable in that it is difficult to induce poor development.

(Thermal polymerization initiation component)
Specific examples of the thermal polymerization initiation component (thermal polymerization initiator) that may be contained in the colored resin composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used. More specifically, for example, a thermal polymerization initiator described in International Publication No. 2009/107734 pamphlet or the like can be used.
These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.

[Optional ingredients]
In addition to the above components, the colored resin composition of the present invention comprises a surfactant, an organic carboxylic acid and / or an organic carboxylic acid anhydride, a thermosetting compound, a plasticizer, a thermal polymerization inhibitor, a storage stabilizer, a surface It may contain a protective agent, an adhesion improver, a development improver, and the like. Moreover, when a pigment is contained as a coloring matter, a dispersant or a dispersion aid may be contained. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used.

[Surfactant]
The colored resin composition of the present invention may further contain a surfactant. Various types of surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as surfactants, but they may adversely affect various properties such as voltage holding ratio and compatibility with organic solvents. It is preferable to use a nonionic surfactant in terms of low properties.

As the surfactant, for example, those described in JP-A-2009-25813 can be used.
The content of these surfactants is preferably 0.001% by weight or more, more preferably 0.005% by weight or more, and still more preferably 0.01% by weight in the total solid content of the colored resin composition of the present invention. That's it. Further, it is preferably used in the range of 10% by weight or less, more preferably 5% by weight or less, and further preferably 1% by weight or less.

[Preparation Method of Colored Resin Composition]
In the present invention, the colored resin composition can be prepared by an appropriate method. For example, the (A) pigment, (B) solvent, (D) dispersant and the specific resin of the present invention and other additions can be used. It can be prepared by mixing with the agent.

A more preferable preparation method is as follows. In the presence of a pigment in a solvent, (D) a dispersant, the specific resin of the present invention, and a dispersing aid to be added if necessary, (C) a part of the binder resin. In addition, for example, a pigment dispersion is prepared by mixing and dispersing while pulverizing using a paint shaker, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like. By adding (C) a binder resin, (E) a polymerizable monomer, (F) a photopolymerization initiating component and / or a thermal polymerization initiating component, and additives that are added as necessary to the pigment dispersion, and mixing them. The method of preparation can be mentioned.

[Application of colored resin composition]
The colored resin composition of the present invention is usually in a state where all the constituent components are dissolved or dispersed in a solvent. This colored resin composition is supplied onto the substrate to form components such as a color filter, a liquid crystal display device, and an organic EL display device.
Hereinafter, as an application example of the colored resin composition of the present invention, an application as a color filter, and a liquid crystal display device (panel) and an organic EL display device using them will be described.

<Color filter>
The color filter of the present invention has a pixel formed from the colored resin composition of the present invention.
The method for forming the color filter of the present invention will be described below.
The pixel of the color filter can be formed by various methods. Here, although the case where it forms by the photolithographic method using a photopolymerizable colored resin composition is demonstrated to an example, a manufacturing method is not limited to this.

  First, on the surface of the substrate, if necessary, a black matrix is formed so as to partition a portion for forming pixels, and after applying the colored resin composition of the present invention on this substrate, pre-baking is performed. The solvent is evaporated to form a coating film. Then, after exposing this coating film through a photomask, developing with an alkali developer, dissolving and removing the unexposed portion of the coating film, and then post-baking, each of red, green, and blue A color filter can be manufactured by forming a pixel pattern.

The substrate used for forming the pixel is not particularly limited as long as it is transparent and has an appropriate strength. For example, a polyester resin, a polyolefin resin, a polycarbonate resin, an acrylic resin, or a thermoplastic resin is used. A sheet, an epoxy resin, a thermosetting resin, various glass, etc. are mentioned.
In addition, these substrates may be appropriately subjected to pretreatment as desired, such as thin film formation treatment with a silane coupling agent or urethane resin, surface treatment such as corona discharge treatment or ozone treatment, if desired.
When applying the colored resin composition to the substrate, a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, a spray coating method, and the like can be given. Of these, the slit and spin method and the die coating method are preferable.

