JP2010014961A - Pigment dispersion, colored composition, color filter, liquid crystal display and organic el display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored composition etc. in which a highly microparticulate pigment can be efficiently dispersed with a small additive amount, and which has high viscosity stability and substantially avoids "chipping" of a formed pixel. <P>SOLUTION: A pigment dispersion containing a pigment, a solvent and a dispersant is provided. The pigment dispersion further contains an aromatic carboxylic acid compound. The dispersant is a dispersant comprising a block copolymer consisting of A blocks having an affinity for a solvent and B blocks having a nitrogen atom-containing functional group, wherein the block copolymer has an amine value of 80-150 mgKOH/g (in terms of available solid content). The colored composition contains the pigment dispersion. Uses of the colored composition are also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a pigment dispersion, a coloring composition, a color filter, a liquid crystal display device, and an organic EL display. More specifically, a pigment dispersion containing a pigment, a specific dispersant, a solvent, and an aromatic benzoic acid compound; a colored composition containing the pigment dispersion and a binder resin; a pigment, a specific dispersant, a solvent, and a binder Colored composition containing resin, photopolymerization initiator and aromatic carboxylic acid compound; color filter in which pixels are formed using these colored composition, and liquid crystal display device and organic EL display provided with this color filter About.

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 has been rapid, and higher transmittance and high contrast have been required for color filters. In order to form a high-contrast color filter, it is necessary to disperse a pigment that is highly atomized and whose particle size distribution is narrowly controlled, and the technology for controlling the pigment particle size is rapidly developing. Naturally, the surface area of the pigment tends to increase, and the amount of the dispersant added tends to increase.
On the other hand, it is also necessary to limit components other than the pigment so that the color density and the pixel thickness are constant. For this reason, the component which contributes to image formation property, such as photosensitivity, solubility, and sclerosis | hardenability, reduces relatively, and the problem that the image formation performance required originally is lost tends to arise. That is, for example, when an attempt is made to reduce the pixel thickness (reducing the film thickness) by increasing the concentration of the pigment, the curability of the composition is reduced, so that the surface smoothness of the pixel is lowered, resulting in poor alignment of the liquid crystal. Further, the solubility in the developer decreases due to the increase in the amount of the dispersant, and the solubility in the developer decreases depending on the type of the dispersant. In some cases, the undissolved product of the coloring composition in the non-image area after development may easily remain. Furthermore, if undissolved colored composition remains on the non-pixel portion on the substrate, the resulting color filter causes a decrease in transmittance and contrast, and if it remains on the pattern edge portion, the ITO film is peeled off. In addition, there is a situation in which the sealing process is deteriorated in the liquid crystal cell forming process and the subsequent process is affected.
In recent years, electrical reliability has also been greatly emphasized. The charge charged between the electrodes of the liquid crystal display element may decay with time due to various factors, and a problem that a predetermined charge is not applied to the liquid crystal layer (decrease in voltage holding ratio) may occur. Many known dispersants cause this and have low electrical reliability.

In order to solve these problems, an acrylic block copolymer having an improved structure and acid value has been proposed, and attempts have been made to improve dispersibility by adding a small amount (Patent Documents 1, 2, 3 and 4). reference).
However, such known dispersants have insufficient dispersibility in order to efficiently disperse recent highly atomized pigments with a small addition amount.
As a result of repeated studies to cope with such a situation, the present inventors have used a block copolymer having a specific structure with a relatively high amine value as a dispersant, so that a fine pigment can be added in a small amount. It was found that the added amount can be dispersed uniformly and stably.

In addition, the pigment dispersion and the coloring composition containing the dispersant tend to increase in viscosity with the passage of time, and tend to cause “over” in the formed pixels.
As a result of further studies, the present inventors have found that such problems can be solved by including an aromatic carboxylic acid compound, and have reached the present invention.
JP 2004-287298 A JP 2004-287366 A JP 2006-265528 A JP 2006-321979 A

The present invention has been made in view of the above-mentioned problems, and its object is as follows.
(1) To provide a coloring composition that can efficiently disperse recent highly atomized pigments with a small addition amount, has high viscosity stability, and does not easily cause “splash” on formed pixels. thing.
(2) Furthermore, the solubility in the developer is good, development is possible within a predetermined time in the development process, and the undissolved matter of the coloring composition does not remain in the non-image area on the substrate. To provide a coloring composition that is excellent in adhesion to a substrate and that can produce a color filter with high transmittance, high contrast, and low film thickness without reducing image forming ability such as curability.
(3) To provide a high-quality liquid crystal display device or organic EL display using the color filter substrate.

As a result of diligent studies to solve the above problems, the present inventors have used a block copolymer having a specific structure with a relatively high amine value as a dispersant, so that a sufficiently high contrast region for a liquid crystal television can be used. As for the pigment atomized so as to be, it has been found that sufficient dispersion stability, developability and the like can be realized, and has been proposed previously (see Japanese Patent Application No. 2007-196441).
Furthermore, by containing an aromatic carboxylic acid-based compound, it suppresses thickening over time, achieves high viscosity stability, has little “over”, and can be used to form pixels with excellent linearity. It was found that a composition was obtained. The present invention has been accomplished based on these findings.

That is, the present invention comprises a plurality of related inventions, and the gist of each invention is as follows (1) to (21).
[1] A pigment dispersion containing a pigment, a solvent, and a dispersant, the pigment dispersion further containing an aromatic carboxylic acid compound, and the dispersant has an A block having solvophilicity and A block copolymer comprising a B block having a functional group containing a nitrogen atom, the block copolymer having an amine value of 80 mgKOH / g or more and 150 mgKOH / g or less (effective solid content conversion) A pigment dispersion characterized by the above.

[2] The aromatic carboxylic acid compound is represented by the following general formula (A)

(In the general formula (A), Z represents a methylene group or —O—, and n represents an integer of 0 to 3. However, when n is 2 or 3, the n Zs may be the same, May be different.
X ¹ is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyl group, a phenethyl group, a benzyloxy group, or —COOX ² (However, X ² is a number 1-7 alkyl group or a phenyl group having a carbon) indicates, none of these groups may have a substituent. )
The pigment dispersion according to [1], which is a compound represented by the formula:

[3] The block copolymer according to [1] or [2], in which at least 20 mol% of the repeating units having a functional group containing a nitrogen atom are repeating units having a primary to tertiary amino group. Pigment dispersion.
[4] In the block copolymer, the repeating unit having a functional group containing a nitrogen atom is a repeating unit having a tertiary amino group, and the repeating unit is derived from dimethylaminoethyl (meth) acrylate [1]. Thru | or the pigment dispersion liquid in any one of [3].
[5] The pigment dispersion according to any one of [1] to [4], wherein the pigment is a pigment containing brominated zinc phthalocyanine.
[6] The pigment dispersion according to any one of [1] to [5], wherein the average primary particle size of the pigment is 0.025 μm or less.
[7] The pigment dispersion according to any one of [1] to [6], further containing a dispersion resin.

[8] A coloring composition comprising the pigment dispersion according to any one of [1] to [7] and a binder resin.
[9] The coloring composition according to [8], further containing a polymerizable monomer.
[10] The colored composition according to [8] or [9], further comprising a photopolymerization initiation system and / or a thermal polymerization initiator.

[11] A colored composition containing a pigment dispersion containing a pigment, a solvent and a dispersant, and a binder resin, the colored composition further containing an aromatic carboxylic acid compound, and the dispersant Is a block copolymer comprising an A block having a solvophilic property and a B block having a functional group containing a nitrogen atom, the block having an amine value of 80 mgKOH / g or more and 150 mgKOH / g or less (effective solid content conversion) A coloring composition, which is a dispersant containing a copolymer.

