JP6977502B2 - Coloring compositions and color filters for color filters - Google Patents

Description

The present invention is a coloring composition used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, an organic EL display device, electronic paper, etc., and a photosensitive coloring composition, and using the same. It relates to a color filter having a formed filter segment.

In the photosensitive composition for a color filter, a resin-type dispersant is generally used in order to maintain a good dispersion state of the colorant, and a basic dispersant is used for a pigment having an acidic surface. The properties of the colorant vary greatly depending on the structure. In recent years, in the field of color filters used in color liquid crystal display devices and the like, there are increasing demands for high brightness / high contrast, thin film formation, and miniaturization of patterns. Along with this, it is necessary to disperse the fine pigment with a limited amount of dispersant, and it is very difficult to achieve both dispersibility and required physical properties at present.

Primary to tertiary amines and quaternary ammonium salts are generally used as dispersants (Patent Documents 1 to 6). These uses are effective in stably dispersing the finely divided pigment. However, it is difficult to realize high demands for achieving both high contrast of color filters in recent years and various characteristics such as alkali developability, glass adhesion, and heat resistance, and improvement of these characteristics is strongly required.

Published Japanese Patent Application Laid-Open No. 8-038875 Published Japanese Patent Application Laid-Open No. 8-1438313 Published Japanese Patent Application Laid-Open No. 2009-185277 Published Japanese Patent Application Laid-Open No. 2002-31713 Published Japanese Patent Laid-Open No. 2004-287366 Published Japanese Patent Application Laid-Open No. 2010-134419

An object of the present invention is to achieve the following object.
That is, an object of the present invention is a photosensitive coloring composition that not only has good brightness, contrast, heat resistance, and storage stability, but also has excellent adhesion and developability, and a color formed by using the photosensitive coloring composition. To provide a filter.

［一般式（１）において、Ｒ¹¹は水素原子又はメチル基を表し、Ｒ¹²及びＲ¹³は、それぞれ独立に、２価の連結基を表し、Ｘ⁺は、２価のカチオン性連結基を表し、Ｙ^-は、１価のアニオン性基を表す。］
The present invention is a coloring composition for a color filter containing a colorant, a dispersant [A], a binder resin and a solvent, and the dispersant [A] is represented by the general formula (1) in the side chain. The present invention relates to a coloring composition for a color filter, which is a block copolymer [A1] containing an A block having a repeating unit and a B block having no repeating unit represented by the general formula (1).
General formula (1)

[In the general formula (1), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² and R ¹³ each independently represent a divalent linking group, and X ⁺ represents a divalent cationic linking group. represents, Y ^- represents a monovalent anionic group. ]

［一般式（２）において、Ｒ²¹及びＲ²²は、それぞれ独立に、１価の有機基を表す。
＊¹はＲ¹²との結合手を表し、＊²はＲ¹³との結合手を表す

一般式（３）

［一般式（３）において、Ｒ³¹及びＲ³²は、それぞれ独立に、１価の有機基を表す。
＊¹はＲ¹²との結合手を表し、＊²はＲ¹³との結合手を表す。］ Further, the present invention is the ^{coloring composition for a color filter, wherein X +} in the general formula (1) is a divalent linking group represented by the following general formula (2) or the following general formula (3).
General formula (2)

[In the general formula (2), R ²¹ and R ²² each independently represent a monovalent organic group.
* ¹ represents the bond with R ^{12 and * 2} represents the bond with R ^13.

General formula (3)

[In the general formula (3), R ³¹ and R ³² each independently represent a monovalent organic group.
* ¹ represents a bond with R ^{12 and * 2} represents a bond with R ¹³ . ]

The present invention also relates to the ^{coloring composition for a color filter, wherein X +} in the general formula (1) is a divalent linking group represented by the general formula (3).

The present invention also relates to the coloring composition for a color filter, wherein ^{R 31} and R ^{32 of the general formula (3) are monovalent aliphatic hydrocarbon groups.}

Further, the present invention, the Y in the general formula (1) ^- is, -CO ₂ ^- relating to the color filter colored composition for a ^- or -SO _3.

Further, in the present invention, the ^{coloring composition for a color filter, wherein R 12} of the general formula (1) is a group composed of a combination of an alkanediyl group having 1 to 8 carbon atoms and -COO- or -CONRb-. Regarding things.
[Rb represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

The present invention also relates to the ^{coloring composition for a color filter, wherein R 13} of the general formula (1) is an alkanediyl group having 1 to 5 carbon atoms.

Further, the present invention is for the color filter in which the content of the repeating unit represented by the general formula (1) is 50 to 100% by weight with respect to the A block contained in the block copolymer [A1]. Concerning coloring compositions.

The present invention also relates to the coloring composition for a color filter, which comprises a dispersant [B] having an aromatic carboxyl group.

Further, in the present invention, the colorant is one of a phthalocyanine pigment, a diketopyrrolopyrrole pigment, a quinophthalone pigment, an isoindoline pigment, an anthraquinone pigment, an azo pigment, and a dioxazine pigment. The present invention relates to a coloring composition for a filter.

The colorant further comprises C.I. I. Pigment Red 177, 254, C.I. I. Pigment Yellow 138, 139, 185, 231, C.I. I. The coloring composition for a color filter, which comprises Pigment Green 58, 62, 63, Pigment Blue 15: 6, or Pigment Violet 23.

Further, the present invention relates to the coloring composition for a color filter, which contains at least one selected from the group consisting of a photopolymerizable monomer and a photopolymerization initiator.

Furthermore, the present invention relates to a color filter including a filter segment formed from the coloring composition for a color filter.

Hereinafter, the constituent elements of the present invention will be described in detail.
In the present application, when the term "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", or "(meth) acrylate" is used, unless otherwise specified, "(meth) acrylate" is used. It shall represent "acryloyl and / or methacrylic acid", "acrylic and / or methacrylic acid", "acrylic acid and / or methacrylic acid", or "acrylate and / or methacrylate". Further, "CI" mentioned in the present specification means a color index (CI).

<Colorant (a)>
The coloring composition for a color filter of the present invention contains a coloring agent such as an organic pigment, an inorganic pigment, an organic dye, and an inorganic dye. These can be used alone or in any combination of two or more. Organic pigments are preferably used in the coloring composition for color filters of the present invention, for example, azo pigments (soluble azo lake pigments, insoluble azo pigments, condensed azo pigments, etc.), azomethine pigments, phthalocyanine pigments, quinacridone pigments. Pigments, isoindolinone pigments, isoindolin pigments, quinophthalone pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, diketopyrrolopyrrole pigments, dye lake pigments, triarylmethane pigments, Examples thereof include squarylium pigments. Among these, the colorants used in the coloring composition for color filters of the present invention include phthalocyanine pigments, diketopyrrolopyrrole pigments, quinophthalone pigments, and isoindolin pigments from the viewpoint of color characteristics as color filters. , Anthraquinone-based pigments, azo-based pigments, and dioxazine-based pigments are preferably used.
(Parthalocyanine pigment)
Examples of the phthalocyanine pigment include copper phthalocyanine, metal-free phthalocyanine, zinc phthalocyanine, aluminum phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine, iron phthalocyanine, and halogenated phthalocyanine obtained by halogenating these phthalocyanines. For example, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17: 1, 75, 79, C.I. I. Pigment Green 7, 36, 58, Japanese Patent No. 4893859, Japanese Patent Application Laid-Open No. 2016-57635, Japanese Patent Application Laid-Open No. 2016-153481 and the like. Of these, zinc phthalocyanines and aluminum phthalocyanines are preferable from the viewpoint of lightness, and among them, C.I. I. Pigment Green 58, Japanese Patent No. 4893859, and JP-A-2016-153481 are preferred.

(Diketopyrrolopyrrole pigment)
Examples of the diketopyrrolopyrrole pigment include C.I. I. Pigment Red 254, 255, 264, 270, 272, C.I. I. Pigment Orange 71, 73, 81, Japanese Patent Application Laid-Open No. 2012-21970 and the like. Above all, from the viewpoint of brightness, C.I. I. Pigmen Red 254 is preferred.

(Kinophthalone pigment)
Examples of the quinophthalone pigment include C.I. I. Pigment Yellow 138, Japanese Patent Application Laid-Open No. 6-9891, Japanese Patent Application Laid-Open No. 4993026, Japanese Patent Application Laid-Open No. 2012-82337, International Publication No. 2013/081140, Japanese Patent Application Laid-Open No. 2013-133448 and the like. Above all, from the viewpoint of brightness and heat resistance, C.I. I. Pigment Yellow 138 and those described in Japanese Patent No. 4993026 are preferable.

(Isoindoline pigment)
Examples of the isoindoline pigment include C.I. I. Pigment Yellow 139, 185, C.I. I. Pigment Orange 66, 69, C.I. I. Pigment Red 260, C.I. I. Pigment Brown 38 and other pigments can be mentioned. Above all, from the viewpoint of coloring power, C.I. I. Pigment Yellow 139 and 185 are preferred.

(Anthraquinone pigment)
Anthraquinone pigments are a general term for pigments containing anthraquinone or anthrone, which are quinones derived from anthracene in the structure, and are anthraquinone azo, aminoanthraquinone, indanthrone, anthrapyrimidine, anthranthrone, flavanthrone, pyranthrone, and isobiolance. Ron and the like can be mentioned. For example, C.I. I. Pigment Yellow 24, 99, 108, 123, 193, 199, C.I. I. Pigment Orange 40, 51, C.I. I. Pigment Red 83, 89, 168, 177, 182, 216, 226, 251, 263, C.I. I. Pigment Blue 60, 64, C.I. I. Pigment Biot 5: 1, etc. Above all, from the viewpoint of contrast ratio, C.I. I. Pigment Red 177 is preferred.

(Azo pigment)
Azo pigments are a general term for pigments having an azo group (-N = N-), and include azo lake pigments, monoazo pigments, disazo pigments, benzimidazolone pigments, β-naphthol pigments, condensed azo pigments, and azo metal complex pigments. Can be mentioned. The following are typical examples.
Azolake pigment: C.I. I. Pigment Yellow 61, 62, 100, 104, 133, 168, 169, 183, 191, 191: 1, 206, 209, 212, C.I. I. Pigment Red 48, 49, 52: 1, 53: 1, 54, 57: 1, 52: 2, 58, 60: 1, 63, 64: 1, 68, 193, 200, 211, 237, 239, 245, 247, C.I. I. Pigment Orange 17, 17: 1, 19, 46
Monoazo pigment: C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 49, 60, 65, 73, 74, 75, 97, 98, 105, 111, 116, 130, 165, 167, 205, C. I. Pigment orange 1
Disazo pigment: C.I. I. Pigment Yellow 12, 13, 14, 15, 16, 17, 55, 63, 77, 81, 83, 87, 106, 113, 114, 124, 126, 127, 152, 155, 170, 172, 174, 176, 214, 219, C.I. I. Pigment Red 38, 41, C.I. I. Pigment Orange 15, 16
Benzimidazolone pigment: C.I. I. Pigment Yellow 120, 151, 154, 167, 175, 180, 181 and 194, C.I. I. Pigment Orange 36, 60.62, 64, 72, C.I. I. Pigment Red 171, 175, 176, 185, 208, C.I. I. Pigment Violet 32, C.I. I. Pigment Brown 25, 32
β-naphthol pigment: C.I. I. Pigment Orange 4, 22, 24, 38, 74, C.I. I. Pigment Red 2, 5, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 95, 112, 114, 119, 136, 146, 147, 150, 164, 170, 183, 184, 187, 188, 210, 213, 238, 245, 253, 256, 258, 266, 269, 269, Japanese Patent Application Laid-Open No. 2013-145321, C.I. I. Pigment Violet 13, 17, 50, C.I. I. Pigment Blue 25, 26
Condensation azo pigment: C.I. I. Pigment Yellow 93, 94, 95, 128.166, C.I. I. Pigment Red 144, 166, 214, 220, 221, 242, 248, 262, C.I. I. Pigment Orange 31, C.I. I. Pigment Brown 23, 41, 42, etc. Azo metal complex pigment: C.I. I. Pigment Yellow 150, JP-A-2014-12832, among others, from the viewpoint of hue, lightness, and contrast ratio, C.I. I. Pigment Red 242, C.I. I. Pigment Yellow 150 is preferred.
(Dioxazine pigment)
For example, C.I. I. Pigment Violet 23, 34, 35, 37, C.I. I. Pigment Blue 80 pigments.
(Other organic pigments)
Examples of other organic pigments include known and commonly used pigments. For example, organic pigments such as quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, azomethine pigments, thioindigo pigments, and metal complex pigments can be mentioned.
(Quinacridone pigment)
For example, C.I. I. Pigment Violet 19, 42, C.I. I. Pigment Red 122, 202, 206, 207, 209, C.I. I. Pigment Orange 48, 49 and other pigments can be mentioned.

(Perylene / perinone pigment)
C. I. Pigment Violet 29, C.I. I. Pigment Red 123, 149, 178, 179, 190, C.I. I. Pigment Black 31, 32, C.I. I. Pigment Orange 43 and other pigments can be mentioned.