The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, particularly preferably 0.8 to 5.0 μm as the film thickness after drying.
Within the above range, it is preferable in that the gap can be easily adjusted in the pattern development or liquid crystal cell forming step, and a desired color can be easily expressed.
For example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used as the radiation used when forming the pixels, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

A light source for using radiation having a wavelength of 190 to 450 nm used for image exposure is not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, Lamp light sources such as medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, and the like. An optical filter can also be used when used by irradiating light of a specific wavelength.
Exposure of radiation, 10~10,000J / ^{m 2} is preferred.

  Examples of the alkaline developer 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, Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-di- or tri-ethanolamine, mono-di-, or tri -Methylamine, mono-, di-, or tri-ethylamine, mono-, or di-isopropylamine, n-butylamine, mono-, di-, or tri-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium Hydroxide (TMAH) Aqueous solution of an organic alkaline compound choline are preferred.

An appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or the like can be added to the alkali developer. In addition, it is usually washed with water after alkali development.
As the development processing method, any method such as an immersion development method, a spray development method, a brush development method, and an ultrasonic development method can be used. The development conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

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 developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

  When the color filter thus produced is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is, and is used as a part of a color display, a liquid crystal display device, or the like. Although used, in order to improve surface smoothness and durability, 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. In the vertical alignment type driving method (MVA mode), ribs may be formed. Also, a column structure (photo spacer) made of photolithography may be formed instead of the bead dispersion type spacer.

<Liquid crystal display device>
The liquid crystal display device of the present invention has the above-described color filter of the present invention. There is no restriction | limiting in particular about the model and structure of the liquid crystal display device of this invention, It can assemble in accordance with a conventional method using the color filter of this invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun, September 29, 1989, Japan Society for the Promotion of Science 142nd Committee).

<Organic EL display device>
When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, on a blue color filter in which pixels 20 are formed on a transparent support substrate 10 by the colored resin composition of the present invention. A multicolor organic EL element is manufactured by laminating the organic light-emitting body 500 through the organic protective layer 30 and the inorganic oxide film 40.

  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. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

Next, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the following examples, “part” represents “part by weight”.
[1] Synthesis of Resin <Synthesis Example 1: Synthesis of polymerizable monomer A>
Polyethylene glycol monomethacrylate (n = 4.5), a hydroxyl group of polyethylene glycol monomethacrylate, and an equimolar amount of phthalic anhydride were reacted to obtain monomer A. ^As confirmed by ¹ H-NMR, the monomer A was the following structure, an 80:20 mixture of the monomer A-1 and polyethylene glycol monomethacrylate.

The results of NMR are shown below. ¹ H NMR (CDCl ₃ , 400 MHz) δ 7.6-7.9 (m, 4H, H-4), 6.1 (m, 1H, H-1b), 5.6 (m, 1H, H— 1a), 4.3-3.6 (m, 18H, H-3), 2.0 (m, 3H, H-2)
<Synthesis Example 2: Synthesis of polymerizable monomer B>
Monomer B was reacted by replacing phthalic anhydride of monomer A with succinic anhydride. ^As confirmed by ¹ H-NMR, the monomer B was a 97: 3 mixture of the following structure, monomer B-1 and polyethylene glycol monomethacrylate.

The results of NMR are shown below.
¹ H NMR (CDCl ₃ , 400 MHz) δ 6.1 (m, 1H, H-1b), 5.6 (m, 1H, H-1a), 4.3-3.6 (m, 18H, H- 3) 2.6-2.7 (m, 4H, H-4), 2.0 (m, 3H, H-2)
<Synthesis Example 3: Synthesis of Resin P-1>
160.7 parts by weight of propylene glycol monomethyl ether acetate was placed in a 500 ml four-necked flask and heated to 85 ° C. while bubbling nitrogen. To this, 60.0 parts by weight of benzyl methacrylate, 10.0 parts by weight of methacrylic acid, 30.0 parts by weight of polymerizable monomer A, and 4.925 parts by weight of 2,2′-azobis (isobutyronitrile) were added to propylene glycol monomethyl ether. It melt | dissolved in 25.0 weight part of acetate, and was dripped over 4 hours. After dropping, the reaction solution was further stirred for 2 hours while maintaining the temperature at 85 ° C., and thereafter nitrogen bubbling was stopped, the temperature was raised to 100 ° C., and the mixture was stirred for 1 hour. The weight average molecular weight measured by GPC of the resin P-1 thus obtained was 14000, and the acid value was 100 mgKOH / g in terms of solid content.