[12] The aromatic carboxylic acid compound is represented by the following general formula (A)

(In the general formula (A), Z represents a methylene group or —O—, and n represents an integer of 0 to 3. However, when n is 2 or 3, the n Zs may be the same, May be different.
X ¹ is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyl group, a phenethyl group, a benzyloxy group, or —COOX ² (However, X ² is a number 1-7 alkyl group or a phenyl group having a carbon) indicates, none of these groups may have a substituent. )
The coloring composition as described in [11] which is a compound represented by these.

[13] The block copolymer according to [11] or [12], wherein among the repeating units having a functional group containing a nitrogen atom, at least 20 mol% is a repeating unit having a primary to tertiary amino group. Coloring composition.
[14] In the block copolymer, the repeating unit having a functional group containing a nitrogen atom is a repeating unit having a tertiary amino group, and the repeating unit is derived from dimethylaminoethyl (meth) acrylate. ] To [13].
[15] The colored composition according to any one of [11] to [14], wherein the pigment is a pigment containing brominated zinc phthalocyanine.
[16] The colored composition according to any one of [1] to [15], wherein the average primary particle size of the pigment is 0.025 μm or less.
[17] The colored composition according to any one of [11] to [16], further comprising a photopolymerization initiation system and / or a thermal polymerization initiator.
[18] The colored composition according to any one of [11] to [17], further containing a polymerizable monomer.

[19] A color filter comprising a pixel produced using the colored composition according to any one of [8] to [18].
[20] A liquid crystal display device comprising the color filter according to [19] and a liquid crystal driving substrate facing each other and liquid crystal sealed between them.
[21] An organic EL display comprising the color filter according to [19].

The present invention has the following effects.
(1) To provide a coloring composition that can efficiently disperse recent highly atomized pigments with a small addition amount, has high viscosity stability, and does not easily cause “splash” on formed pixels. .
(2) Furthermore, the solubility in the developer is good, development is possible within a predetermined time in the development process, and the undissolved matter of the coloring composition does not remain in the non-image area on the substrate. Provided is a coloring composition that is excellent in adhesion to a substrate and that can produce a color filter having high transmittance, high contrast, and low film thickness without reducing image forming ability such as curability.
(3) To provide a high-quality liquid crystal display device or organic EL display using the color filter substrate.

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

[1] Aromatic carboxylic acid compound The pigment dispersion and colored composition of the present invention contain an aromatic carboxylic acid compound as an essential component. The aromatic carboxylic acid compound may have any structure as long as it has an aromatic group and a carboxyl group. Examples of the aromatic group include a phenyl group and a naphthyl group. Of these, a phenyl group is particularly preferred.
These aromatic groups may have a substituent, and the type and number of the substituent are not particularly limited. Specifically, for example, a substituent represented by X in general formula (A) described later is preferable. Further, the number of carboxyl groups may be one or plural, for example, 2 to 3, but preferably 1 per molecule from the point that the effect of the present invention is remarkable.

  The molecular weight of the aromatic carboxylic acid compound is usually 500 or less, preferably 350 or less, and usually 150 or more. By setting the molecular weight to 500 or less, as described later, the approach of the compound to the pigment is facilitated, and the effect of suppressing the increase in viscosity can be reliably exhibited.

  Furthermore, as an aromatic carboxylic acid type compound, for example, the following general formula (A)

(In the general formula (A), Z represents a methylene group or —O—, and n represents an integer of 0 to 3. However, when n is 2 or 3, the n Zs may be the same, May be different.
X ¹ is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyl group, a phenethyl group, a benzyloxy group, or —COOX. ² (wherein X ² represents an alkyl group having 1 to 7 carbon atoms or a phenyl group), and any of these groups may have a substituent. )
The compound represented by these is mentioned as a preferable thing.

As described above, X ¹ in the general formula (A) is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyl group, A phenethyl group, a benzyloxy group or —COOX ² (wherein X ² represents an alkyl group having 1 to 7 carbon atoms or a phenyl group);
Specific examples of the alkyl group having 1 to 4 carbon atoms, the alkenyl group having 2 to 5 carbon atoms, and the alkoxy group having 1 to 4 carbon atoms in the definition of X ¹ will be described below.
An alkyl group having 1 to 4 carbon atoms; for example, an alkyl group having 4 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a secondary butyl group, and a tertiary butyl group.
An alkenyl group having 2 to 5 carbon atoms; for example, an alkenyl group having 5 or less carbon atoms such as vinyl group, allyl group, 1-propenyl group, 2-butenyl group, 1,3-butadienyl group and the like.
An alkoxy group having 1 to 4 carbon atoms; for example, an alkoxy group having 4 or less carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group.
Also in the definition of ^{X 1, X 2} in COOX ² is an alkyl group or a phenyl group having 1 to 7 carbon atoms. Examples of the alkyl group having 1 to 7 carbon atoms include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a secondary butyl group, a tertiary butyl group, an n-pentyl group, and an isopentyl group. , Neopentyl group, tertiary pentyl group, n-hexyl group, isohexyl group, 5-methylhexyl group and the like.

Any of these groups may have a substituent, and specific examples of the substituent include the following groups.
A hydroxy group;
Lower alkyl group; for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, secondary butyl group, tertiary butyl group, n-pentyl group, isopentyl group, neopentyl group, tertiary pentyl group Alkyl groups having 7 or less carbon atoms such as n-hexyl group, isohexyl group, 5-methylhexyl group and the like.
Lower alkoxy group; for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, second butoxy group, tertiary butoxy group, n-hexyl group, isohexyl group, 5-methylhexyl group, etc. An alkoxy group having 7 or less carbon atoms, such as
A lower alkenylcarbonyloxy group; for example, an alkenylcarbonyloxy group having 3 or less carbon atoms in the alkenyl group moiety such as an acryloyloxy group and a crotonyloxy group.
Phenyl group; benzyl group; phenoxy group; benzyloxy group.

Moreover, in the compound represented by the general formula (A), the substituent X ¹ may have an optionally substituted alkyl group having 1 to 4 carbon atoms because the effect of the present invention is remarkable. And a group selected from an alkenyl group having 2 to 5 carbon atoms which may have a substituent and -COOX ² group. More preferred specific examples of the substituent X ¹ include benzyloxycarbonyl group, methoxycarbonyl group, vinylcarbonyloxyethyleneoxycarbonyl group, isopropyl group, t-butyl group, methylol group, vinyl group and the like.

Further, the position of the substituent X ¹ is not particularly limited as long as it is within the possible range. However, the o-position or p-position with respect to the — (Z) _n —COOH group on the benzene ring is preferable, and the o-position is preferred. The case where only has a substituent is particularly preferable.
In the substituents X ^1, the groups which are not specifically described above, in combination from already group mentioned optionally, or is chosen according to common sense may know generally.

  The compound represented by the general formula (A) is particularly preferably a phthalic acid monoester compound. Specific examples include the following compounds, but are not limited thereto.

  The aromatic carboxylic acid compound, more specifically, the aromatic carboxylic acid compound represented by the general formula (A) can be obtained by purchasing a commercially available product or synthesizing it by a method known per se. It is easily available.

The content of the aromatic carboxylic acid compound in the pigment dispersion or colored composition of the present invention is not particularly limited as long as the effect as the colored composition is not impaired, but the finally prepared colored composition It is usually 20% by weight or less, preferably 10% by weight or less, more preferably 5% or less, and usually 0.1% or more with respect to the total solid content of the product.
If the amount of the aromatic carboxylic acid compound is too large, an image may not be obtained. If the amount is too small, an increase in the viscosity of the pigment dispersion or coloring composition may not be prevented. That is, by containing the aromatic carboxylic acid in the above range, it is possible to suppress the increase in the viscosity of the pigment dispersion or the coloring composition, and to form a pixel with less “over” and excellent linearity.