(Isoindolenone pigment)
C. I. Pigment Yellow 109, 110, 173, 179, C.I. I. Pigment Orange 61 and other pigments can be mentioned.

(Metal complex pigment) Azomethin For example, C.I. I. Pigment Yellow 117, 129, 150, 153, C.I. I. Pigment Orange 65, 68, C.I. I. Pigment Red 257, 271 and other pigments.
(Thioindigo pigment)
For example, C.I. I. Pigment Red 88, 279, C.I. I. Pigment Violet 36, 38 and other pigments can be mentioned.

(dye)
In the coloring composition of the present invention, a dye may be used as a coloring agent. In addition to the pigment, a dye may be used in combination. As the dye, any of acidic dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, medium dyes, building dyes, sulfide dyes and the like can be used. Further, these derivatives or a lake pigment obtained by converting a dye into a lake may be used.

Further, an acidic dye having an acidic group such as sulfonic acid or carboxylic acid, or in the case of a direct dye form, an inorganic salt of the acidic dye, an acidic dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, Alternatively, a salt-forming compound with a nitrogen-containing compound such as a primary amine compound, or chloride-forming using a resin component having these functional groups to be used as a salt-forming compound, or sulfonamide formation and use as a sulfonic acid amide compound. In order to obtain excellent resistance, a coloring composition having excellent fastness can be obtained, which is preferable. Further, a salt-forming compound of an acid dye and a compound having an onium base is also preferable because it has excellent fastness, and more preferably, the compound having an onium base is a resin having a cationic group in the side chain.

In the case of the basic dye form, it can be used by chlorinating with an organic acid, perchloric acid or a metal salt thereof. Among them, the salt-forming compound of the basic dye is preferable because it has excellent resistance and compatibility with the pigment. Further, the basic dye and the counter component that works as a counter ion, organic sulfonic acid, organic sulfuric acid, and fluorine group-containing phosphorus are preferable. It is possible to use a salt-forming compound obtained by salting an anionic compound, a fluorine group-containing boron anionic compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugated base of an organic acid having a halogenated hydrocarbon group, or an acidic dye. It is more preferable.

Further, when the dye skeleton has a polymerizable unsaturated group, the dye can be a dye having excellent resistance, which is preferable.

The chemical structure of the dye includes, for example, azo dye, azomethin dye (Indian aniline dye, Indian phenol dye, etc.), dipyrromethene dye, quinone dye (benzoquinone dye, naphthoquinone dye, anthraquinone dye, anthra). Pyridone dyes, etc.), Carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridin dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes, etc. Dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline Examples thereof include dye structures derived from dyes selected from based dyes, nitro dyes, nitroso dyes, and their metal complex dyes.

Among these dye structures, from the viewpoint of color characteristics such as hue, color separability, and color unevenness, azo dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, and quinophthalones. The dye structure derived from the dye selected from the dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferable, and the dyes selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, and dipyrromethene dyes. The derived dye structure is more preferred. For specific dye compounds that can form a dye structure, see "New Edition Dye Handbook" (Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyeers and colorists), "Dye Handbook" (Okawara et al.) Hen; Kodansha, 1986).

<Pigment miniaturization>
When the colorant used in the coloring composition for a color filter of the present invention is a pigment, it is preferable to use it in a finely divided form from the viewpoint of contrast. The miniaturization method is not particularly limited, and for example, wet grinding, dry grinding, and dissolution precipitation method can be used, and as illustrated in the present invention, salt milling treatment by the kneader method, which is a kind of wet grinding, can be used. And so on, it can be miniaturized. The average primary particle size determined by the TEM (transmission electron microscope) of the pigment is preferably in the range of 5 to 90 nm. If it is smaller than 5 nm, it becomes difficult to disperse it in an organic solvent, and if it is larger than 90 nm, a sufficient contrast ratio may not be obtained. For this reason, the more preferable average primary particle size is in the range of 10 to 70 nm.

The salt milling treatment is a batch type or continuous type of a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent, such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, a sand mill, and a planetary mixer. This is a treatment in which a water-soluble inorganic salt and a water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a kneader. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of price. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, most preferably 300 to 1000 parts by weight, based on 100 parts by weight of the pigment.

The water-soluble organic solvent has a function of wetting the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

When the pigment is subjected to salt milling treatment, a resin may be added if necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins and the like can be used. The resin used is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Dye derivative>
The coloring composition for a color filter of the present invention can arbitrarily select and contain various conventionally known dye derivatives. Examples of the dye derivative include compounds in which an organic pigment, anthraquinone, acridone or triazine is introduced with a basic substituent, an acidic substituent, or a phthalimidemethyl group which may have a substituent. 63-305173, 57-15620, 59-40172, 63-17102, 5-1469, 2001-335717, 2003- 128669, 2003-167112, 2004-091497, 2004-307854, 2007-156395, 2008-094873, 2008-094986. The ones described in Japanese Patent Application Laid-Open No. 2008-095007, Japanese Patent Application Laid-Open No. 2008-195916, Japanese Patent Application Laid-Open No. 4585781, and the like can be used, but the present invention is not limited thereto. The dye derivative may be added at the time of pigmentation such as salt milling treatment, or may be added at the time of dispersion.

<Dispersant [A]>
The coloring composition for a color filter of the present invention contains the block copolymer [A1] described later as an essential component as a dispersant.

<Block Copolymer [A1]>
The block copolymer [A1], which is an essential component of the present invention, contains a repeating structural unit represented by the general formula (1), and the structural unit has a cationic moiety and an anionic moiety in the same side chain. It has a zwitterionic structure.
^{X +} in the general formula (1) has an A block having a structure represented by the following general formula (2) or the following general formula (3), and a repeating structural unit represented by the general formula (1). It is a dispersant containing a block copolymer (B) composed of a B block that does not.
Since the A block having the repeating structural unit represented by the general formula (1) has high polarity, it can not only make the pigment finer by strongly adhering (adsorbing) to the surface of the pigment or the dye derivative, but also developability and adhesion to the substrate. Can be made excellent. ^{Further, regarding X +} in the general formula (1), the general formula (3) is more preferable from the viewpoint of heat resistance.

一般式（１）


［一般式（１）において、Ｒ¹¹は水素原子又はメチル基を表し、Ｒ¹²及びＲ¹³は、それぞれ独立に、２価の連結基を表し、Ｘ⁺は、カチオン性の２価の連結基を表し、Ｙ^-は、アニオン性の１価の基を表す。］

［一般式（２）において、Ｒ²¹及びＲ²²は、それぞれ独立に、１価の有機基を表す。
＊¹はＲ¹²との結合手を表し、＊²はＲ¹³との結合手を表す。］

［一般式（３）において、Ｒ³¹及びＲ³²は、それぞれ独立に、１価の有機基を表す。
＊¹はＲ¹²との結合手を表し、＊²はＲ¹³との結合手を表す。］ [A block]

General formula (1)


[In the general formula (1), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² and R ¹³ each independently represent a divalent linking group, and X ⁺ represents a cationic divalent linking group. the stands, Y ^- represents an anionic monovalent group. ]

[In the general formula (2), R ²¹ and R ²² each independently represent a monovalent organic group.
* ¹ represents a bond with R ^{12 and * 2} represents a bond with R ¹³ . ]

[In the general formula (3), R ³¹ and R ³² each independently represent a monovalent organic group.
* ¹ represents a bond with R ^{12 and * 2} represents a bond with R ¹³ . ]

^{As the divalent linking group of R 12} and R ¹³ of the general formula (1), a divalent hydrocarbon group, a divalent hydrocarbon group and a linking group containing a carbon atom and an atom other than a hydrogen atom are combined. Examples thereof include a group consisting of a group, or a group in which a part of the hydrogen atom of these groups is replaced with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of such a divalent linking group include an alkanediyl group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, an arylene alkanediyl group having 7 to 20 carbon atoms, or an arylene alkanediyl group having 1 to 10 carbon atoms. At least one selected from the alkanediyl group and the arylene group having 6 to 20 carbon atoms, and -O-, -S-, -COO-, -CONRb- (Rb is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). ) And a group composed of a combination of at least one selected from _{−SO 2−.}

The alkanediyl group having 1 to 10 carbon atoms may be a linear group or a branched chain, and may be, for example, a methylene group, an ethylene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, or a propane-1,2. -Diyl group, propane-1,3-diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane -1,4-diyl group, pentane-1,5-diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, octane-1,8-diyl group, decan-1,10- Examples thereof include an alkanediyl group having 1 to 10 carbon atoms such as a diyl group.

Examples of the arylene group include an arylene group having 6 to 12 carbon atoms such as a phenylene group, a naphthylene group, a biphenylene group and an anthrylene group.

The arylene alkandyl group is a divalent group consisting of a combination of an arylene group and an alkandyl group. For example, a phenylene methylene group, a phenylenedi methylene group, a phenylene trimethylene group, a phenylene tetramethylene group and a phenylene pentamethylene group. , A phenylene C1-6 alkandyl group such as a phenylene hexamethylene group can be mentioned.

Further, at least one selected from an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms, and -O-, -S-, -COO-, -CONRb- (Rb is a hydrogen atom or carbon). An alkyl group having a number of 1 to 8 is shown.) _{And a group composed of a combination of at least one selected from −SO 2} − are an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms. A group consisting of a combination of at least one selected and at least one selected from -O-, -COO- and -SO _2- is preferable, and an alkanediyl group having 1 to 10 carbon atoms and an alkanediyl group having 6 to 20 carbon atoms is preferable. A group consisting of a combination of at least one selected from an arylene group and at least one selected from −O− and −SO _{2 − is more preferable.} Specific examples of the alkyl group having 1 to 8 carbon atoms according to Rb include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and the like. Examples thereof include a hexyl group, a heptyl group, and an octyl group.

Among them, the divalent linking group in R12 is an alkandiyl group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an alkandiyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms. A group consisting of a combination of at least one selected from the groups and at least one selected from -O-, -S-, -COO-, -CONRb- and -SO _{2- is preferable, and the group has 6 to 10 carbon atoms.} At least one selected from an arylene group or an alcandiyl group having 1 to 8 carbon atoms and an arylene group having 6 to 10 carbon atoms and at least one selected from -O-, -COO-, -CONRb- and -SO _2-. A group composed of a combination of one type is more preferable.
It should be noted that it is selected from at least one selected from an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms, and -O-, -S-, -COO-, -CONRb- and -SO _2-. In a group composed of a combination of at least one of these groups, it is preferable that an alkanediyl group having 1 to 10 carbon atoms is bonded to X + or Y−.
Examples of the divalent linking group for more preferred ^{_{R 12, -COOCH 2 CH 2 -}} , -CONHCH 2 CH 2 - is.
Further, ^{as the divalent linking group in R 13,} an alkanediyl group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an arylene alkanediyl group having 7 to 20 carbon atoms is preferable, and an arylene alkanediyl group having 7 to 20 carbon atoms is preferable. The alkanediyl group of ~ 5 is more preferable, and a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group and a pentane-1,5-diyl group are further preferable.

The cationic divalent linking group in X ⁺ is preferably a group represented by the general formula (2) or the general formula (3), and more preferably a group represented by the general formula (3). be. Further, R ²¹ , R ²² , R ³¹ and R ³² are preferably a monovalent aliphatic hydrocarbon group, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

The monovalent group of the anionic in, CO ₂ ^{- -} Y of the general formula (1), SO ₃ ^- or PO ₄ ^- and others as mentioned, CO ₂ from the viewpoint of availability and heat resistance of the material ^-, SO ₃ ^- is preferable.

The B block is not particularly limited as long as it has a polymer structure obtained by copolymerizing a copolymerizable monomer having no structural unit represented by the general formula (1), and can be appropriately selected depending on the intended use. .. The copolymerizable monomers are shown below.

For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), tertiary butyl (meth) acrylate, isoamyl (meth) acrylate. , Octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate , Linear or branched alkyl (meth) acrylates such as isomiristyl (meth) acrylates, stearyl (meth) acrylates, and isostearyl (meth) acrylates;
Cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, tertiary butyl cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate;
(Meta) acrylates having a heterocycle such as tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;
(Meta) acrylates having an aromatic ring of benzyl (meth) acrylate and phenoxyethyl (meth) acrylate;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl Ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, tripropylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol Monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, polyethylene glycol monostearyl ether (meth) acrylate, and octoxypolyethylene glycol. -(Poly) alkylene glycol monoalkyl ether (meth) acrylates such as polypropylene glycol (meth) acrylate;
Phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, parac Milphenoxyethylene glycol (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, and nonylphenoxypoly (ethylene glycol-propylene glycol) (meth). ) (Poly) alkylene glycol (meth) acrylates having an aromatic ring such as acrylate;
Alkyloxy such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane (Meta) acrylates having a silyl group;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate;
(Meta) Acryloxy-modified polydimethylsiloxane (silicone macromer);
N-substituted (meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloylmorpholin; In addition, nitriles such as (meth) acrylonitrile may be mentioned.

In addition, styrene and styrenes such as α-methylstyrene;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate can be mentioned.