<Synthesis Example 4: Synthesis of Resin P-2>
160.7 parts by weight of propylene glycol monomethyl ether acetate was placed in a 500 ml four-necked flask and heated to 85 ° C. while bubbling nitrogen. To this, 60.0 parts by weight of benzyl methacrylate, 10.0 parts by weight of methacrylic acid, 30.0 parts by weight of polymerizable monomer B, and 4.925 parts by weight of 2,2′-azobis (isobutyronitrile) were added to propylene glycol monomethyl ether. It melt | dissolved in 25.0 weight part of acetate, and was dripped over 4 hours. After dropping, the reaction solution was further stirred for 2 hours while maintaining the temperature at 85 ° C., and thereafter nitrogen bubbling was stopped, the temperature was raised to 100 ° C., and the mixture was stirred for 1 hour. The weight average molecular weight measured by GPC of the resin P-2 thus obtained was 14000, and the acid value was 100 mgKOH / g in terms of solid content.

<Synthesis Example 3: Synthesis of Resin P-3>
125.0 parts by weight of propylene glycol monomethyl ether acetate was placed in a 500 ml four-necked flask and heated to 85 ° C. while bubbling nitrogen. To this, 84.7 parts by weight of benzyl methacrylate, 15.3 parts by weight of methacrylic acid, and 4.925 parts by weight of 2,2′-azobis (isobutyronitrile) were dissolved in 25.0 parts by weight of propylene glycol monomethyl ether acetate. It was dripped over 4 hours. After dropping, the reaction solution was further stirred for 2 hours while maintaining the temperature at 85 ° C., and thereafter nitrogen bubbling was stopped, the temperature was raised to 100 ° C., and the mixture was stirred for 1 hour. Propylene glycol monomethyl ether acetate was added to the obtained resin solution to adjust the solid content concentration to 40% by weight. The weight average molecular weight measured by GPC of the resin P-3 thus obtained was 12000, and the acid value in terms of solid content was 100 mgKOH / g.

<Synthesis Example 4: Synthesis of Resin P-4>
The mixture was stirred while purging 145.0 parts by weight of propylene glycol monomethyl ether acetate with nitrogen, and the temperature was raised to 120 ° C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate and 66 parts by weight of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto, and 2.2′-azobis-2-methyl 8.47 parts by weight of butyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 part by weight of trisdimethylaminomethylphenol and 0.12 part by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The weight average molecular weight measured by GPC of the resin P-4 thus obtained was 8400, and the acid value in terms of solid content was 80 mgKOH / g.

[2] Preparation of Red Pigment Dispersion [2-1] Preparation of Red Pigment Dispersion (1) 69.90 parts by weight of propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as “PGMEA”), C as red pigment . I. 12.00 parts by weight of Pigment Red 177, 6.67 parts by weight of LPN6919 (solid concentration 60% by weight) (manufactured by Big Chemie) as a dispersant, and 11.43 parts by weight of resin P-1 (solids concentration 35% by weight) The parts were mixed and stirred with a stirrer for 3 hours to prepare a mill base having a solid content concentration of 20% by weight.
The mill base was subjected to a dispersion treatment using 600 parts by weight of 0.5 mmφ zirconia beads in a bead mill apparatus at a peripheral speed of 10 m / s and a residence time of 3 hours to obtain a red pigment dispersion (1).

[2-2] Preparation of red pigment dispersion (2) [2-1] In preparation of red pigment dispersion (1), resin P-1 was changed to resin P-2 (solid content concentration 35% by weight). Others were carried out in the same manner as in the preparation of [2-1] red pigment dispersion (1) to obtain a red pigment dispersion (2).
[2-3] Preparation of red pigment dispersion (3) [2-1] In the preparation of red pigment dispersion (1), resin P-1 was changed to resin P-3 (solid content concentration 40% by weight). [2-1] Similar to the preparation of the red pigment dispersion (1) except that the content of resin P-3 was changed to 10.00 parts by weight and the content of PGMEA was changed to 71.33 parts by weight. A red pigment dispersion (3) was obtained.