Although not bound by any theory and the details are unknown, the reason for preventing the increase in viscosity by containing an aromatic carboxylic acid compound is estimated as follows. That is, the block copolymer used as a dispersant in the present invention has an amino group, and in a certain composition, there is a possibility that the amino group of this dispersant reacts with other components to increase the viscosity. is there.
Here, the pigment is usually present as fine particles, and the dispersant is adsorbed on the pigment particles and exhibits a dispersing ability. The pigment is generally a compound having an aromatic group, and has an affinity with other aromatic groups.

  Due to the affinity of the aromatic group of the aromatic carboxylic acid compound according to the present invention, if the compound approaches the pigment particles, the carboxyl group also inevitably approaches the pigment and interacts with the dispersant adsorbed on the pigment. I think that it can act. It is considered that an increase in viscosity involving the amino group of the dispersant is suppressed by the interaction between the carboxyl group of the aromatic carboxylic acid compound and the amino group of the dispersant due to the pigment surface. Furthermore, the approach to the pigment particles is difficult with a polymer compound, and in order to facilitate this, it is considered effective to have a molecular weight of 500 or less.

[2] Pigment Dispersion The pigment dispersion of the present invention contains a pigment, a solvent, a dispersant, and an aromatic carboxylic acid compound as essential components, and if necessary, other additives other than the above components. You may do it.
Hereinafter, each component will be described.

[2-1] Pigment As the pigment, pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. Terms such as “CI Pigment Red 2” mentioned below mean the color index (CI).

  Examples of red 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, preferably C.I. I. Pigment Red 48: 1, 122, 166, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc., more preferably C.I. I. Pigment red 166, 177, 209, 224, 242, 254 and the like.

  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, and the like. Of these, C.I. I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, etc., more preferably C.I. I. Pigment blue 15: 6.

  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, and C.I. I. Examples thereof include brominated zinc phthalocyanine represented by Pigment Green 58. Of these, C.I. I. Pigment green 7, 36, and C.I. I. Examples thereof include brominated zinc phthalocyanine represented by Pigment Green 58. The details of brominated zinc phthalocyanine will be described later.

  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, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 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 the like. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, etc., more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180, 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. Among these, Preferably, C.I. I. And CI pigment oranges 38 and 71.

  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. And CI Pigment Violet 23.

  As the black pigment, a single black pigment or a black pigment obtained by mixing red, green, blue, or the like can be used. These black pigments can be appropriately selected from inorganic or organic pigments and dyes, and can be used alone or in combination.

  Examples of the single black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black. Among these, carbon black and titanium black are particularly preferable from the viewpoints of light shielding rate and image characteristics. Examples of commercially available carbon black include the following brands.

  Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA220, MA230, # 52, # 50, # 47, # 45, # 2700, # 2650, # 2200, # 1000, # 990, # 900, etc.

  Made by Degussa: Printex95, Printex90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30, Printex3, PrintexA, PrintexG, Special BlackS, 350c, p

  Manufactured by Cabot Corporation: Monarch 460, Monarch 430, Monarch 280, Monarch 120, Monarch 800, Monarch 4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, BLACK PEARLS480, PEARLS480, etc.

  Made by Colombian Carbon: Raven11, Raven15, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven890H, Raven1000, Raven1020, Raven1040 and the like.

  Next, the black pigment by mixing will be described. Specific examples of the color material used as a base for mixing include Victoria Pure Blue (42595), Auramine O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK70: 100 (50240), Erioglaucine X (42080), no. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean the color index (CI)).

  In addition, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, etc., C.I. I. Orange pigments 36, 43, 51, 55, 59, 61 etc., C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, etc., C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, etc., C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64 etc., C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

  The carbon black may be used in combination with other black or colored inorganic or organic pigments. Other pigments naturally have a light shielding property or image characteristic lower than that of carbon black, so the mixing ratio is naturally limited.

  Titanium black is produced by heating a mixture of titanium dioxide and metal titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, No. 61-201610), and a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610). It is not a thing.

  Examples of commercially available titanium black include Titanium Black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.

  These pigments may be used alone or in combination of two or more. The average primary particle size of these pigments is usually 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.04 μm or less, particularly preferably 0.025 μm or less, and usually 0.005 μm or more. is there. When the pigment is atomized, a technique such as solvent salt milling described later is preferably used.

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

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

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

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

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

As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used. Further, the particle diameter of these inorganic salts is more preferably 0.5 to 50 μm. Such an inorganic salt can be easily obtained by pulverizing a normal inorganic salt.
The brominated zinc phthalocyanine thus obtained may be used alone, but the brominated zinc phthalocyanine having a different bromination rate or chlorination rate or other metals as long as the effect of the present invention is not impaired. It can be used by mixing with brominated phthalocyanine substituted with metal. By changing the chlorination rate and bromination rate, or by changing the central metal, it is expected that the color tone of the pigment will change and that variations in the reproducible hue will increase. In addition, C.I. I. You may mix with halogenated copper phthalocyanines, such as pigment green (PG) 36 or 7.

The average primary particle size of the green pigment containing brominated zinc phthalocyanine is usually 0.1 μm or less, preferably 0.04 μm or less, more preferably 0.03 μm or less, and even more preferably 0.025 μm or less. 005 μm or more.
If the average primary particle size is too large, the depolarization characteristics will deteriorate and the contrast will be insufficient, and if it is severe, the transmittance will be lowered. , Production problems such as a decrease in the yield of color filters due to protrusion foreign matter and the cause of blockage of the process filter may occur.On the other hand, if it is too small, the dispersion stability is poor due to an increase in specific surface area, Problems such as deterioration of heat resistance and light resistance due to the pigment approaching the molecular state may occur.

The average primary particle size of the pigment 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). The primary particle diameter is measured from this image, the number average value is calculated according to the following formula, and the average particle diameter is obtained.
In the case of an organic pigment, the particle diameter of each pigment particle is defined as an area equivalent circle diameter converted to the diameter of a circle having the same area, and after calculating the particle diameter for each of the plurality of pigment particles, the following formula Calculate the average particle size by calculating the number average value as follows.
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

  In addition, in order to adjust to a desired color, two or more colors among the above-described various pigments may be mixed and used. For example, when preparing a red or green pigment dispersion or a colored composition, each of the red pigment and the green pigment can be combined with at least one yellow pigment in order to adjust the hue. Examples of such yellow pigments include the various yellow pigments described above. Further, when preparing a blue pigment dispersion or a colored composition, a purple pigment can be combined with a blue pigment.

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.
The pigment content in the color filter coloring composition of the present invention is usually 75% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, and usually 10% by weight, based on the total amount of solids. % By weight or more, preferably 20% by weight or more, more preferably 25% 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.

[2-2] Solvent In the pigment dispersion according to the present invention and the coloring composition described later, the solvent adjusts the viscosity by dissolving or dispersing the pigment, the dispersant, and other components other than the above optionally blended. It has a function.
Any solvent can be used as long as it can dissolve or disperse each component.

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.

<When forming color filter pixels by photolithography>
When forming color filter pixels by photolithography, a solvent having a boiling point in the range of 100 to 200 ° C. (under a pressure of 101.25 [hPa], hereinafter the same applies to the boiling point) is selected. Is preferred. More preferably, it has a boiling point of 120 to 190 ° C.
Glycol alkyl ether acetates are preferred from the viewpoints of good balance between the coating properties, surface tension and the like in the solvent, and relatively high solubility of the constituent components in the composition.