Further, a carboxyl group-containing ethylenically unsaturated monomer may be used in combination, for example, (meth) acrylic acid, crotonic acid, α-chloracrylic acid, succinic acid, and succinic acid mono [2- (meth) acrylic acid. Unsaturated monocarboxylic acids such as leuroxyethyl], mono-phthalic acid [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate; maleic acid, maleic anhydride, fumaric acid, itaconic acid. , Unsaturated dicarboxylic acids such as itaconic acid anhydride, citraconic acid, citraconic acid anhydride, mesaconic acid and the like, or an anhydride thereof.

Further, an ethylenically unsaturated monomer containing an amino group may be used in combination, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-. (Meta) acrylates having a tertiary amino group such as dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (Meta) acrylamides having a tertiary amino group such as (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide; and dimethylaminostyrene, diethylaminostyrene and the like. Can be mentioned. Of these, ethylenically unsaturated monomers selected from the group consisting of benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and hydroxyethyl (meth) crylate are preferable.

<Manufacturing method of block copolymer [A1]>
The block copolymer [A1] used in the present invention may be a copolymer composed of the A block and the B block represented above, and may be an AB block, a BAB block, or an AB-. A is preferable, and AB block and BAB block can be more preferably used. Such block copolymers are prepared, for example, by the living polymerization method shown below. Here, the living polymerization is a polymerization method for easily synthesizing a block polymer or a resin having a uniform molecular weight because side reactions that occur in general radical polymerization are suppressed and the growth of the polymerization occurs uniformly. The molecular weight of the polymer and the ratio of the monomer to be block-copolymerized can be freely controlled by the charging ratio of the polymerization initiator added at the time of polymerization to the vinyl-based monomer. Can be used in the production of terminal functional polymers and the like.

The block copolymer [A1] of the present invention can be synthesized by a known radical living polymerization method. As a specific example, the methods listed below have been developed and extensively researched and developed. Nitroxide mediated conduction (NMP method) utilizing the dissociation and binding of amine oxide radicals (see References 1 and 2). Atom transfer radical polymerization (ATRP method) that polymerizes a halogen compound as an initiating compound using heavy metals such as copper, ruthenium, nickel, and iron, and a ligand that forms a complex with them (Reference 2, Reference 2, See Reference 3 and Reference 4). Reversible addition-fragation chain transfer (RAFT method) that polymerizes using an addition-polymerizable monomer and a radical initiator with a dithiocarboxylic acid ester or xanthate compound as the starting compound (references). 5) and Macromolecular Designvia Interchange of Xanthate (MADIX method) (see Reference 6). Examples thereof include methods using heavy metals such as organic tellurium, organic bismuth, organic antimony, halogenated antimony, organic germanium, and halogenated germanium (Degenerative transfer: DT method) (see References 7 and 8). Not limited to these.

(Reference 1) Chemical Reviews (2001) 101,3661
(Reference 2) Macromolecules, 1994, 27, 7228
(Reference 3) Japanese Patent Laid-Open No. 2000-500516 (Reference 4) Japanese Patent Publication No. 2000-514479 (Reference 5) Chemical Reviews (2001) 101,3689
(Reference 6) Japanese Patent Application Laid-Open No. 2000-515181 (Reference 7) Refer to International Publication No. 1999-05099 (Reference 8) Japanese Patent Application Laid-Open No. 2007-277533 (Reference 9) Journal of American Chemical Society (2002) ) 124,2874

Among these radical living polymerization methods, the atom transfer radical polymerization method (ATRP method) and the nitroxide method (NMP method) can be applied not only from the viewpoint of controlling the molecular weight and molecular weight distribution of the polymer but also to a wide range of monomers. In terms of points, it is preferable in that a polymerization temperature applicable to existing equipment can be adopted, and further, the nitroxide method (NMP method) is more preferable in that a transition metal or the like that can cause coloring or the like is not used.

[Atom transfer radical polymerization method (ATRP method)]
In the atom transfer radical polymerization method, a transition metal complex such as copper, ruthenium, iron, or nickel is used as a redox polymerization catalyst. Specific examples of the transition metal complex include low atomic value halogenated transition metals such as copper (I) chloride and copper (I) bromide.

An organic ligand is used for the transition metal complex. Organic ligands are used to allow solubility in polymerization solvents and reversible changes in redox polymerization catalysts. Examples of the coordination atom of the transition metal include a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom.

As the initiator used in the atomic radical polymerization method, known ones can be used, but mainly organic halides having highly reactive carbon halogen bonds, halide sulfonyl compounds and the like are used. Specific examples thereof include ethyl bromoisobutyrate, ethyl bromobutyrate, ethyl chloroisobutyrate, ethyl chlorobutyrate, p-toluenesulfonic acid chloride, 1-bromoethylbenzene, chloroethylbenzene and the like. These are used alone or in combination.

[Nitroxide method (NMP method)]
The living radical polymerization method mediated by nitroxide is carried out by using a stable nitroxy-free radical (= NO ·) as a radical capping agent. The stable nitroxy-free radical is not particularly limited, and is, for example, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1-pi. Peridinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1,1 , 3,3-Tetramethyl-2-isoindolinyl oxy radical, N, N-di-t-butylamine oxy radical and the like. Stable free radicals such as galvinoxyl free radicals may be used instead of the nitroxy free radicals.

The radical capping agent is used in combination with a radical polymerization initiator. The combined use ratio of both is not particularly limited, but 0.1 to 10 mol of the radical initiator is suitable for 1 mol of the radical capping agent.

The radical polymerization initiator is appropriately selected according to the weight average molecular weight (Mw) of the resin to be synthesized, and is a (meth) acryloyl group in the monomer used when synthesizing the copolymer [A1]. It is used at a ratio of 0.0001 to 1 mol, preferably 0.001 to 0.1 mol, per 1 mol.

As the radical polymerization initiator, a known one can be used, but there is no particular limitation as long as it is a compound capable of generating radicals under polymerization temperature conditions. For example, di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-di (t). − Butyl peroxy) Dialkyl peroxides such as hexin-3;
Peroxyesters such as t-butylperoxybenzoate, t-butylperoxyacetate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane;
Ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide;
2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-) Butyl peroxy) cyclohexane, n-butyl-4,4-bis (t-butyl peroxy) barates, and other peroxyketals;
Hydroperoxides such as cumenehydroperoxide, diisopropylbenzenehydroperoxide, 2,5-dimethylcyclohexane-2,5-dihydroperoxide;
Diacyl peroxides such as benzoyl peroxide, decanoyle peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide;
Examples thereof include organic peroxides such as peroxydicarbonates such as bis (t-butylcyclohexyl) peroxydicarbonates, or mixtures thereof.

Further, an azo compound can also be used as a radical polymerization initiator. For example, 2,2'-azobisbutyronitrile such as 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis (2-methylbutyronitrile), 2, 2,2'-azobisvaleronitriles such as 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2' -2,2'-azobis propionitriles such as azobis (2-hydroxymethylpropionitrile), 1,1'-azobis-1- such as 1,1'-azobis (cyclohexane-1-carbonitrile) Alcan nitriles can be used.

Further, as reported in Macromolecules 1995, 28, 2993, instead of using the radical capping agent and the radical polymerization initiator in combination, the alkoxyamine compound represented by the following compound (N-1 to 4) is started. It may be used as an agent.

In the step of producing a block copolymer composed of an A block having an amphoteric ion structure in the side chain and a B block having no amphoteric ion structure, or a B-AB block copolymer of the present invention. No solvent or optionally a solvent can be used. Examples of the solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene. Glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like are used, but the present invention is not particularly limited thereto. Two or more kinds of these polymerization solvents may be mixed and used.

[Method for producing polymer (A)]
The polymer (A) containing the repeating unit represented by the general formula (1) can be obtained by using a known synthetic method, and the production method is not particularly limited. As a preferable manufacturing method, the following method (i)
) (Ii).
<Manufacturing method (i)>
A method of polymerizing an ethylenically unsaturated monomer (b1), which is a precursor of a repeating unit represented by the general formula (1), and another ethylenically unsaturated monomer (b3) by a known polymerization reaction.
<Manufacturing method (ii)>

An ethylenically unsaturated monomer (b2) capable of reacting with the modified species (b4) and another ethylenically unsaturated monomer (b3) are added to the intermediate polymer (a) obtained by a known polymerization method. A method for reacting a modified species (b4).

≪Manufacturing method (i) ≫
Examples of the ethylenically unsaturated monomer (b1) which is a precursor of the repeating unit represented by the general formula (1) include a monomer represented by the following general formula (4).
(Ethylene unsaturated monomer (b1))

〔一般式（４）において、Ｒ⁴¹は、水素原子又はメチル基を表し、Ｒ⁴²及びＲ⁴³は、それぞれ独立に、２価の連結基を表し、Ｘ⁺は、下記一般式（５）又は一般式（６）で表される基を表し、Ｙ^-は、−ＣＯ₂ ^-又は−ＳＯ₃ ^-を表す。〕

[In the general formula (4), R ⁴¹ represents a hydrogen atom or a methyl group, R ⁴² and R ⁴³ each independently represent a divalent linking group, and X ⁺ represents the following general formula (5) or It represents a group represented by the general formula (6), Y ^- is, -CO ₂ ^- or -SO ₃ ^- represents a. ]

[In the general formula (5), R ⁵¹ and R ⁵² each independently represent a monovalent organic group. * ¹ represents the bond with R ^{42, and * 2} represents the bond with R ⁴³ .

[In the general formula (6), R ⁶¹ and R ⁶² each independently represent a monovalent organic group.
* ¹ represents the bond with R ^{42, and * 2} represents the bond with R ⁴³ . ]

中でも化合物（４−１）、（４−２）、（４−５）、（４−６）、（４−９）、（４−１０）、（４−１３）、（４−１４）が好ましく、より好ましくは化合物（４−１）、（４−５）、（４−９）、（４−１０）、（４−１３）、（４−１４）であり、さらに好ましくは（４−９）、（４−１０）、（４−１３）、（４−１４）であり、最も好ましくは（４−９）である。 Examples of the compound represented by the general formula (4) include the following compounds (4-1 to 4-16).

Among them, compounds (4-1), (4-2), (4-5), (4-6), (4-9), (4-10), (4-13) and (4-14) are It is preferable, more preferably compound (4-1), (4-5), (4-9), (4-10), (4-13), (4-14), and even more preferably (4-14). 9), (4-10), (4-13), (4-14), most preferably (4-9).

(Other ethylenically unsaturated monomers (b3))
Examples of the other ethylenically unsaturated monomer (b3) include an acrylic monomer and a monomer other than the acrylic monomer.
As the acrylic monomer, for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2- Alkyl (meth) acrylates such as ethylhexyl (meth) acrylate, stearyl (meth) acrylate, and lauryl (meth) acrylate;
Alicyclics such as cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate. Formula alkyl (meth) acrylates;
(Meta) acrylates having heterocyclic substituents such as tetrahydrofurfuryl (meth) acrylates and 3-methyloxetanyl (meth) acrylates;
(Meta) acrylates having aromatic substituents such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethylene oxide modified (meth) acrylate, and paracumylphenoxyethylene oxide modified (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate;
(Meta) acrylamide (Note that when referred to as "(meth) acrylamide", it means acrylamide and / or methacrylamide. The same shall apply hereinafter), N, N-dimethyl (meth) acrylamide, N, N. -Examples include (meth) acrylamides such as diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloylmorpholin.

Further, as a monomer other than the acrylic monomer, for example,
Styrene and styrenes such as α-methylstyrene;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether;
Examples thereof include vinyl acetate and fatty acid vinyls such as vinyl propionate. The monomer other than the acrylic monomer can also be used in combination with the acrylic monomer.

Further, the carboxyl group-containing ethylenically unsaturated monomer can be used alone or in combination with the monomer.

Examples of the carboxyl group-containing ethylenically unsaturated monomer include, for example.
One or more can be selected from acrylic acid, methacrylic acid, ε-coupler lactone-added acrylic acid, ε-coupler lactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like. ..

≪Manufacturing method (ii) ≫
Examples of the ethylenically unsaturated monomer (b2) capable of reacting with the modified species (b4) described later include a monomer represented by the following general formula (7).

〔式（７）において、
Ｒ⁷¹は、水素原子又はメチル基を示し、Ｒ⁷²は２価の有機基を示す。
Zは、−Ｎ（Ｒ⁷³）（Ｒ⁷⁴）、又は−Ｐ（Ｒ⁷⁵）（Ｒ⁷⁶）、又は下記一般式（８）で表される基を表し、 Ｒ⁷³〜Ｒ⁷⁶は、それぞれ独立に、１価の有機基を示す。〕 General formula (7)

[In equation (7)
R ⁷¹ represents a hydrogen atom or a methyl group, and R ⁷² represents a divalent organic group.
Z represents a group represented by -N (R ⁷³ ) (R ⁷⁴ ), -P (R ⁷⁵ ) (R ⁷⁶ ), or the following general formula (8), and R ^{73 to} R ⁷⁶ are independent of each other. Shows a monovalent organic group. ]

［一般式（８）において、Ｒ⁸¹及びＲ⁸²は、それぞれ独立に、１価の有機基を表す。］ General formula (8)

[In the general formula (8), R ⁸¹ and R ⁸² each independently represent a monovalent organic group. ]

^{The divalent organic group in R 72} of the general formula (7) is synonymous with the divalent linking group in ^{R 12} of the general formula (1).
^{The monovalent organic group in R 73 to} R ⁷⁶ of the general formula (7) is synonymous with the monovalent organic group in the general formulas (2) and (3).
^{The monovalent organic group in R 81} and R ⁸² of the general formula (8) is synonymous with the monovalent organic group in ^{R 31} and R ³² of the general formula (3).