[3] Evaluation of viscosity of red pigment dispersion, contrast of red colored resin composition, dissolution time Viscosity immediately after dispersion of red pigment dispersion prepared in [2-1] to [2-3] It was measured. The viscosity was measured at room temperature (23 ° C.) and 20 rpm using an E-type viscometer “RE-80L” (manufactured by Toki Sangyo Co., Ltd.). The results are summarized in Table 2.
Next, a red colored resin composition was prepared with the composition shown in Table 1, and the contrast was measured.

Specifically, using the red pigment dispersion prepared in [2-1] to [2-3], resin P-4, dipentaerythritol hexaacrylate, IRGACURE OXE02 (BASF), 2-methyl-1 -[4- (Methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907 BASF) and surfactant F-475 (made by DIC) were mixed at a weight ratio shown in Table 1 and solidified with a solvent PGMEA The partial concentration was adjusted to 20% to obtain red colored resin compositions (1) to (3).

Each red colored resin composition was spin-coated on a glass substrate AN100 (manufactured by Asahi Glass Co., Ltd.), and prebaked on an 80 ° C. hot plate for 3 minutes. The coating rotation speed was adjusted so that the color coordinate x = 0.640 after post-baking.
Next, after exposure at 60 mJ / cm ² with a high-pressure mercury lamp, 0.04 wt% potassium hydroxide aqueous solution was used, and spray development was performed at a developer temperature of 23 ° C. and 0.25 MPa pressure for 40 seconds.
The red colored resin composition (3) was spray developed for 200 seconds. After development, the substrate was rinsed with sufficient water and then dried with clean air. Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes.

Next, the substrate is placed between two polarizing plates in close contact with no gap therebetween, and a light intensity A (cd / cm ² ) when the polarizing plates are orthogonal using a color luminance meter BM-5AS (Topcon). The contrast was calculated from the ratio of the light quantity B (cd / cm ² ) in parallel with the following formula (1). These results are summarized in Table 2.
C = B / A (1)
Table 2 summarizes the measurement results of contrast.

As shown in Table 2, it is possible to provide a colored resin composition having high solubility in a developer by using a pigment dispersion containing the specific resin of the present invention.
Furthermore, the red pigment dispersion containing the specific resin of the present invention has little viscosity increase after one week from immediately after dispersion, and is excellent in viscosity stability. That is, since the red colored resin composition containing the red pigment dispersion of the present invention is difficult to increase in viscosity, it can suppress a decrease in yield in the color filter manufacturing process.

DESCRIPTION OF SYMBOLS 100 Organic EL element 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 500 Organic light-emitting body 51 Hole injection layer 54 Electron injection layer

Claims (6)

(A) A resin for a liquid crystal display device member comprising a pigment, (B) a solvent, (D) a dispersant, (E) a polymerizable monomer, and a polymer having a repeating unit represented by the following formula (I): A colored resin composition characterized by the above.

(In said formula, R < ¹ > -R < ³ > represents a hydrogen atom or a methyl group each independently.
m represents an integer of 2 to 4,
n represents an integer of 4 to 20. ) The colored resin composition according to claim 1, wherein the resin for a liquid crystal display device member is a polymer further containing a repeating unit represented by the following formula (II).

(In said formula, R < ¹¹ > -R < ¹³ > represents a hydrogen atom or a methyl group each independently.
p represents an integer of 2 to 4,
q represents the integer of 1-20. ) And (F) a photopolymerization initiating component and / or a thermal polymerization initiating component.
The colored resin composition according to claim 1 or 2 . It has a pixel formed using the colored resin composition as described in any one of Claims 1-3 , The color filter characterized by the above-mentioned. A liquid crystal display device comprising the color filter according to claim 4 . An organic EL display device comprising the color filter according to claim 4 .

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