  In addition, glycol alkyl ether acetates may be used alone or in combination with other solvents. As the solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigments tend to aggregate, and the storage stability tends to decrease such as the viscosity of the colored composition obtained later increases. The proportion of glycol monoalkyl ethers in them is preferably 5% by weight to 30% by weight, and more preferably 5% by weight to 20% by weight.

  It is also preferable to use a solvent having a boiling point of 150 ° C. or higher in combination. By using such a high-boiling solvent in combination, the colored composition is difficult to dry, but it has the effect of making it difficult for the pigment dispersion to break apart due to rapid drying. The content of the high boiling point solvent is preferably 3% by weight to 50% by weight, more preferably 5% by weight to 40% by weight, and particularly preferably 5% by weight to 30% by weight with respect to the solvent. If the amount of the high boiling point solvent is too small, for example, coloring material components may precipitate and solidify at the tip of the slit nozzle to cause foreign matter defects, and if it is too large, the drying temperature of the composition will be slow, which will be described later. There is a concern that it may cause problems such as tact defects in the vacuum drying process and pre-baked pin marks in the color filter manufacturing process.

  The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be separately contained.

<When forming color filter pixels by inkjet method>
When forming a pixel of a color filter by the inkjet method, the boiling point of the solvent is usually 130 ° C. or higher and 300 ° C. or lower, preferably 150 ° C. or higher and 280 ° C. or lower. When the boiling point is too low, the uniformity of the resulting coating film tends to be poor. On the other hand, if the boiling point is too high, the effect of inhibiting drying of the curable resin composition is high as described later, but there are many residual solvents in the coating film even after heat firing, which may cause quality problems. In some cases, the drying time in vacuum drying or the like becomes long, resulting in problems such as an increase in tact time.

  The solvent vapor pressure is usually 10 mmHg or less, more preferably 5 mmHg or less, and still more preferably 1 mmHg or less, from the viewpoint of the uniformity of the resulting coating film.

  In addition, in the production of color filters by the ink jet method, the ink emitted from the nozzle is very fine, from several to several tens of pL, so the solvent evaporates and concentrates before landing on the periphery of the nozzle opening or in the pixel bank.・ Tends to dry. In order to avoid this, it is preferable that the solvent has a high boiling point. Specifically, it is preferable to include a solvent having a boiling point of 180 ° C. or higher. More preferably, it contains a solvent having a boiling point of 200 ° C. or higher, particularly preferably a boiling point of 220 ° C. or higher. Further, the high boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by weight or more, more preferably 70% by weight or more in the total solvent contained in the pigment dispersion and / or the color filter coloring composition, 90% by weight or more is most preferable. When the high boiling point solvent is less than 50% by weight, the effect of preventing evaporation of the solvent from the droplets may not be sufficiently exhibited.

  Preferred examples of the high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol. Examples thereof include diacetate and triacetin.

  Furthermore, it is also effective to partially contain a solvent having a boiling point lower than 180 ° C. in order to adjust the viscosity of the pigment dispersion and the coloring composition and the solubility of the solid content. As such a solvent, a solvent having low viscosity, high solubility, and low surface tension is preferable, and ethers, esters, ketones, and the like are preferable. Of these, cyclohexanone, dipropylene glycol dimethyl ether, cyclohexanol acetate, and the like are particularly preferable.

  On the other hand, when the solvent contains alcohols, the ejection stability in the ink jet method may deteriorate. Therefore, the alcohol is preferably 20% by weight or less in the total solvent, more preferably 10% by weight or less, and particularly preferably 5% by weight or less.

  Although there is no restriction | limiting in particular in content of the solvent which occupies for the whole coloring composition of this invention, The upper limit shall be 99 weight% or less normally. If the solvent exceeds 99% by weight, the amount of pigment, dispersant, etc. will be too small, which is inappropriate for forming a coating film. On the other hand, the lower limit of the solvent content is usually 67% by weight or more, preferably 70% by weight or more, and more preferably 73% by weight or more in consideration of viscosity suitable for coating.

[2-3] Dispersant The dispersant used in the pigment dispersion according to the present invention is a block copolymer composed of an A block having solvophilicity and a B block having a functional group containing a nitrogen atom, The block copolymer whose amine value is 80 mgKOH / g or more and 150 mgKOH / g or less (effective solid content conversion) is contained.
As the block copolymer, a (meth) acrylic block copolymer is preferable. Hereinafter, the dispersant will be described by taking a case of a (meth) acrylic block copolymer as an example.

The B block has a functional group containing a nitrogen atom, and the functional group is preferably a primary to tertiary amino group. The content ratio of the primary to tertiary amino groups is preferably 20 mol% or more, more preferably 50 mol% or more of the entire nitrogen atom-containing functional group.
Of the primary to tertiary amino groups, tertiary amino groups are more preferred. The tertiary amino group is particularly preferably —NR ⁴¹ R ⁴² (wherein R ⁴¹ and R ⁴² each independently has a cyclic or chain alkyl group which may have a substituent, or a substituent. An aryl group which may optionally be substituted, or an aralkyl group which may have a substituent.), And a preferred partial structure (repeating unit) containing this is, for example, the following formula It is represented by

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

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

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

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

(In the formula, n represents an integer of 1 to 5, and R ₁ represents a hydrogen atom or a methyl group.)
The partial structure represented by the above formula (VIII) is particularly preferably contained in the A block in an amount of 5 to 40 mol%.

  Although the detailed mechanism of action is unknown, it has a partial structure derived from polyalkylene glycol (meth) acrylate, in particular a partial structure represented by the above formula, so that it is possible to increase hydrogen bonding properties, It is thought that the affinity for the dispersion improves and the stability of the dispersion increases.

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

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

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

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

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

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

  The pigment dispersion according to the present invention is an AB block copolymer or an ABA block copolymer 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 mgKOH / g. It is essential to use a dispersant that is greater than or equal to (effective solid content conversion). By using such a block copolymer as a dispersant, it is possible to satisfy both strong polymer adsorption on the pigment surface and high solvent affinity at the same time, so that high dispersion stability can be expressed. Further, by increasing the amine value, the adsorptive power on the surface of the pigment that has been particularly acid-treated is increased, so that the dispersion stability is further improved.

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

  In addition, the pigment dispersion liquid and coloring composition which concern on this invention may contain dispersing agents other than the dispersing agent which consists of a block copolymer mentioned above in the range which does not impair the effect of this invention. Examples of such a dispersant include a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyallylamine-based dispersant, a dispersant composed of a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether-based dispersant, Examples thereof include oxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants. Specific examples of such a dispersant are trade names of EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Lubrizol) , KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like. These dispersants may be used alone, or two or more dispersants including the above-described dispersant composed of a block copolymer may be mixed and used in any combination and ratio. .

The dispersant in the present invention is usually 5 to 200% by weight, preferably 10 to 100% by weight, more preferably 12.5 to 50% by weight, still more preferably 14 to 33.% by weight based on the total amount of the pigment in the pigment dispersion. It is preferable to use about 3% by weight.
If the amount of the dispersant is too large, the brightness and heat resistance tend to be lowered. If the amount is too small, the pigment dispersion is insufficient and the pigment dispersion tends to thicken.

[2-4] 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.

[2-5] Dispersing Resin The pigment dispersion of the present invention may contain a part or all of a resin selected from binder resins that can be used in the coloring composition. 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.