As a specific example of the ethylenically unsaturated monomer (b2) represented by the general formula (7),
N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, 2,2 (Meta) acrylates having a secondary or tertiary amino group such as 6,6-tetramethylpiperidylmethacrylate, 1,2,2,6,6-pentamethylpiperidylmethacrylate;
Tertiary such as N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide. (Meta) acrylamides with amino groups;
Etc., preferably N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (methacrylate), N, N-dimethylaminopropyl (meth) acrylamide, 1, 2, 2, 6, and the like. 6-Pentamethylpiperidylmethacrylate, particularly preferably 1,2,2,6,6-pentamethylpiperidylmethacrylate.

(Other ethylenically unsaturated monomers (b3))
The other ethylenically unsaturated monomer (b3) is synonymous with the ethylenically unsaturated monomer (b3) in the production method (i).

(Denatured species (b4))
The modified species (b4) can react with Z in the general formula (7), which is a constituent unit of the polymerized intermediate polymer (a), and is particularly capable of reacting with the structure of the general formula (1) after the reaction. There is no limitation, and examples thereof include a compound represented by the following general formula (9) and a compound represented by the following general formula (10).

General formula (9)
X- (CH ₂ ) n-Q
[In the general formula (9), X represents a halogen atom, n represents an integer of 1 to 4, Q is CO ₂ ^-, SO ₃ ^- or PO ₄ ^- represents a. ]

[式（１０）中、Ｒ¹⁰¹は炭素原子又はＳ＝Ｏを表し、ｎは２〜６の整数を表す。] General formula (10)

[In equation (10), R ¹⁰¹ represents a carbon atom or S = O, and n represents an integer of 2 to 6. ]

Examples of the compound represented by the general formula (9) include chloroacetic acid, fluorinated acetic acid, bromoacetic acid, iodoacetic acid, chloropropionic acid, fluorinated propionic acid, bromopropionic acid, iodopropionic acid, chlorobutanoic acid and fluorinated butanoic acid. , Bromobutanoic acid, Iodobutanoic acid chloromethanesulfonic acid, Methylfluorosulfonic acid, Bromomethanesulfonic acid, Iodomethanesulfonic acid, Chloropropanesulfonic acid, Propanefluorosulfonic acid, Bromopropanesulfonic acid, Iodopropanesulfonic acid, Chlorobutane sulfone Acid, butane fluorinated sulfonic acid, bromobutane sulfonic acid, iodobutane sulfonic acid chloromethanephosphonic acid, methyl fluorinated phosphonic acid, bromomethanephosphonic acid, iodomethanephosphonic acid, chloropropanephosphonic acid, propanephosphonic acid fluoride, bromopropanephosphonic acid Acids, iodopropanephosphonic acid, chlorobutanephosphonic acid, fluorinated butanephosphonic acid, bromobutanephosphonic acid, iodobutanephosphonic acid and the like can be mentioned.
Bromoacetic acid, chloropropionic acid, and chloroacetic acid are preferable, and chloroacetic acid is particularly preferable.

Examples of the compound represented by the general formula (10) include propane sultone, butane sultone, α-acetolactone, β-propiolactone, γ-butyrolactone and δ-valerolactone ε-caprolactone, among which propane sultone, Butan sultone is preferred.

The molecular weight of the block copolymer [A1] used in the present invention is not particularly limited, but the converted weight average molecular weight measured by gel permeation chromatography (GPC) is 1,000 to 500,000. It is preferably present, and more preferably 3,000 to 15,000.

The amount of the solvent used is preferably 10 to 300 parts by weight, more preferably 50 to 100 parts by weight, based on 100 parts by weight of the monomer composed of A block and B block. After the reaction is completed, the used solvent can be removed by an operation such as distillation, or can be used as it is as a part of the product of the composition.

The content of A block (a block containing a partial structure having a zwitterionic structure represented by the general formula (1)) with respect to the solid content of the block copolymer [A1] is preferably 1% by weight to 99% by weight. Further, it is preferably contained in an amount of 20% by weight to 80% by weight, and particularly preferably 20% by weight to 50% by weight. When the A block contains 20% by weight to 50% by weight, the remaining 50% by weight to 80% by weight constitutes the B block. Therefore, the pigment can be stably present in the dispersion medium by allowing the B block to be compatible with the solvent which is the dispersion medium. Further, by introducing the zwitterionic structure into the A block, the polarity of the dispersant is increased, and the adsorption ability to the pigment is increased, so that the dispersion stability is further improved.

The content of the repeating unit represented by the general formula (1) with respect to the A block (100% by weight) contained in the block copolymer [A1] is preferably 1% by weight to 100% by weight, more preferably 20% by weight. It is preferably contained in an amount of% to 100% by weight, and particularly preferably 50% by weight to 100% by weight. Since the repeating unit represented by the general formula (1) acts as a pigment adsorbing group, the above-mentioned content rate improves the dispersibility. Further, the monomer constituting the remaining 0 to 50% by weight in the A block is preferably an ethylenically unsaturated monomer having an amino group, but is an ethylenically unsaturated monomer having no amino group. It is also possible to copolymerize even with a weight.

Further, the molecular weight of the block copolymer [A1] of the present invention is a polystyrene-equivalent weight average, usually preferably in the range of 3,000 or more and 20,000 or less, and more preferably in the range of 5,000 or more and 15,000 or less. The range of 7,000 or more and 12,000 or less is particularly preferable. If the molecular weight of the block copolymer is less than 3,000, the dispersion stability tends to decrease, and if it exceeds 20,000, the developability tends to decrease.

The content of the block copolymer [A1] to be used is preferably 5 to 50 parts by weight, more preferably 10 to 45 parts by weight, and particularly preferably 15 to 30 parts by weight with respect to 100 parts by weight of the pigment. When the compounding amount of the block copolymer [A1] is less than 5 parts by weight, it may be difficult to obtain the effect of pigment dispersibility. On the other hand, if it exceeds 50 parts by weight, the alkali developability may decrease when a pigment dispersion resist containing the pigment dispersion composition is used and a pixel pattern of a color filter is produced by a photolithography method.

<Dispersants other than block copolymer [A1]>
A dispersant other than the block copolymer [A1] can be used in combination with the coloring composition for a color filter in the present invention. It has a colorant-affinitive moiety having a property of adsorbing to the additive colorant and a moiety compatible with the colorant carrier, and has a function of adsorbing to the additive colorant and stabilizing dispersion in the colorant carrier. It is a thing. Specifically, the dispersant includes a dispersant having an aromatic carboxyl group, a polycarboxylic acid ester such as polyurethane and polyacrylate, an unsaturated polyamide, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, and a polycarboxylic acid ammonium salt. , Polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamidophosphates, hydroxyl group-containing polycarboxylic acid esters and their modifications, poly (lower alkyleneimine) by reaction with polyesters with free carboxyl groups. Oily dispersants such as formed amides and salts thereof, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol , Water-soluble resin such as polyvinylpyrrolidone, water-soluble polymer compound, polyester type, modified polyacrylate type, ethylene oxide / propylene oxide addition compound, phosphate ester type, etc. are used, and these are used alone or in admixture of two or more. However, the present invention is not limited to these.

Commercially available dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168 manufactured by Big Chemie Japan. , 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, or Anti-TeRRa-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc., SOLPERSE-3000, 9000, 11200, 13000, 13240, 13650, 13940, 16000, 17000 , 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 3300, 33500, 32600, 34750, 35100, 35200, 36600, 37500, 38500, 39000, 41000, 41090, 53095, 56000. , 55000, 7100, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, manufactured by BASF. 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, Examples thereof include Ajinomoto Fine-Techno's Azispar PA111, PB711, PB821, PB822, PB824 and the like, such as 1503.

<Binder resin>
The binder resin is one that disperses a colorant or dyes and permeates a salt-forming compound, and examples thereof include a thermoplastic resin and a thermosetting resin.

Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. , Polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin and the like.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin.

The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Further, since the coloring composition for a color filter of the present invention is in the form of an alkali-developable colored resist material, it is preferable to use an alkali-soluble vinyl-based resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer.

Examples of the alkali-soluble resin obtained by copolymerizing the acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group and a sulfone group. Specifically, the alkali-soluble resin includes an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples thereof include isobutylene / (anhydrous) maleic acid copolymer. Among them, an acrylic resin having an acidic group and at least one resin selected from a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

In order to improve the photosensitivity of the alkali-soluble resin copolymerized with the acidic group-containing ethylenically unsaturated monomer, an energy ray-curable resin having an ethylenically unsaturated active double bond can also be used. Further, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain because it has an effect of improving the solvent resistance of the resist material.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenically double bond introduced by the methods (a) to (c) shown below.

[Method (a)]
As the method (a), for example, the side chain epoxy group of the copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group with one or more other types of monomers can be used. , A carboxyl group of an unsaturated monobasic acid having an unsaturated ethylenic double bond is added and reacted, and a polybasic acid anhydride is reacted with the generated hydroxyl group to form an unsaturated ethylenic double bond and a carboxyl group. There is a way to introduce it.

Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. , And 3,4-epoxycyclohexyl (meth) acrylates, which may be used alone or in combination of two or more. From the viewpoint of reactivity with unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferable.

Examples of the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano-substituted products. Examples thereof include monocarboxylic acids, which may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. It doesn't matter. If necessary, such as by increasing the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic acid anhydride or a tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride may be used to obtain the remaining anhydride. It is also possible to hydrolyze the group. Further, when tetrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the unsaturated ethylenic double bond can be further increased.

[Method (b)]
As a method similar to the method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group with one or more other monomers. There is a method of adding an unsaturated ethylenic monomer having an epoxy group to a part of the carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.
In this method, more hydroxyl groups derived from unsaturated ethylenic monomers having an epoxy group are generated as compared with the method (a). When the resin having a cationic group in the side chain used to obtain the salt-forming compound of the present invention contains an oxetanyl group or a t-butyl group as a thermally crosslinkable functional group, the method as a binder resin ( It is preferable to use the resin obtained in b) because it exhibits higher heat resistance.

[Method (c)]
As the method (c), an unsaturated ethylenic monomer having a hydroxyl group is used, and by copolymerizing with another unsaturated monobasic acid monomer having a carboxyl group or another monomer. There is a method of reacting the side chain hydroxyl group of the obtained copolymer with the isocyanate group of the unsaturated ethylenic monomer having an isocyanate group.

Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, a polyether mono (meth) acrylate obtained by superpolymerizing the above hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, and (poly) ε-caprolactone. , And / or (poly) ester mono (meth) acrylates to which (poly) 12-hydroxystearic acid and the like are added can also be used. 2-Hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable from the viewpoint of suppressing foreign matter in the coating film.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, but the present invention is limited thereto. However, two or more types can be used together.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to preferably disperse the colorant. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

When the binder resin is used as a photosensitive composition, it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g from the viewpoint of dispersibility, permeability, developability, and heat resistance of the pigment and the salt-forming compound. If the acid value is less than 20 mgKOH / g, the solubility in a developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, fine patterns may not remain.

Since the binder resin has good film forming properties and various resistances, it is preferable to use the binder resin in an amount of 30% by weight or more based on the total weight of the colorant (100% by weight), and the colorant concentration is high and good. Since it can exhibit color characteristics, it is preferably used in an amount of 500% by weight or less.

(Thermosetting compound)
In the present invention, a thermosetting compound may be further contained in combination with a thermoplastic resin which is a binder resin. Examples of the thermosetting compound include epoxy compounds and / or resins, oxetane compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, and the like. Examples thereof include, but are not limited to, melamine compounds and / or resins, urea compounds and / or resins, phenol compounds and / or resins.

<Organic solvent>
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and permeated into the coloring agent carrier, and the colored film is applied onto a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm to form a colored film. It contains an organic solvent to facilitate its formation. The organic solvent is selected in consideration of the solubility of each component of the coloring composition and the safety in addition to the good coatability of the coloring composition.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone and 2-methyl-. 1,3-Propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, N, N-dimethyl Acetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propylacetate, o-xylene, o-diethylbenzene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, Isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether. Acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, Diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, Dipropylene glycol mono Methyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene Glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate , Propyl acetate, dibasic acid ester and the like. These solvents can be used alone or in admixture of two or more at any ratio, if necessary.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl have good dispersibility, permeability, and coatability of the coloring composition. It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol, diacetone alcohol and 3-methoxybutanol, and ketones such as cyclohexanone.

Further, since the organic solvent can adjust the coloring composition to an appropriate viscosity and form a coloring film having a desired uniform film thickness, it should be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the coloring agent. Is preferable.

<Photopolymerizable monomer>
The photopolymerizable monomer that may be added to the coloring composition of the present invention includes a monomer or an oligomer that is cured by ultraviolet rays, heat, or the like to produce a transparent resin.

Examples of the monomer and oligomer that cure with ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, 1,6-Hexanediol Diglycidyl Ether Di (Meta) Acrylate, Bisphenol A Diglycidyl Ether Di (Meta) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (Meta) acrylic acid ester, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol tri Examples thereof include, but are not limited to, vinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile. These photopolymerizable compounds may be used alone or in admixture of two or more at any ratio as required.

The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight based on the total weight of the colorant (100 parts by weight), and 10 to 300 parts by weight from the viewpoint of photocurability and developability. Is more preferable.

<Photopolymerization initiator>
The coloring composition for a color filter of the present invention is a solvent-developed or alkali-developing colored resist material to which a photopolymerization initiator or the like is added when the composition is cured by irradiation with ultraviolet rays to form a filter segment by a photolithography method. Can be prepared in the form of. When the photopolymerization initiator is used, the blending amount is preferably 5 to 200% by weight based on the total amount of the colorant (100% by weight), and is 10 to 150% by weight from the viewpoint of photocurability and developability. % Is more preferable.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1-. Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 -Acetophenone compounds such as [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one; benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4' -Methyldiphenyl sulfide, or benzophenone compounds such as 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 -Thioxanthone compounds such as diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-( p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6- Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4- Triazine compounds such as trichloromethyl- (4'-methoxystyryl) -6-triazine; 1- (N-4-benzoylphenyl-carbazole-3-yl) -butane-1,2-dione -2-Oxime-O-acetate, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-) Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime), or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ) Ethiliden) Oxime ester compounds such as hydroxylamine; phosphin compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 9,10-fe A quinone-based compound such as nanslenquinone, camphorquinone, and ethylanthraquinone; a borate-based compound; a carbazole-based compound; an imidazole-based compound; or a titanosen-based compound is used.

These photopolymerization initiators can be used alone or in admixture of two or more at any ratio, if necessary. These photopolymerization initiators are preferably 5 to 200% by weight based on the total amount of the colorant in the coloring composition for a color filter (100% by weight), and are 10 from the viewpoint of photocurability and developability. More preferably, it is ~ 150% by weight.

<Sensitizer>
Further, the coloring composition for a color filter of the present invention may contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, aclysine derivatives, azine derivatives, thiadine derivatives, oxadin derivatives, indolin derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, α-Acyloxy ester , Acylphosphine oxide, methylphenylglycilate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4,4'- Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone and 4,4'-diethylaminobenzophenone.

More specifically, Okawara Nobu et al., "Dye Handbook" (1986, Kodansha), Okawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And " Examples thereof include, but are not limited to, the sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.

Two or more kinds of sensitizers may be used at an arbitrary ratio, if necessary. When the sensitizer is used, the blending amount is preferably 3 to 60% by weight based on the total weight of the photopolymerization initiator contained in the coloring composition (100% by weight), and is photocurable. From the viewpoint of developability, it is more preferably 5 to 50% by weight.

<Amine compounds>
Further, the coloring composition of the present invention may contain an amine compound having a function of reducing dissolved oxygen.

Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
It is preferable to add a leveling agent to the coloring composition of the present invention in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning Co., Ltd., BYK-333 manufactured by Big Chemie Co., Ltd., and the like. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Big Chemie. Didimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can also be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to a coloring composition, the same. It is useful to have a feature of low surface tension lowering ability and good wettability to the glass plate despite low surface tension lowering ability, and the amount of addition does not cause defects in the coating film due to foaming. Those capable of sufficiently suppressing chargeability can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

The binding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are repeatedly bonded alternately. Didimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. 2207, but is not limited to these.

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used.

Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalline sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include ester.

Examples of the chaotic surfactant added as an auxiliary to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphoric acid ester, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazolin, and fluorocarbon and silicone-based surfactants.

<Epoxy compound>
An epoxy compound may be added to the coloring composition of the present invention, and a known compound having an epoxy group can be used without particular limitation.

Examples of the epoxy compound include phenol novolac type epoxy resin, cresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadienephenol type epoxy resin, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, and biphenol type epoxy. Examples thereof include a resin, a bisphenol-A novolak type epoxy resin, a naphthalene skeleton-containing epoxy resin, an alicyclic epoxy resin, and a heterocyclic epoxy resin.

Specific examples of the phenol novolac type epoxy resin include Epicron N-740, Epicron N-770, Epicron N-775 manufactured by DIC Corporation, and D.D. E. Examples thereof include N438, RE-306 manufactured by Nippon Kayaku Co., Ltd., jER152 and jER154 manufactured by Mitsubishi Chemical Corporation.

Specific examples of the cresol novolak type epoxy resin include Epicron N-660, Epicron N-665, Epicron N-670, Epicron N-673, Epicron N-680, Epicron N-695, and Epicron N-665, manufactured by DIC Corporation. Examples thereof include EXP, Epicron N-672-EXP, EOCN-102S manufactured by Nippon Kayaku Co., Ltd., EOCN-103S, EOCN-104S, UVR-6650 manufactured by Union Carbide Co., Ltd., ESCN-195 manufactured by Sumitomo Chemical Industries, Ltd. and the like.

Specific examples of the trishydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H manufactured by Nippon Kayaku Corporation, TACTIX-742 manufactured by Dow Chemical Corporation, and jER E1032H60 manufactured by Mitsubishi Chemical Corporation. Can be mentioned.

Specific examples of the dicyclopentadiene phenol type epoxy resin include Epicron EXA-7200 manufactured by DIC Corporation, TACTIX-556 manufactured by Dow Chemical Corporation, and the like.

Specific examples of the bisphenol type epoxy resin include jER828 and jER1001 manufactured by Mitsubishi Chemical Co., Ltd., UVR-6410 manufactured by Union Carbide Co., Ltd., and D.C. E. R-331, bisphenol-A type epoxy resin such as YD-8125 manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd., UVR-6490 manufactured by Union Carbide Co., Ltd., bisphenol-F type such as YDF-8170 manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd. Epoxy resin and the like can be mentioned.

Specific examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000 and NC-3000H manufactured by Nippon Kayaku Corporation, and bixylenol type epoxies such as jER YX-4000 and jER YL-6121 manufactured by Mitsubishi Chemical Corporation. Examples include resin.

Specific examples of the bisphenol A novolak type epoxy resin include Epicron N-880 manufactured by DIC Corporation and jER E157S75 manufactured by Mitsubishi Chemical Corporation.

Specific examples of the naphthalene skeleton-containing epoxy resin include NC-7000 and NC-7300 manufactured by Nippon Kayaku Co., Ltd., EXA-4750 manufactured by DIC Corporation, and the like.

Specific examples of the alicyclic epoxy resin include Seikiside 2021P, 2081, 2000, Epolide PB3600, PB4700, GT401, EHPE-3150, Cyclomer M100 and the like manufactured by Daicel Corporation.

Specific examples of the heterocyclic epoxy resin include TEPIC-L, TEPIC-H, and TEPIC-S manufactured by Nissan Chemical Industries, Ltd.

These epoxy compounds may be used alone or in admixture of two or more at any ratio as required.

The content of the epoxy compound used in the coloring composition of the present invention is (usually 0.5 to 50% by weight, preferably 1 to 40% by weight, based on 100% by weight of the solid content of the coloring composition). When the content is in the above range, the heat resistance is high and an excellent coating film can be obtained, which is preferable.

<Oxetane compound>
An oxetane compound may be added to the coloring composition of the present invention, and a known compound having an oxetane group can be used without particular limitation. Examples of the oxetane compound include those in which the oxetane group is monofunctional, those in which the oxetane group is bifunctional, and those in which the oxetane group is bifunctional or higher.

Examples of monofunctional oxetane groups include (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methylmethacrylate, 3-ethyl-3-hydroxymethyloxetane, and 3-ethyl-. 3- (2-Ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-methacryloxymethyl) oxetane, 3-ethyl-3-{[3-( Triethoxysilyl) propoxy] methyl} oxetane and the like.
Specific examples include OXE-10 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101 and 212 manufactured by Toagosei Co., Ltd., and the like.

Examples of bifunctional oxetane groups include 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl) and 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl]. Benzene, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether, di [1-ethyl (3-oxetanyl)] methyl Ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3,7-bis (3-bis) Oxetanyl) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene Glycosbis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-Ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, polyethylene glycol bis ( 3-Ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) Ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A-bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3) -Oxetanylmethyl) ether and the like can be mentioned.
Specific examples include OXBP and OXTP manufactured by Ube Industries, Ltd., OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

If the oxetane group is bifunctional or higher,
Pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta Kiss (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl-3-oxettanylmethyl) ether, caprolactone-modified di Pentaerythritol Pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, resin containing an oxetane group (eg, oxetane-modified phenol according to Patent No. 3783462). Examples thereof include polymers obtained by radically polymerizing a (meth) acrylic monomer such as novolak resin) or the above-mentioned OXE-30. Such a polymer can be obtained by using a known polymerization method.

The content of the oxetane compound used in the coloring composition of the present invention is usually 0.5 to 50% by weight, preferably 1 to 40% by weight, based on 100% by weight of the solid content of the coloring composition. When the content of the oxetane compound is in the above range, the heat resistance is high and an excellent coating film can be obtained, which is preferable.

<Curing agent, curing accelerator>
Further, the coloring composition of the present invention may contain a curing agent, a curing accelerator, or the like, if necessary, in order to assist the curing of the thermosetting resin. As the curing agent, a phenol-based resin, an amine-based compound, an acid anhydride, an active ester, a carboxylic acid-based compound, a sulfonic acid-based compound, and the like are effective, but the curing agent is not particularly limited thereto, and is a thermosetting resin. Any curing agent may be used as long as it can react with. Further, among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably mentioned. Examples of the curing accelerator include amine compounds (eg, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, eg). Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6). − Methacyoyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6- Methacryloyloxyethyl-S-triazine, isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the thermosetting resin.
<UV absorber>
Further, the coloring composition of the present invention may contain an ultraviolet absorber, if necessary. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples thereof include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds. ..

The content of the ultraviolet absorber is preferably 5 to 70% by weight based on 100% by weight of the total of the photopolymerization initiator and the ultraviolet absorber. If the content of the UV absorber is less than the above, the effect of the UV absorber is small and the resolution cannot be ensured, and if it is more than the above, the sensitivity is low and the pixel peeling and the hole diameter are larger than the design value. There may be a problem such as becoming.

At this time, when the photosensitive coloring composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by weight based on 100% by weight of the solid content of the photosensitive coloring composition. If the total content of the photopolymerization initiator and the ultraviolet absorber is less than the above, the adhesion is weakened and pixel peeling occurs, and if it is more than the above, the sensitivity may be too high and the resolution may be deteriorated.

At this time, when the photosensitive coloring composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

Examples of the benzotriazole-based organic compound include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, and octyl-3 [3-tert-butyl. -4-Hydroxy-5- (5-chloro-2H-benzotriazole-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H) -Phenyltriazole-2-yl) phenyl] propionate mixture, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-t butyl- 5-Methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t- Octylphenyl) benzotriazole, 5% by weight 2-methoxy-1-methylethyl acetate and 95% by weight benzenepropanoic acid, 3- (2H-benzotriazole-2-yl)-(1,1-dimethylethyl)- 4-Hydroxy, C7-9 side chain and linear alkyl ester compounds, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- ( Examples thereof include 2H-benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol.

More specifically, BASF's "TINUVIN P", "TINUVIN PS", "TINUVIN 109", "TINUVIN 234", "TINUVIN 326", "TINUVIN 328", "TINUVIN 329", "TINUVIN 360", " "TINUVIN 384-2", "TINUVIN 900", "TINUVIN 928", "TINUVIN 99-2", "TINUVIN 1130", "ADEKA STAB LA-29" manufactured by ADEKA, "RUNA-93" manufactured by Otsuka Chemical Co., Ltd., etc. Will be.

Examples of the triazine-based organic compound include 2- [4,6-di (2,4-kisilyl) -1,3,5-triazine-2-yl] -5-octyloxyphenol 2- [4,6-bis. (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl)- Reaction product of 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl-glycidate ester, 2,4-bis "2-hydroxy-4-butoxyphenyl" -6- (2,4-dibutoxyphenyl) -1,3-5-triazine and the like can be mentioned.

More specifically, "KEMISORB 102" manufactured by Chemipro Kasei Co., Ltd., "TINUVIN 400", "TINUVIN 405", "TINUVIN 460", "TINUVIN 477-DW", "TINUVIN 479", "TINUVIN 1577", manufactured by BASF Corporation, Examples thereof include "ADEKA STAB LA-46" and "ADEKA STAB LA-F70" manufactured by ADEKA, and "CYASORB UV-1164" manufactured by Sun Chemical.

Examples of the benzophenone-based organic compound include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid-3 water temperature, and 2-hydroxy-4-n-. Examples thereof include octoxybenzophenone and 2,2-di-hydroxy-4-methoxybenzophenone.

More specifically, "KEMISORB 10", "KEMISORB 11", "KEMISORB 11S", "KEMISORB 12", "KEMISORB 111" manufactured by Chemipro Kasei Co., Ltd., "SEESORB 101", "SEESORB 107", ADEKA manufactured by Cypro Kasei Co., Ltd. Examples thereof include "ADEKA STAB 1413" manufactured by the company.