[3] Coloring composition
The coloring composition of the present invention comprises at least the pigment, solvent, dispersant, and aromatic carboxylic acid compound described above, for example, the aromatic carboxylic acid compound represented by the general formula (A), and a binder resin described later. Containing.
In addition, the aromatic carboxylic acid-based compound can be prevented from increasing in viscosity over time of the pigment dispersion itself by being contained during the preparation of the pigment dispersion, and is prepared using such a pigment dispersion. The time-dependent thickening of the coloring composition for a color filter can also be suppressed. In addition, when preparing a color filter coloring composition by adding various components to the pigment dispersion, by adding it as one of the components added later, the color filter coloring composition can be thickened over time. It is also possible to suppress it. Furthermore, when preparing the coloring composition by mixing the components constituting the coloring composition for a color filter at one time or sequentially without preparing a pigment dispersion, any one of the constituent components may be used. You may mix | blend with timing.

As a component other than the above-mentioned essential components contained in the colored composition of the present invention, any component can be used without particular limitation as long as it can be used as a color filter forming material. For example, a thermosetting resin composition used in a so-called lift-off type color filter manufacturing process described in JP-A-60-184202 and the like, and an inkjet type color filter manufacturing described in JP-A-2004-220036 Examples thereof include a thermosetting resin composition used in the process and a photopolymerizable resin composition described later. A suitable type of resin composition may be selected depending on the means by which the colored composition is cured to produce a color filter.
In addition, when a coloring composition is a photopolymerizable composition, it is preferable to contain a photoinitiation system.
Hereinafter, the case where the coloring composition of the present invention is a photopolymerizable resin composition will be described in detail, but the present invention is not limited thereto.

[3-1] Binder resin
As described above, as the binder resin, a preferable resin varies depending on a coloring composition that is cured by any means.
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 [3-1-1 ] 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,
[3-1-2] A linear alkali-soluble resin containing a carboxyl group in the main chain,
[3-1-3] 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”;
[3-1-4] (Meth) acrylic resin,
[3-1-5] An epoxy (meth) acrylate resin having a carboxyl group is exemplified. Hereinafter, each of these resins will be described.

[3-1-1] Unsaturated monobasic acid in at least part of the epoxy group of the copolymer with respect to the copolymer of epoxy group-containing (meth) acrylate and other radical polymerizable monomer Or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. As one 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 “[3-1-1] 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.

  [3-1-1] 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, 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.
[3-1-1] The polystyrene-converted weight average molecular weight (Mw) of the resin measured by GPC 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.

[3-1-2] A 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 “[3-1-2] 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.

  [3-1-2] 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.

  [3-1-2] 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.
[3-1-2] The acid value of the resin is usually 30 to 500 mgKOH / g, preferably 40 to 350 mgKOH / g, and 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.

[3-1-3] 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 “main chain contains a carboxyl group” Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group part of the “linear alkali-soluble resin” (that is, [3-1-2] resin) (hereinafter referred to as [3-1-3] 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 technique can be used to add the epoxy group-containing unsaturated compound to the carboxyl group portion of the [3-1-2] 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.

[3-1-3] 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.

[3-1-4] (Meth) acrylic resin
(Meth) acrylic resin (hereinafter sometimes referred to as “[3-1-4] resin”) includes (meth) acrylic acid and / or (meth) acrylic acid ester as monomer components. Refers to a polymer obtained by polymerizing Preferred examples of the (meth) acrylic resin include a polymer [3-1-4a] obtained by polymerizing a monomer component containing (meth) acrylic acid and benzyl (meth) acrylate, and the following general formula (4). And / or a polymer [3-1-4b] obtained by polymerizing a monomer component essentially containing 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.

[3-1-4a] A polymer obtained by polymerizing a monomer component containing (meth) acrylic acid and benzyl (meth) acrylate. A monomer component containing (meth) acrylic acid and benzyl (meth) acrylate is polymerized. 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.

[3-1-4b] A polymer obtained by polymerizing a monomer component essentially comprising the compound represented by the general formula (4) and / or (5)
First, the compound of General formula (4) is demonstrated.
In the ether dimer represented by the general formula (4), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ^1a and R ^2a is not particularly limited. Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance. R ^1a and R ^2a may be the same type of substituent or different substituents.

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

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

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

  In the monomer component constituting the [3-1-4b] 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 [3-1-4] resin in the present invention preferably has an acid group, including the polymers of [3-1-4a] and [3-1-4b]. 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.

  [3-1-4] In order to introduce an acid group into a 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.

[3-1-4] 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.
[3-1-4] The resin may have a radically polymerizable double bond.

  [3-1-4] 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.

[3-1-4] When the monomer component for 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 [3-1-4] resin is a polymer having the compound of the general formula (4) described in [3-1-4a] as an essential monomer component, 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.

[3-1-4] 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.
[3-1-4] 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 [3-1-4] 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 a 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 for obtaining the [3-1-4] 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, a method for producing (3-1-4) resin (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 above-mentioned monomer capable of imparting an acid group as a monomer component when obtaining the [3-1-4] resin, a treatment for imparting an 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 in obtaining the [3-1-4] 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.

  [3-1-4] 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.

[3-1-4] When the resin has an acid group, the 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 [3-1-4] 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. Examples include compounds described in Japanese Patent No. 300204.

[3-1-5] Epoxy acrylate resin having carboxyl group
The “epoxy acrylate resin having a carboxyl group” (hereinafter sometimes referred to as “[3-1-5] 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 [3-1-5] 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.

  In addition, as the [3-1-5] resin, for example, a naphthalene-containing resin 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 above-mentioned various binder resins, [3-1-1] “copolymer of (epoxy group-containing (meth) acrylate) and other radical polymerizable monomer, Resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group of the copolymer, or an alkali obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction A “soluble 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 to be used as the dispersion resin, [3-1-4] resin is particularly preferable, and among them, a polymer obtained by polymerizing a monomer component essentially including the compound represented by the general formula (4) is most 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 fragile and the adhesion to the substrate may be lowered. On the other hand, when the amount is larger than this range, the permeability of the developing solution to the exposed portion increases, and the surface smoothness and sensitivity of the pixel may deteriorate.

[3-2] Other solid contents (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. Such components include polymerizable monomers, photopolymerization initiation components, organic carboxylic acids, organic carboxylic acid anhydrides, surfactants, thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protective agents, adhesion improvers, Examples include development improvers and dyes.

[3-2-1] Polymerizable monomer The polymerizable monomer is not particularly limited as long as it is a low molecular weight compound that can be polymerized. However, an addition polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylene”). Preferred compound "). When the colored composition of the present invention is irradiated with actinic rays, the ethylenic compound undergoes addition polymerization and curing by the action of a photopolymerization initiation system described later or by the action of a thermal polymerization initiator described later by heating. It is a compound having such an ethylenic double bond. In addition, the monomer in this invention means the concept opposite to what is called a polymeric substance, and means the concept which also includes a dimer, a trimer, and an oligomer other than a monomer in 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.