<Thiol chain transfer agent>
The coloring composition of the present invention may contain a thiol-based chain transfer agent, if necessary. By using a thiol-based chain transfer agent together with a photopolymerization initiator, a chile radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation. High sensitivity.

Further, a polyfunctional aliphatic thiol bonded to an aliphatic group such as methylene or ethylene group having two or more SH groups is preferable. More preferably, it is a polyfunctional aliphatic thiol having 4 or more SH groups. By increasing the number of functional groups, the polymerization initiation function is improved, and the pattern can be cured from the surface to the vicinity of the substrate.

Examples of the polyfunctional thiol include hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropio. Nate, Trimethylol Propanetristhioglycolate, Trimethylol Prothanitristhiopropionate, Trimethylol Propanthris (3-mercaptobutyrate), Pentaerythritol Tetrakissthioglycolate, Pentaerythritol Tetrakissthiopropionate, Trimercaptopropionic Acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s- Examples thereof include triazine, and preferred examples include ethylene glycol bisthiopropionate, trimethylolpropanetristhiopropionate, and pentaerythritol tetrakisthiopropionate.

These thiol-based chain transfer agents can be used alone or in admixture of two or more.

The content of the thiol-based chain transfer agent is preferably 1 to 10% by weight, more preferably 2.0 to 8.0% by weight, based on the total solid content (100% by weight) of the photosensitive composition. be. In this range, the effect of the chain transfer agent is increased, and the sensitivity, taper shape, wrinkles, film shrinkage rate, etc. are improved.

<Antioxidant>
The coloring composition of the present invention can contain an antioxidant. The antioxidant can increase the transmittance of the coating film in order to prevent the composition contained in the coloring composition from being oxidized and yellowed by the thermal step at the time of thermosetting or ITO annealing. In particular, when the colorant concentration of the photosensitive coloring composition is high, the amount of the cross-linking component of the coating film is small, so that the yellowing of the thermal process is strong in order to take measures such as using a highly sensitive cross-linking component and increasing the amount of the photopolymerization initiator. The phenomenon is seen.
Therefore, by containing an antioxidant, it is possible to prevent yellowing due to oxidation during the heating step and obtain a high transmittance of the coating film.

The "antioxidant" in the present invention may be a compound having an ultraviolet absorption function, a radical capture function, or a peroxide decomposition function, and specifically, the antioxidant is a hindered phenol-based or a hindered amine-based compound. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, sulcylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. Further, the antioxidant used in the present invention preferably does not contain a halogen atom.

Among these antioxidants, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, the preferred ones are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants or sulfur-based antioxidants. Agents are mentioned.

Examples of the hindered phenolic antioxidant include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), and the like. 1,3,5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di) -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-t-butyl-5-methylphenol), 2,2'-thio- Bis- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) )-Propionate, 1,1,3-Tris- (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -butane, 2,2'-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro) Phenol) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.
Specific examples include ADEKA's ADEKA STUB AO-20, AO-30, AO-40, AO50, AO60, AO80, AO320, Chemipro's KEMINOX101, 179, 76, 9425, BASF's IRGANOX1010, 1035, 1076, 1098, Examples thereof include 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, Sianox CY-1790 and CY-2777 manufactured by Sun Chemical.

Examples of the hindered amine antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate. N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4) -Piperidyl) Amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3) 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6) -Tetramethyl-4-piperidyl) imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazin-2,4) -Diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-Hydroxyethyl) -4-hydroxy-2,2,6,6-polycondensate with tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazine-2-yl] -4,7-diazadecan-1,10-diamine and the like. In addition, oligomer-type and polymer-type compounds having a hindered amine structure can also be used.
Specific examples include ADEKA's ADEKA STUB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA. -402F, LA-502XP, KAMISTAB29, 62, 77, 29, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin249 manufactured by BASF, TINUVIN111FDL, 123, 144, 292, 5100, Siasorb UV-3346, UV-3329 manufactured by Sun Chemical Co., Ltd. UV-3853 and the like can be mentioned.

Phenyl antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecyl. Phenylphosphite, diphenyltridecylphosphite, triphenylphosphite, tris (nonylphenyl) phosphite, 4,4'isopropyridendiphenol alkylphosphite, trisnonylphenylphosphite, trisdinonylphenylphosphite, tris (2) , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonyl) Phenyl) Pentaerythritol diphosphite, Phenylbisphenol A Pentaerythritol diphosphite, Tetratridecyl 4,4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphite, Hexatridecyl 1,1,3- Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butanetriphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis (4-t-butylphenyl) Phosphite, Sodium-2,2-Methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3-bis (diphenoxyphosphonyloxy) -benzene, ethylbis phosphite (2, 4-Ditert-butyl-6-methylphenyl) and the like. In addition, oligomer-type and polymer-type compounds having a phosphite structure can also be used.
Specific examples include ADEKA's ADEKA TAB PEP-36, PEP-8, HP-10, ADEKA TAB 2112, 1178, 1500, C, 3013, TPP, BASF's IRGAFOS 168, Clariant Chemicals' Hostanox P-EPQ, and the like. ..

Examples of sulfur-based antioxidants include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 2,4-bis [(octylthio) methyl]-. o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol, 2,2-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diylbis [3- (Dodecylthio) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like. In addition, oligomer-type and polymer-type compounds having a thioether structure can also be used.
Specific examples include ADEKA ADEKA STAB AO-412S and AO-503 manufactured by ADEKA, and KEMINOXPLS manufactured by Chemipro Kasei Co., Ltd.

As the benzotriazole-based antioxidant, an oligomer-type compound and a polymer-type compound having a benzotriazole structure can be used.
As specific examples, ADEKA's ADEKA STAB LA-29, LA-31RG, LA-32, LA-36, -412S, Chemipro Kasei's KEMISORB71, 73, 74, 79, 279, BASF's TINUVIN PS, 99- 2, 384-2, 900, 928, 1130 and the like can be mentioned.

Benzophenone-based antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4. -Octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy- Examples thereof include 4-methoxy-5 sulfobenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. In addition, oligomer-type and polymer-type compounds having a benzophenone structure can also be used.
Specific examples include ADEKA TAB 1413 manufactured by ADEKA, KEMISORB10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., UV-12 manufactured by Sun Chemical Co., Ltd., UV-329, and the like.

Examples of the triazine-based antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.
Specific examples include ADEKA's ADEKA STAB LA-46 and F70, Chemipro Kasei's KEMISORB102, BASF's TINUVIN400, 405, 460, 477, 479, and Sun Chemical's Siasorb UV-1164.

Examples of the salicylic acid ester-based antioxidant include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butyl phenyl salicylate. In addition, oligomer-type and polymer-type compounds having a sulcylic acid ester structure can also be used.

These antioxidants can be used alone or in admixture of two or more at any ratio as required.

Further, the content of the antioxidant is more preferably 0.5 to 5.0% by weight based on 100% by weight of the solid content of the coloring composition because the spectral characteristics and the sensitivity are good.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Further, an adhesion improving agent such as a silane coupling agent can be contained in order to enhance the adhesion with the transparent substrate.

Examples of the storage stabilizer include quaternary ammonium chloride such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphoric acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine. Examples thereof include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total amount of the colorant (100% by weight).

Examples of the adhesion improver include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β- (3,). 4-Epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino) Ethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of the colorant in the coloring composition (100% by weight).

<Manufacturing method of coloring composition>
In the coloring composition of the present invention, a colorant is mixed with a dispersant, a dispersant such as a binder resin, a single colorant and / or a solvent, preferably a dispersion aid (dye derivative or surfactant), and a kneader. It can be finely dispersed and manufactured by using various dispersion means such as a roll mill, a double roll mill, a ball mill, a sand mill, an annular type bead mill, or an attritor (colorant dispersion resistance). Further, the coloring composition of the present invention can also be produced by mixing pigments, salt-forming compounds, other coloring agents and the like separately dispersed in a coloring agent carrier. If the colorant such as a dye is highly soluble, specifically, if it is highly soluble in the solvent used, dissolved by stirring, and no foreign matter is confirmed, the above-mentioned fine dispersion step is performed. It does not have to be.

When used as a photosensitive coloring composition (resist material) for a color filter, it can be prepared as a solvent-developing type or alkali-developing type coloring composition. The solvent-developed or alkaline-developed coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and if necessary, a solvent, other dispersion aids, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Dispersion aid>
When the colorant is dispersed in the colorant carrier, a dispersion aid such as a dye derivative, a dispersant, or a surfactant can be appropriately contained. Since the dispersion aid has a great effect of preventing the reaggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has brightness, contrast, and storage stability. The sex becomes good. The dye derivative and the dispersant are as described above.

<Surfactant>
Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalline sulfonate, and sodium alkyldiphenyl ether disulfonate. , Monoethanolamine lauryl sulfate, Triethanolamine lauryl sulfate, Ammonium lauryl sulfate, Monoethanolamine stearate, Monoethanolamine styrene-acrylic acid copolymer, Anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazolin, which may be used alone or in combination of two or more. They can be mixed and used, but are not necessarily limited to these.

When a surfactant is added, it is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight, based on 100 parts by weight of the colorant. If the blending amount of the surfactant is less than 0.1 parts by weight, it is difficult to obtain the effect of addition, and if the content is more than 55 parts by weight, the dispersion may be affected by the excess dispersant. ..

<Removal of coarse particles>
The colored composition of the present invention comprises coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more, and coarse particles of 5 μm or more, preferably coarse particles of 0.5 μm or more, by means such as centrifugation, filtration with a sintering filter or a membrane filter. It is preferable to remove the mixed dust. As described above, it is preferable that the coloring composition does not contain particles having a size of 0.5 μm or more. It is more preferably 0.3 μm or less.
<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment. Further, the color filter may further include a magenta color filter segment, a cyan color filter segment, and a yellow filter segment. In the color filter of the present invention, at least one of a red filter segment, a green filter segment, and a yellow filter segment is formed from the pigment composition of the present invention. In particular, those in which the green filter segment is formed from the pigment composition of the present invention are preferable.

<Manufacturing method of color filter>
The color filter can be manufactured by a printing method or a photolithography method. Since the formation of the filter segment by the printing method can be patterned only by repeating printing and drying of the coloring composition prepared as the printing ink, it is low cost and excellent in mass productivity as a manufacturing method of the color filter. Furthermore, with the development of printing technology, it is possible to print fine patterns having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and it is possible to adjust the ink viscosity with a dispersant or an extender pigment.

When the filter segment is formed by the photolithography method, the coloring composition prepared as the solvent-developable or alkali-developable colored resist material is applied onto a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed (irradiation of radiation) through a mask having a predetermined pattern provided in contact with or without contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to manufacture a color filter. be able to. Further, in order to promote the polymerization of the colored resist material, heating can be applied as needed. According to the photolithography method, a color filter having higher accuracy than the above printing method can be manufactured.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution.
In order to increase the exposure sensitivity, the colored resist is applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film for preventing polymerization inhibition by oxygen. , Exposure can also be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an inkjet method or the like in addition to the above method, and the coloring composition of the present invention can be used in any method. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. .. Further, the transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

A black matrix can be formed in advance before forming each color filter segment on the transparent substrate or the reflective substrate. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but the black matrix is not limited thereto. Further, it is also possible to form a thin film transistor (TFT) in advance on the transparent substrate or the reflective substrate, and then form each color filter segment. Further, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention, if necessary.

The color filter of the present invention is bonded to a facing substrate using a sealing agent, liquid crystal is injected from an injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or a retardation film is attached to the substrate as necessary. A color liquid crystal display device is manufactured by sticking it on the outside of the surface. This color liquid crystal display device is twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optical convensend bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as).

In addition to the color liquid crystal display device, the color filter of the present invention can also be used for manufacturing a color image pickup device, an organic EL display device, electronic paper, and the like.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" and "%" mean "parts by weight" and "% by weight".

(Average primary particle size of pigment)
The average primary particle size of the pigment was measured by a method of directly measuring the size of the primary particle from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle size of the pigment primary particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating it to a cube having the obtained particle size, and the volume average particle size was defined as the average primary particle size.

(Weight average molecular weight of binder resin)
The weight average molecular weight (Mw) of the resin is converted to polystyrene measured by using a TSKgel column (manufactured by Tosoh) and a GPC (manufactured by Tosoh, HLC-8120GPC) equipped with an RI detector and using THF as a developing solvent. Weight average molecular weight (Mw).

(Acid value of binder resin and dispersant)
The resin acid value is a value obtained by converting the measured acid value (mgKOH / g) into a solid content in accordance with the potentiometric titration method of JIS K 0070.

(Average molecular weight of block copolymer [A1] and intermediate polymer (a))
For the number average molecular weight (Mn) and weight average molecular weight (Mw) of the basic resin type dispersant, HLC-8320GPC (manufactured by Tosoh Corporation) was used as an apparatus, SUPER-AW3000 was used as a column, and 30 mM triethylamine was used as an eluent. And 10 mM LiBr N, N-dimethylformamide solution, polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw).

(Amine values of block copolymer [A1] and intermediate polymer (a))
The amine value of the basic resin type dispersant is a value obtained by converting the measured total amine value (mgKOH / g) into a solid content according to the method of ASTM D 2074.

Subsequently, a method for producing a binder resin solution, a block copolymer solution, a pigment, a dye derivative, a coloring composition for a color filter, and a photosensitive coloring composition used in Examples and Comparative Examples will be described.

<Manufacturing method of binder resin solution>
(Preparation of acrylic resin solution 1)
Put 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable 4-neck flask, and heat to 120 ° C. while injecting nitrogen gas into the vessel. Azobisisobutyro as a catalyst required for the reaction of 16.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 25.0 parts of dicyclopentanyl methacrylate, 16 parts of methyl methacrylate and the precursor at this stage from the dropping tube at temperature. A mixture of 1.0 part of nitrile was added dropwise over 2.5 hours to carry out a polymerization reaction. Next, the inside of the flask was replaced with air, and 17.0 parts of acrylic acid and 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, and the temperature was 120 ° C. The reaction was carried out for 5 hours to obtain a resin solution having a weight average molecular weight of about 12000 (measured by GPC). Since the added acrylic acid is ester-bonded to the epoxy group terminal of the glycidyl methacrylate constituent unit, a carboxyl group is not generated in the resin structure. Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine as a catalyst required for the reaction of the precursor at this stage were added and reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of the two carboxyl groups generated by cleavage of the carboxylic acid anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxyl group terminal. Propylene glycol monomethyl ether acetate was added so that the non-volatile content was 40% to obtain an acrylic resin solution 1.

<Manufacturing of block copolymer [A1]>
(Production Example 1: Block Copolymer Solution (A1-1))
A reactor equipped with a gas inlet, a condenser, a stirring blade, and a thermometer includes 23 parts of methyl methacrylate, 13 parts of n-butyl methacrylate, 8 parts of n-butyl acrylate, 8 parts of t-butyl acrylate, and methacrylic acid. Eight parts of 2-hydroxyethyl, 1.1 parts of AIBN (2,2'-azobisisobutyronitrile), and 2.8 parts of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester are added to propylene glycol monomethyl ether acetate 100. The inside of the system was replaced with nitrogen by dissolving in the part and subjecting to nitrogen bubbling for 30 minutes. Then, the mixture was gently stirred, and the mixture was stirred at 60 ° C. for 24 hours while continuing to flow nitrogen to carry out living radical polymerization.
Next, 1.3 parts of AIBN (2,2'-azobisisobutyronitrile) and 40 parts of the compound represented by the above formula (4-9) are dissolved in 70 parts of propylene glycol monomethyl ether acetate, and nitrogen is used for 30 minutes. The substituted solution was added to the above reaction solution, and living radical polymerization was carried out at 60 ° C. for 24 hours. The polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 97% or more in terms of the non-volatile content. Then, propylene glycol monomethyl ether acetate was added so that the volatile content became 40% to obtain a block copolymer liquid (A1-1) having no ionic group. As a result of the molecular weight measurement, it was Mw9000.

(Production Example 2; Preparation of Polymer A1-2)
A reactor equipped with a gas inlet, a condenser, a stirring blade, and a thermometer includes 25 parts of methyl methacrylate, 15 parts of n-butyl methacrylate, 10 parts of n-butyl acrylate, 10 parts of t-butyl methacrylate, and methacrylic acid. 10 parts of 2-hydroxyethyl, 1.1 parts of AIBN (2,2'-azobisisobutyronitrile), and 2.8 parts of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester are added to propylene glycol monomethyl ether acetate 100. The inside of the system was replaced with nitrogen by dissolving in the part and subjecting to nitrogen bubbling for 30 minutes. Then, the mixture was gently stirred, and the mixture was stirred at 60 ° C. for 24 hours while continuing to flow nitrogen to carry out living radical polymerization.
Next, 1.3 parts of AIBN (2,2'-azobisisobutyronitrile) and 30 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (ADEKA "Adecastab LA82") were added to propylene glycol monomethyl ether acetate. A solution dissolved in 70 parts and subjected to nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 60 ° C. for 24 hours. The polymerization solution was sampled, the solid content was measured, and converted from the non-volatile content. After confirming that the polymerization conversion was 97% or more, a solution of the intermediate polymer (a-1) was obtained. Subsequently, 17.1 part of chloroacetic acid and 100 parts of propylene glycol monomethyl ether acetate were put into the above container. Then, the reaction was continued at 100 ° C. for 7 hours, and the reaction was terminated when the solid content amine value disappeared. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Then, propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight to prepare a polymer (A1-2).

(Production Examples 3 to 11; Preparation of Polymers A1-3 to A1-9 and A1-11 to A1-12)
The polymer solution (A) was synthesized in the same manner as the basic resin (A1-2) except that the raw materials were changed as shown in Table 1, and the polymers (A1-3) to (A1-9) were prepared. Solutions (A1-11) to (A1-12) were obtained.

(Production Example 12; Preparation of Polymer A1-10)
A reaction device equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer includes 25 parts of methyl methacrylate, 15 parts of n-butyl methacrylate, 10 parts of n-butyl acrylate, 10 parts of t-butyl methacrylate, and methacrylic acid. 10 parts of 2-hydroxyethyl, 1.1 parts of AIBN (2,2'-azobisisobutyronitrile), and 2.8 parts of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester are added to propylene glycol monomethyl ether acetate 100. The inside of the system was replaced with nitrogen by dissolving in the part and subjecting to nitrogen bubbling for 30 minutes. Then, the mixture was gently stirred, and the mixture was stirred at 60 ° C. for 24 hours while continuing to flow nitrogen to carry out living radical polymerization.
Next, 1.3 parts of AIBN (2,2'-azobisisobutyronitrile) and 30 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (ADEKA "Adecastab LA82") were added to propylene glycol monomethyl ether acetate. A solution dissolved in 70 parts and subjected to nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 60 ° C. for 24 hours. The polymerization solution was sampled, the solid content was measured, and converted from the non-volatile content. After confirming that the polymerization conversion was 97% or more, a solution of the intermediate polymer (a-1) was obtained. Subsequently, 8.5 parts of chloroacetate and 100 parts of propylene glycol monomethyl ether acetate were put into the above container. Then, the reaction was continued at 100 ° C. for 7 hours, and the reaction was terminated when the solid content amine value reached 35.2 KOHmg / g. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes. Then, the non-volatile content was measured, and propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight to prepare a polymer (A1-10).

The abbreviations in Table 1 are as follows.
MMA: Methyl Methacrylate nBMA: n-Butyl Methacrylate nBA: n-Butyl Acrylic Acid tBA: t-Butyl Acrylic Acid HEMA: 2-Hydroxyethyl Methacrylic Acid LA82: 1,2,2,6,6-Pentamethylpiperidyl Methacrylate DMAEMA : Dimethylaminoethyl methacrylate DMAPMA: 2- (dimethylamino) propyl methacrylate

<Production Examples of Block Copolymers (A2-1) and (A2-2)>
(Production Example 12: Preparation of Block Copolymer Solution (A2-1))
A reaction device equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer includes 25 parts of methyl methacrylate, 15 parts of n-butyl methacrylate, 10 parts of n-butyl acrylate, 10 parts of t-butyl acrylate, and methacrylic acid. 10 parts of 2-hydroxyethyl, 1.1 parts of AIBN (2,2'-azobisisobutyronitrile), and 2.8 parts of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester are added to propylene glycol monomethyl ether acetate 100. The inside of the system was replaced with nitrogen by dissolving in the part and subjecting to nitrogen bubbling for 30 minutes. Then, the mixture was gently stirred, and the mixture was stirred at 60 ° C. for 24 hours while continuing to flow nitrogen to carry out living radical polymerization.
Next, 1.3 parts of AIBN (2,2'-azobisisobutyronitrile) and 430 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (ADEKA "Adecastab LA82") were added to propylene glycol monomethyl ether acetate. A solution dissolved in 70 parts and subjected to nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was carried out at 60 ° C. for 24 hours. The polymerization solution was sampled, the solid content was measured, and converted from the non-volatile content. After that, it was confirmed that the polymerization conversion rate was 97% or more. Then, propylene glycol monomethyl ether acetate was added so that the volatile content became 40%, and the block copolymer solution (A2-1) having no ionic radical was added. As a result of molecular weight measurement, Mw9000 and the amine value per solid content were 70.4 mgKOH / g.

(Production Example 12: Preparation of Block Copolymer Solution (A2-2))
A polymer solution (A) was synthesized in the same manner as the basic resin (A2-1) except that the raw materials were changed as shown in Table 1, and the polymer (A2-2) having only a cationic group in the side chain was synthesized. ) A solution was obtained.

The abbreviations in Table 2 are as follows.
DMC: Dimethylaminoethylmethyl chloride salt methacrylic acid

<Pigment manufacturing method>
(Manufacturing method of aluminum phthalocyanine pigment 1)
To a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of hydroxyaluminum phthalocyanine and 18.2 parts of diphenyl phosphate were added, heated to 90 ° C., and reacted for 8 hours. After cooling this to room temperature, this reaction solution was injected into 4000 parts of water. The product was filtered, washed with methanol and dried to give an aluminum phthalocyanine pigment 1.

(Manufacturing method of aluminum phthalocyanine pigment 2)
To a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of hydroxyaluminum phthalocyanine, and 99.1 parts of N-bromosuccinimide (NBS) were added, stirred, and reacted at 20 ° C. for 3 hours. Then, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added, and the mixture was stirred at 80 ° C. for 1 hour. Then, this mixture was collected by filtration, washed with water and dried to obtain a crude halogenated aluminum phthalocyanine pigment. Subsequently, 500 parts of N-methylpyrrolidone, 50 parts of crude halogenated aluminum phthalocyanine pigment and 18.2 parts of diphenyl phosphate were added to a three-necked flask, and the mixture was heated to 90 ° C. and reacted for 8 hours. After cooling this to room temperature, this reaction solution was injected into 4000 parts of water. The product was filtered, washed with methanol and dried to give an aluminum phthalocyanine pigment 2.

(Manufacturing method of quinophthalone pigment 1)
To 300 parts of methyl benzoate, 100 parts of compound (A), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. Further, after cooling to room temperature, the reaction mixture was added to 3510 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol and dried to obtain 120 parts of quinophthalone pigment 1.

Compound (A)

<Manufacturing method of miniaturized pigment>
(Manufacturing of miniaturized green pigment P-1)
Zinc phthalocyanine green pigment C.I. I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , A finely divided green pigment P-1 was obtained.

(Manufacturing of refined green pigment P-2)
200 parts of the synthesized aluminum phthalocyanine pigment 1, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , A finely divided green pigment P-2 was obtained.

(Manufacturing of miniaturized green pigment P-3)
200 parts of the synthesized aluminum phthalocyanine pigment 2, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , A finely divided green pigment P-3 was obtained.

(Manufacturing of refined yellow pigment P-4)
Kinoftalone yellow pigment C.I. I. 200 parts of Pigment Yellow 138 (“Pariotor Yellow L 0962HD” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8 liters of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , A finely divided yellow pigment P-4 was obtained.

(Manufacturing of refined yellow pigment P-5)
200 parts of the synthesized quinophthalone pigment 1, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8 liters of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , A finely divided yellow pigment P-5 was obtained.

(Manufacturing of refined yellow pigment P-6)
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 (BASF's "Pariotor Yellow D1819") was charged in 200 parts, sodium chloride (1400 parts) and diethylene glycol (360 parts) in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 80 ° C. for 6 hours. This kneaded product is put into 8 liters of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours and finely. A yellow pigment P-6 was obtained.

(Manufacturing of refined yellow pigment P-7)
Isoindoline yellow pigment C.I. I. 200 parts of Pigment Yellow 185 (BASF's "Pariotor Yellow D1155"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. This kneaded product is put into 8 liters of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours and finely. A yellow pigment P-7 was obtained.

(Manufacturing of refined yellow pigment P-8)
Azo-based yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E4GNGT” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8 liters of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , A refined yellow pigment P-8 was obtained.

(Manufacturing of refined red pigment P-9)
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of Pigment Red 254 (“B-CF” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , 190 parts of the finely divided diketopyrrolopyrrole pigment P-9 was obtained.

(Manufacturing of refined red pigment P-10)
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (BASF's "Chromophphthalred A2B"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , Anthraquinone-based miniaturized red pigment P-10 was obtained.

(Manufacturing of miniaturized blue pigment P-11)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Color Co., Ltd., specific surface area 60 m ² / g), 200 parts, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho). It was kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , A finely divided blue pigment P-11 was obtained.

(Manufacturing of refined purple pigment P-12)
Dioxazine-based purple pigment C.I. I. Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyo Color Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water and stirred for 2 hours while heating at 80 ° C. to form a slurry. This slurry was filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours to obtain a finely divided purple pigment P-12.

<Manufacturing method of coloring composition for color filter>
[Example 1]
(Pigment dispersion (GP-1))
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm for 3 hours, and then the pore diameter is 5. The mixture was filtered through a 0 μm filter to prepare a pigment dispersion (GP-1) having a non-volatile component of 20% by weight.