[3-2-2] Photopolymerization initiation system and / or thermal polymerization initiation system
The colored composition of the present invention preferably contains a photopolymerization initiation system and / or a thermal polymerization initiation system 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 a binder resin component, or when it contains an ethylenic compound as the polymerizable monomer described above, 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 initiation system that generates a polymerization active radical by heat.
[3-2-2a] Photopolymerization Initiation System The photopolymerization initiator is usually used as a mixture (photopolymerization initiation system) with an additive such as an accelerator. The photopolymerization initiation system is a component that has a function of directly absorbing light or photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.
Examples of the photopolymerization initiator constituting the photopolymerization initiation system component include metallocene compounds including titanocene compounds described in JP-A Nos. 59-152396 and 61-151197, and the like. Hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, and the like described in Kaihei 10-39503 Described in radical activators such as aryl-α-amino acid esters, α-aminoalkylphenone compounds, JP-A-2006-36750, JP-A-2002-323762, and JP-A-2000-80068. Oxime ester compounds 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-cyclopentagenyl-Ti-2,4-di-fluorophen-1-yl, Di-methylcyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentagenyl-Ti-bis-2,6-di-fluoropheny -1 Yl, di - cyclopentadienyl -Ti-2,6-di - fluoro-3- (pill-1-yl) - titanocene derivatives such as 1-yl;

2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) 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 a 2-4 condensed ring, preferably a divalent group derived from a 2 or 3 condensed ring 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, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroaryl having 4 to 25 carbon atoms. Represents an alkyl group, and these alkyl groups, alkenyl groups, heteroaryl groups, and heteroarylalkyl groups may all have a substituent. 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, and a cyclopentylcarbonyl group, preferably 4 to 8 carbon atoms such as cyclohexylcarbonyl, and more preferably 4 carbon atoms. A cycloalkanoyl group of ˜7.

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. In addition, when Y is a monovalent group derived from an aromatic heterocycle, even if a group in which one or more rings are condensed to a phenyl group, one or more rings are present in a 5- or 6-membered heteroaryl group. 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 is not 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 for Y include, for example, 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.

  The 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 general formula (I) can have [substituents that benzene ring X ¹ in general formula (i) and 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 each independently selected from the following substituents Z.

[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 substituent which the benzene ring X ¹ and the ring X ² condensed thereto in the general formula (i) may have] may be 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-based compound represented by the general formula (I) can be obtained by a method known per se, for example, the method described in WO2002 / 100903, WO2005 / 080337, JP2006-36750, or the like. Can be synthesized.

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

Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-diethyl Aminophenyl) 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. and 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, and more preferably 10% by weight or less.

[3-2-2b] 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-ethylpropionamide], 2,2'-azobis [N-butyl-2-methylpropionamide], 2,2'-azobis ( -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. Among these, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) and the like are included. 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 [3-2-2a], 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 initiators in the colored resin 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 initiators 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 resin composition of the present invention.

[3-2-3] 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.

[3-2-4] 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.

[3-2-5] 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.

[4] 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 aromatic carboxylic acid compound used in the present invention may be contained in any of these steps.
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, pigment, a solvent, a dispersant, and the aromatic carboxylic acid compound represented by the general formula (A) are weighed in predetermined amounts, 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 coloring material is made fine particles, so that the coating characteristics of the coloring composition are improved, and the transmittance of the pixels in the product color filter substrate is improved.

When dispersing the pigment, as described above, it is preferable to use a dispersion aid or a dispersion resin in combination as appropriate.
Further, 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 dispersion time varies depending on the composition of the pigment dispersion, the size of the sand grinder apparatus, and the like, and therefore needs to be adjusted appropriately.

  The pigment dispersion obtained by the dispersion treatment is mixed with a solvent, a binder resin, and in some cases, a predetermined amount of a polymerizable monomer, a photopolymerization initiation system component, and components other than those described above 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.

[5] 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.

[5-1] 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.

[5-2] 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.

[5-3] Pixel formation
The method for forming the pixel differs depending on the type of the coloring composition to be used. Here, a case where a photopolymerizable composition is used as the coloring composition will be described as an example.
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.

[5-4] 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.

[5-5] 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.

[5-6] 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.

[5-7] 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.

  The color filter of the present invention includes (1) a solvent, a pigment, a dispersant used in the present invention, an aromatic carboxylic acid compound, and a polyimide resin as a binder resin in addition to the manufacturing method described above. It can also be produced by a method in which a coloring composition is applied to a substrate and pixels are formed by an etching method. (2) A method of directly forming pixels on a transparent substrate by a printing machine using a coloring composition containing a solvent, a pigment, a dispersant used in the present invention, and an aromatic carboxylic acid compound as a coloring ink (3) A coloring composition containing a solvent, a pigment, a dispersant used in the present invention, and an aromatic carboxylic acid compound is used as an electrodeposition solution, and the substrate is immersed in the electrodeposition solution to form a predetermined pattern. For example, a method of depositing a colored film on the ITO electrode. Further, (4) a film coated with a coloring composition containing a solvent, a pigment, a dispersant used in the present invention, and an aromatic carboxylic acid compound is attached to a transparent substrate, peeled off, exposed, developed, and pixelated. And (5) a method of forming a pixel by an ink jet printer using a coloring composition containing a solvent, a pigment, a dispersant used in the present invention, and an aromatic carboxylic acid compound as a coloring ink, etc. Is mentioned. 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.

[5-8] 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.

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

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

  The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of vacuum in the liquid crystal cell is usually in the range of 1 × 10 ⁻² Pa or more, preferably 1 × 10 ⁻³ Pa or more, and usually 1 × 10 ⁻⁷ Pa or less, preferably 1 × 10 ⁻⁶ Pa or less. . The liquid crystal cell is preferably heated during decompression, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower.
The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. In the liquid crystal cell into which liquid crystal is injected, a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.

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

[7] Organic EL Display When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 5, first, a pixel 20 (however, at least a part of the pixel 20 is formed on a transparent support substrate 10). 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.
[1] Synthesis Example [1-1] Synthesis Example 1: Synthesis of green pigment (brominated zinc phthalocyanine) Zinc phthalocyanine was produced using phthalodinitrile and zinc chloride as raw materials. This 1-chloronaphthalene solution had light absorption at 600 to 700 nm. For halogenation, 3.1 parts by weight of sulfuryl chloride, 3.7 parts by weight of anhydrous aluminum chloride, 0.46 parts by weight of sodium chloride and 1 part by weight of zinc phthalocyanine were mixed at 40 ° C., and 4.4 parts by weight of bromine was added dropwise. I went. The mixture was reacted at 80 ° C. for 15 hours, and then the reaction mixture was poured into water to precipitate a brominated zinc phthalocyanine crude pigment. This aqueous slurry was filtered, washed with hot water at 80 ° C., and dried at 90 ° C. to obtain 3.0 parts by weight of a purified brominated zinc phthalocyanine crude pigment.

Next, 12 parts by weight of crushed sodium chloride, 1.8 parts by weight of diethylene glycol, and 0.09 parts by weight of xylene are charged into a double-arm kneader in 1 part by weight of the above brominated zinc phthalocyanine crude pigment and kneaded at 70 ° C. for 10 hours. After kneading, the mixture was taken out into 100 parts by weight of water at 80 ° C., stirred for 1 hour, and then filtered, washed with hot water, dried and ground to obtain a brominated zinc phthalocyanine pigment.
Brominated zinc phthalocyanine pigment obtained by the average composition ZnPcBr ₁₄ Cl ₂ from halogen content analysis by mass spectrometry (Pc: phthalocyanine) were those containing an average of 14 bromine atoms per molecule. Moreover, the average value of the primary particle size measured with a transmission electron microscope (H-9000UHR manufactured by Hitachi, Ltd.) was 0.023 μm. The average primary particle diameter of the pigment is determined by dispersing the pigment ultrasonically in chloroform, dropping it onto a mesh with a collodion film, drying it, and observing the primary particle image of the pigment by observation with a transmission electron microscope (TEM). The primary particle size was measured from this image, and the number average value (average particle size) was determined.

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

  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 A total of 5.2 parts by weight of hexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate were charged, and 5.2 parts by weight of n-dodecyl mercaptan and 27 parts by weight of propylene glycol monomethyl ether acetate were charged in a chain transfer agent tank. After the temperature was stabilized at 90 ° C., dropping was started from the monomer tank and the chain transfer agent tank to start 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 solution was cooled to room temperature to obtain a polymer (resin D) solution having a weight average molecular weight of 8000 and an acid value of 101 mgKOH / g.

[1-3] Synthesis Example 3: Synthesis of Resin E 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. 114 parts by weight of benzyl methacrylate, 26 parts by weight of methacrylic acid, and 9.9 parts by weight of 2,2′-azobis (isobutyronitrile) were dissolved in 96 parts by weight of propylene glycol monomethyl ether acetate and added dropwise over 4 hours. did.

  After the dropwise addition, the reaction solution was further stirred for 2 hours while maintaining the temperature at 85 ° C., and then the nitrogen bubbling was stopped, the temperature was raised to 100 ° C. and stirred for 1 hour. To this, 0.7 parts by weight of tetraethylammonium chloride was added, stirred and dissolved at 80 ° C., and further mixed with 16 parts by weight of 3,4-epoxycyclohexyl-1-methyl acrylate and 24 parts by weight of propylene glycol monomethyl ether acetate. The solution was added dropwise over 1 hour. The reaction solution was stirred for 30 hours while being kept at 80 ° C. to obtain a polymer (resin E) solution having a weight average molecular weight of 8000 and an acid value of 90 mgKOH / g.

[1-4] Synthesis Example 4: Synthesis of Resin F 10 parts by weight of a monoacrylate having a tricyclodecane skeleton (“FA-513M” manufactured by Hitachi Chemical Co., Ltd.), 43.5 parts by weight of cyclohexyl methacrylate, 3.0 of methyl methacrylate Part by weight and 43.5 parts by weight of methacrylic acid were dissolved in 150 parts by weight of propylene glycol monomethyl ether acetate, and 1.25 parts by weight of azobisisobutyronitrile was added in a nitrogen atmosphere and reacted at 80 ° C. for 7 hours. The thus obtained binder resin F had a polystyrene-equivalent weight average molecular weight Mw measured by GPC of about 7200 and an acid value measured by neutralization titration method of 84.

[1-5] Synthesis Example 5: Synthesis of Resin G 145 parts by weight of propylene glycol monomethyl ether acetate was stirred while being replaced 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 stirring was continued 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. Then, 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 G thus obtained was about 15,000.

[1-6] Synthesis Example 6: Synthesis of Resin H A separable flask equipped with a cooling tube was prepared as a reaction tank, charged with 400 parts by weight of propylene glycol monomethyl ether acetate, purged with nitrogen, and then stirred in an oil bath. The temperature of the reaction vessel was raised to 90 ° C. by heating.
Meanwhile, in the monomer tank, 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 benzyl 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 103 mgKOH / g was obtained.

[2] Preparation of green pigment dispersion
As a green pigment, 7.24 parts by weight of brominated zinc phthalocyanine obtained in Synthesis Example 1 and C.I. I. 2.54 parts by weight of Pigment Yellow 150, 60.00 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 1.96 parts by weight of a dispersant “BYK-LPN6919” manufactured by Big Chemie as a dispersant, and a synthesis example Fill the stainless steel container with 3.26 parts by weight of the resin D obtained in Step 2 in terms of solid content together with 225 parts by weight of zirconia beads having a diameter of 0.5 mm, and disperse in a paint shaker for 6 hours to disperse the green pigment. A liquid was prepared.

<Dispersant A: Dispersant “BYK-LPN6919” 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 of the repeating unit represented by the following formula (ii), The ratio in the A block was 11 mol%.

[3] Preparation of red pigment dispersion [3-1] R. Preparation of 254 pigment dispersion C.I. I. 8.50 parts by weight of Pigment Red 254, 3.4 parts by weight of the dispersant “LPN6919” manufactured by Big Chemie Co., and 2.83 parts by weight of the resin F obtained in Synthesis Example 4 in terms of solids, As a solvent, 50.16 parts by weight of propylene glycol monomethyl ether acetate was added, filled in a stainless steel container with 225 parts by weight of zirconia beads having a diameter of 0.5 mm, and dispersed in a paint shaker for 6 hours. R. A 254 pigment dispersion was prepared.

[3-2] P.I. R. 177 / P. Preparation of Y.150 pigment dispersion C.I. I. Pigment Red 177, 22.40 parts by weight, C.I. I. 5.60 parts by weight of Pigment Yellow Y150, 8.48 parts by weight of the dispersant “Disperbyk2001” manufactured by Big Chemie, and 9.03 parts by weight of Resin E obtained in Synthesis Example 3 in terms of solids, 157.66 parts by weight of propylene glycol monomethyl ether acetate as a solvent and 675 parts by weight of zirconia beads having a diameter of 0.5 mm are filled in a stainless steel container, and dispersed in a paint shaker for 6 hours to obtain a red pigment dispersion (PR .177 / PY 150 pigment dispersion).

[4] Examples 1-3 and Comparative Examples 1-4: Preparation of red coloring composition R. 254 pigment dispersion 3.87 parts by weight R. 177 / P. Y. 150 pigment dispersion 4.15 parts by weight propylene glycol monomethyl ether acetate 5.63 parts by weight, resin G obtained in Synthesis Example 5 0.44 parts by weight in terms of solid content, manufactured by Ciba Specialty Chemicals 0.05 part by weight of a photopolymerization initiator “Irgacure OXE02”, 0.07 part by weight of a photopolymerization initiator “Irgacure 907” manufactured by Ciba Specialty Chemicals, and a surfactant “F475” manufactured by Dainippon Ink as a surfactant. "0.003 part by weight, 0.70 part by weight of TO1382 manufactured by Toagosei Co., Ltd. as a polymerizable monomer (however, 0.78 part by weight only in Comparative Example 4), and the aromatic carboxylic acid based on Table 1 A red coloring composition was prepared by adding 0.08 parts by weight of a compound (or a compound to be compared with the compound).
The photopolymerization initiator “Irgacure OXE02” manufactured by Ciba Specialty Chemicals is the following compound.

[5] Examples 4 to 6 and Comparative Examples 5 to 8: Preparation of Green Coloring Composition Into 10.55 parts by weight of the green pigment dispersion obtained in the above [4] preparation of the green pigment dispersion, propylene glycol monomethyl was added. 5.96 parts by weight of ether acetate, 0.42 parts by weight of the resin H obtained in Synthesis Example 6, 0.1 g of photopolymerization initiators “Irgacure OXE02” and “Irgacure 907” manufactured by Ciba Specialty Chemicals, respectively. 10 parts by weight, a surfactant “F475” manufactured by Dainippon Ink Co., Ltd. as a surfactant, and 0.77 parts by weight of a pentaerythritol tetraacrylate as a polymerizable monomer (however, in Comparative Example 8 only, 0.86) Parts by weight), and 0.085 parts by weight of an aromatic carboxylic acid compound (or a compound to be compared with this) as shown in Table 2, Color colored composition was prepared.

  In addition, the aromatic carboxylic acid type compound (and the compound compared with this) used in each Example and each Comparative Example is as shown in Table 3, respectively.

[6] Evaluation of the colored composition The colored composition obtained in the above Examples and Comparative Examples,
(1) After preparation, left at 23 ° C. for 1 day, and
(2) (1) was further left in a constant temperature bath at 35 ° C. for 6 days,
The following evaluations were made. The results are shown in Tables 1 and 2.

[6-1] Method for measuring viscosity stability
The colored compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 8 were allowed to stand by the methods (1) and (2) described above, and the viscosity (20 rpm) was obtained for each of the obtained compositions. Each was measured using an E-type viscometer “RE-80L” manufactured by Toki Sangyo Co., Ltd. The results are shown in Tables 1 and 2.

[6-2] Measurement of application of linear pattern The green coloring compositions obtained in Examples 4 to 6 and Comparative Examples 5 to 8 were allowed to stand by the methods (1) and (2) above. The following evaluation was performed using each obtained composition.
That is, the colored composition was spin-coated on a glass substrate on which chromium was vapor-deposited, and prebaked for 3 minutes on a hot plate at 80 ° C. At the time of coating, after drying, the rotation speed was adjusted so that the color coordinate y = 0.600 of the coating film.
Next, the sample was exposed at 60 mJ / cm ² through a linear mask pattern having a width of 50 μm and a length of 3 mm with a high-pressure mercury lamp, and then 0.04 wt% potassium hydroxide aqueous solution was used, and the developer temperature was 23 ° C. Spray development was performed at a pressure of 25 MPa.

The development time was set to twice the dissolution time of the colored composition measured in advance. The dissolution time measurement will be described later.
After development, the substrate was rinsed with sufficient water and then dried with clean air. Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes. The film thickness after drying was about 1.8 μm.
Ten of the obtained patterns were observed with an optical microscope at a magnification of 10 times, and the depressions at the edges of the lines were counted as the number of products. In order to confirm reproducibility, this was repeated twice to obtain an average value. A photomicrograph of a representative example of the pattern (pixel) is shown in FIG. The measurement results are shown in Table 2.

[6-3] Measurement of line width The green coloring compositions obtained in Examples 4 to 6 and Comparative Examples 5 to 8 were allowed to stand by the methods (1) and (2) described above. The following evaluation was performed using each composition.
That is, the coloring composition was applied to a glass substrate on which chromium was vapor-deposited and dried in the same manner as that prepared in the above measurement of [6-2] linear pattern. Next, a linear mask pattern having a width of 25 μm is fixed 150 μm apart from the substrate with a high-pressure mercury lamp, and the coated sample is exposed at 60 mJ / cm ² , and then a 0.04 wt% potassium hydroxide aqueous solution is used. Spray development was performed at a temperature of 23 ° C. and a pressure of 0.25 MPa.

The development time was set to twice the dissolution time of the colored composition measured in advance. The dissolution time measurement will be described later. After development, the substrate was rinsed with sufficient water and then dried with clean air. Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes. The film thickness after drying was about 1.8 μm.
The linear pattern thus obtained was observed 10 times using an optical microscope, and the line width was measured. The results are shown in Table 2.

[6-4] Measurement of dissolution time In the same manner as that prepared in the above [6-2] measurement of applying a linear pattern, the colored composition was applied to a glass substrate on which chromium was vapor-deposited and dried. On this dried coating film, a linear mask pattern having a width of 25 μm was fixed 150 μm apart from the substrate and exposed at 60 mJ / cm ² with a high-pressure mercury lamp. Subsequently, when 0.04 wt% aqueous potassium hydroxide solution was used and spray development was performed at a developer temperature of 23 ° C. and a pressure of 0.25 MPa, the unexposed colored composition was completely dissolved in the developer, and the substrate was The exposed time was taken as the dissolution time.

From the above results, the following is clear.
(1) The colored composition of the present invention has a problem when using a pigment dispersant composed of a block copolymer having a high amine value. Can be suppressed.
(2) The color filter produced by using the colored composition of the present invention is of extremely high quality having occurrence of “over” and having pixels having high linearity.

The present invention has the following useful effects, and its industrial utility value is extremely great.
1. In the coloring composition of the present invention, when a pigment dispersant composed of a block copolymer having a high amine value is used, the thickening of the coloring composition with time and the occurrence of cracks in the pattern have occurred. Suppression can be achieved.
2. The colored composition can achieve both high brightness, high contrast, and long-term storage stability.
3. A color filter having pixels formed using the colored composition is extremely high quality.

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

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 (21)

  A pigment dispersion containing a pigment, a solvent, and a dispersant, the pigment dispersion further containing an aromatic carboxylic acid compound, and the dispersant contains an A block and a nitrogen atom having solvophilicity. It is a block copolymer composed of a B block having a functional group containing a dispersant containing a block copolymer having an amine value of 80 mgKOH / g or more and 150 mgKOH / g or less (effective solid content conversion). Characteristic pigment dispersion. The aromatic carboxylic acid compound is represented by the following general formula (A)

(In the general formula (A), Z represents a methylene group or —O—, and n represents an integer of 0 to 3. However, when n is 2 or 3, the n Zs may be the same, May be different.
X ¹ is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyl group, a phenethyl group, a benzyloxy group, or —COOX ² (However, X ² is a number 1-7 alkyl group or a phenyl group having a carbon) indicates, none of these groups may have a substituent. )
The pigment dispersion liquid of Claim 1 which is a compound represented by these.   3. The pigment dispersion according to claim 1, wherein in the block copolymer, at least 20 mol% or more of repeating units having a functional group containing a nitrogen atom are repeating units having a primary to tertiary amino group. .   In the block copolymer, the repeating unit having a functional group containing a nitrogen atom is a repeating unit having a tertiary amino group, and the repeating unit is derived from dimethylaminoethyl (meth) acrylate. The pigment dispersion liquid according to any one of the above.   The pigment dispersion according to any one of claims 1 to 4, wherein the pigment is a pigment containing brominated zinc phthalocyanine.   The pigment dispersion liquid according to any one of claims 1 to 5, wherein an average primary particle size of the pigment is 0.025 µm or less. The pigment dispersion according to any one of claims 1 to 6, further comprising a dispersion resin.   A coloring composition comprising the pigment dispersion according to claim 1 and a binder resin.   Furthermore, the coloring composition of Claim 8 containing a polymerizable monomer.   Furthermore, the coloring composition of Claim 8 or 9 containing a photoinitiation system and / or a thermal-polymerization initiator.   A colored composition containing a pigment dispersion containing a pigment, a solvent and a dispersant, and a binder resin, wherein the colored composition further contains an aromatic carboxylic acid compound, and the dispersant is a parent composition. A block copolymer comprising a solvent A block and a B block having a functional group containing a nitrogen atom, the amine value of which is 80 mg KOH / g or more and 150 mg KOH / g or less (in terms of effective solid content) The coloring composition characterized by being a dispersing agent containing this. The aromatic carboxylic acid compound is represented by the following general formula (A)

(In the general formula (A), Z represents a methylene group or —O—, and n represents an integer of 0 to 3. However, when n is 2 or 3, the n Zs may be the same, May be different.
X ¹ is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyl group, a phenethyl group, a benzyloxy group, or —COOX ² (However, X ² is a number 1-7 alkyl group or a phenyl group having a carbon) indicates, none of these groups may have a substituent. )
The coloring composition of Claim 11 which is a compound represented by these.   The colored composition according to claim 11 or 12, wherein in the block copolymer, at least 20 mol% or more of repeating units having a functional group containing a nitrogen atom are repeating units having a primary to tertiary amino group. .   In the block copolymer, the repeating unit having a functional group containing a nitrogen atom is a repeating unit having a tertiary amino group, and the repeating unit is derived from dimethylaminoethyl (meth) acrylate. The coloring composition as described in any one of these.   The coloring composition according to any one of claims 11 to 14, wherein the pigment is a pigment containing brominated zinc phthalocyanine.   The coloring composition according to any one of claims 1 to 15, wherein an average primary particle size of the pigment is 0.025 µm or less.   Furthermore, the coloring composition as described in any one of Claims 11 thru | or 16 containing a photoinitiation system and / or a thermal-polymerization initiator.   Furthermore, the coloring composition as described in any one of Claims 11 thru | or 17 containing a polymerizable monomer.   A color filter comprising a pixel produced using the colored composition according to claim 8.   20. A liquid crystal display device comprising: the color filter according to claim 19 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 19.