Miniaturized green pigment P-1: 12.0 parts Block copolymer solution (A1-1): 6.0 parts Acrylic resin solution 1: 14.0 parts Propylene glycol monomethyl ether acetate (PGMAc): 68.0 parts

[Examples 2-37, Comparative Examples 1-24]
(Pigment dispersion (GP-2 to 61))
Hereinafter, pigment dispersions (GP-2 to 61) were prepared in the same manner as the pigment dispersion (GP-1) except that the pigment type and the acrylic block copolymer were changed to the compositions shown in Table 3.

<Evaluation of pigment dispersion>
The pigment dispersions (GP-1) to (GP-57) obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Table 4.

(Contrast ratio (CR) evaluation of coating film)
The light emitted from the backlight unit for a liquid crystal display passes through a polarizing plate, is polarized, passes through a coating film of a colored composition coated on a glass substrate, and reaches the other polarizing plate. At this time, if the polarizing plates and the polarizing planes of the polarizing plate are parallel to each other, the light passes through the polarizing plate, but if the polarizing planes are orthogonal to each other, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the coloring composition, scattering or the like occurs due to the colorant particles, and if a part of the polarizing surface is displaced, the light is transmitted when the polarizing plates are in parallel. When the amount of light emitted is reduced and the polarizing plates are orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio of the luminance when the polarizing plates were parallel to the luminance when the polarizing plates were orthogonal was calculated as the contrast ratio.
(Contrast ratio) = (Brightness when parallel) / (Brightness when orthogonal)
Therefore, when scattering occurs due to the colorant in the coating film, the brightness when parallel is reduced and the brightness when orthogonal is increased, so that the contrast ratio is lowered.

A color luminance meter (“BM-5A” manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) was used as the polarizing plate. The measurement was carried out through a black mask having a 1 cm square hole in the measurement portion.

First, the pigment dispersion was applied onto a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm, respectively, using a spin coater, then dried at 70 ° C. for 20 minutes, and then heated at 230 ° C. for 60 minutes and allowed to cool. By doing so, a coated film substrate was produced. The contrast ratio (CR) of the obtained coated substrate was measured. The prepared coating film substrate was adjusted to have a film thickness of 1.5 μm after heat treatment at 230 ° C. The contrast ratio was determined according to the following criteria.

⊚: 9000 or more: extremely good ○: 6000 or more to less than 9000: good △: 3000 or more to less than 6000: practically possible ×: less than 3000: defective

(Viscosity evaluation (dispersion stability))
The viscosity of the pigment dispersion was measured at an initial viscosity at 25 ° C. using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Separately, 25 g of the pigment dispersion was allowed to stand at 40 ° C. for 24 hours in a sealed state in a glass container, and then the viscosity was measured by the same method as described above to obtain the viscosity over time. The dispersion stability was evaluated according to the following criteria based on the viscosity change rate = (initial viscosity-viscosity over time) / initial viscosity x 100 (%). The evaluation criteria are shown below.

○ (Practically good): When the viscosity change rate is within ± 10% and no sediment is formed.
Δ (practical): When the viscosity change rate is ± 10% to 20% and no sediment is formed.
× (Practical useless): When the viscosity change rate exceeds ± 20%, or when the sediment is formed even if the viscosity change rate is within ± 20%.

(Foreign matter evaluation)
To evaluate the generation of foreign matter, a pigment dispersion was applied on a transparent substrate so that the dry coating film had a size of about 1.5 μm, heated in an oven at 250 ° C. for 60 minutes, and allowed to cool. The number of foreign substances inside was measured. The evaluation was performed by observing the surface using a metallurgical microscope "BX60" manufactured by Olympus System Corporation. The magnification was set to 500 times, and the number of foreign substances observable in any five fields of view was measured by transmission.

⊚: Number of foreign substances is less than 3: Very good ○: Number of foreign substances is 3 or more and less than 20: Good △: Number of foreign substances is 21 or more and less than 100: Practical ×: Number of foreign substances is 100 More than one: defective

As shown in Table 4, by using the block copolymer of the present invention, it was possible to prepare a dispersion having excellent contrast ratio, viscosity stability, and foreign matter for various coloring materials.

<Manufacturing of photosensitive coloring compositions for color filters>
[Example 38] (Green photosensitive coloring composition (R-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1 μm to prepare a photosensitive coloring composition (R-1).

PG58 / Pigment dispersion (GP-1): 38.0 parts PY138 / Pigment dispersion (GP-20): 12.0 parts Acrylic resin solution 1: 10.0 parts Photopolymerizable monomer (manufactured by Toa Synthetic Co., Ltd.) "Aronix M-402"): 2.0 parts Photopolymerization initiator (BASF "Irgacure 907"): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodoya Chemical Industry Co., Ltd.): 0. Part 3 Cyclohexanone: 36.7 parts

[Examples 39 to 59, Comparative Examples 25 to 27] (Green photosensitive coloring composition (R-2 to 25))
Photosensitive coloring compositions (R-2) to (R-25) in the same manner as in Example 38, except that the breakdown of 50 parts in total of the coloring liquid was changed to the components and parts by weight shown in Table 5, respectively. ) Was produced.

<Evaluation of photosensitive coloring composition>
The obtained photosensitive coloring composition was evaluated for heat resistance, developability, and adhesion. The results are shown in Table 5.

(Evaluation of heat resistance)
The obtained photosensitive coloring composition was applied to a glass substrate on which a black matrix was formed in advance by a spin coating method, and then dried in a clean oven at 70 ° C. for 20 minutes. Then, after cooling this substrate to room temperature, ultraviolet light was exposed through a photomask using an ultrahigh pressure mercury lamp. Then, this substrate was spray-developed with a 0.2 wt% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, washed with ion-exchanged water, and dried. Further, heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a striped colored pixel layer on the substrate. The produced colored pixel layer was adjusted to have a film thickness of 2.0 μm after heat treatment at 230 ° C. The chromaticity of the obtained coating film was measured with [L * (1), a * (1), b * (1)] using a microspectroscopy meter (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). Further, the chromaticity [L * (2), a * (2), b * (2)] after heat treatment at 250 ° C. for 60 minutes was measured, and the color difference ΔE * ab was determined by the following formula. The heat resistance was determined according to the following criteria.
ΔE * ab = [[L * (2) -L * (1)] 2+ [a * (2) -a * (1)] 2+ [b * (2) -b * (1)] 2] 1/2

⊚: ΔE * ab = less than 1: extremely good ○: ΔE * ab = 1 or more and less than 3: good Δ: ΔE * ab = 3 or more and less than 5: practically possible ×: ΔE * ab = 5 or more: defective

(Evaluation of developability)
Using the obtained photosensitive coloring composition, a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm was coated with a spin coater so that the film thickness after drying was 2.0 μm, and the film thickness was 70 ° C. for 20 minutes. It was dried to prepare a coated substrate. This substrate was spray-developed with a 0.2 wt% sodium carbonate aqueous solution at 23 ° C., and the development time (development time) was calculated until the coating film completely disappeared, and the developability was evaluated. The judgment criteria are shown below.

◎: Less than 20 seconds ○: 20 seconds or more and less than 30 seconds △: 30 seconds or more and less than 40 seconds ×: 40 seconds or more… Unusable level

(Evaluation of adhesion)
A substrate obtained by applying a photosensitive coloring composition on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater at a rotation speed at which the film thickness after drying becomes 2 μm is dried at 70 ° C. for 20 minutes. Ultraviolet rays of 150 mJ / cm2 were irradiated using an ultrahigh pressure mercury lamp through a photomask having 100 openings of 10 μm × 10 μm. Then, it was spray-developed with an alkaline developer consisting of a 0.2 wt% sodium carbonate aqueous solution to remove an unexposed portion, and then washed with ion-exchanged water. At this time, the adhesion was evaluated based on how many patterns of 10 μm × 10 μm remained. The developability evaluation was determined according to the following criteria. × is a level that is difficult to use.

⊚: 90 or more patterns remaining ○: 80 to 89 patterns remaining Δ: 70 to 79 patterns remaining ×: 0 to 69 patterns remaining

When the block copolymer of the present invention was used, excellent results in heat resistance, developability, and adhesion were obtained.

<Making color filters>
A color filter was produced using the photosensitive coloring composition of the present invention. The red photosensitive coloring composition and the blue photosensitive coloring composition used were prepared as follows.

(Red Photosensitive Coloring Composition (R-26))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1 μm to prepare a red photosensitive coloring composition (R-26).

PR254 / Pigment dispersion (GP-30): 30.0 parts PR177 / Pigment dispersion (GP-32): 20.0 parts Acrylic resin solution 1: 10.0 parts Photopolymerizable monomer (manufactured by Toa Synthetic Co., Ltd.) "Aronix M-402"): 2.0 parts Photopolymerization initiator (BASF "Irgacure 907"): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodoya Chemical Industry Co., Ltd.): 0. Part 3 Cyclohexanone: 36.7 parts

(Red Photosensitive Coloring Composition (R-27))
In the preparation of the red photosensitive coloring composition (R-26), except that (GP-30) was changed to (GP-46) and (GP-32) was changed to (GP-47), it was referred to as (R-26). A red photosensitive coloring composition (R-27) was prepared by the same method.

(Blue Photosensitive Coloring Composition (R-28))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1 μm to prepare a blue photosensitive coloring composition (R-28).

PB15: 6 ・ Pigment dispersion (GP-34): 28.1 parts PV23 ・ Pigment dispersion (GP-36): 3.1 parts Acrylic resin solution 1: 6.3 parts Photopolymerizable monomer (Toa Synthetic) "Aronix M-402" manufactured by Aronix M-402): 4.0 parts Photopolymerization initiator (BASF "Irgacure 907"): 2.0 parts Sensitizer ("EAB-F" manufactured by Hodoya Chemical Industry Co., Ltd.): 0.3 part Cyclohexanone: 56.2 parts

(Blue Photosensitive Coloring Composition (R-29))
In the preparation of the red photosensitive coloring composition (R-28), (R-25) except that (GP-34) was changed to (GP-48) and (GP-36) was changed to (GP-49). The blue photosensitive coloring composition (R-29) was prepared in the same manner as in the above.

[Example 60] (color filter (CF-1))
The red photosensitive coloring composition (R-26) was applied to a glass substrate on which a black matrix was previously formed by a spin coating method, and then dried in a clean oven at 70 ° C. for 20 minutes. Then, after cooling this substrate to room temperature, ultraviolet rays were exposed through a photomask using an ultrahigh pressure mercury lamp.
Then, this substrate was spray-developed with a 0.2 wt% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, washed with ion-exchanged water, and dried. Further, heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a striped colored pixel layer on the substrate.
Next, the green photosensitive coloring composition (R-1) of the present invention was used to form a green colored pixel layer in the same manner as the red colored pixel layer. Further, in the same manner, the blue photosensitive coloring composition (R-28) was used to form a blue colored pixel layer to obtain a color filter (CF-1). The film thickness of each colored pixel layer was 2.0 μm.
[Comparative Example 27] (Color Filter (CF-2))
The photosensitive coloring composition used in the production of the color filter (CF-1) was subjected to the red photosensitive coloring composition ((R-27)), the green photosensitive coloring composition (R-23), and the blue photosensitive coloring composition. A method color filter (CF-2) was produced in the same manner as in (CF-1) except that it was changed to the sex coloring composition (R-29). The formation thickness of each colored pixel layer was 2 in each case. It was 0.0 μm.

When the contrast ratio of (CF-1) and (CF-2) was measured, (CF-1) was the better result, demonstrating the effect of the present invention.

Claims (11)

A color composition for a color filter containing a colorant, a dispersant [A], a binder resin and a solvent, wherein the dispersant [A] has an A block having a repeating unit represented by the following general formula (1). A coloring composition for a color filter, which is a block copolymer [A1] containing a B block having no repeating unit represented by the general formula (1) .
General formula (1)

[In the general formula (1), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² and R ¹³ each independently represent a divalent linking group, and X ⁺ represents a divalent cationic linking group. represents, Y ^- represents a monovalent anionic group. ]
General formula (3)

[In the general formula (3), R ³¹ and R ³² each independently represent a monovalent organic group.
* ¹ represents a bond with R ^{12 and * 2} represents a bond with R ¹³ . ]
^{A coloring composition for a color filter in which X +} in the general formula (1) is a divalent linking group represented by the general formula (3). The coloring composition for a color filter according to claim 1 ^{, wherein R 31} and R ³² of the general formula (3) are monovalent aliphatic hydrocarbon groups. Wherein Y in the general formula (1) ^- is, -CO ₂ ^- or -SO ₃ ^- and is claim 1 or a color filter for coloring composition according to 2. The invention according to any one of claims 1 to 3, ^{wherein R 12} of the general formula (1) is a group composed of a combination of an alkanediyl group having 1 to 8 carbon atoms and -COO- or -CONRb-. Coloring composition for color filters.
[Rb represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ] The coloring composition for a color filter according to any one of claims 1 to 4, ^{wherein R 13} of the general formula (1) is an alkanediyl group having 1 to 5 carbon atoms. According to any one of claims 1 to 5 , the content of the repeating unit represented by the general formula (1) is 50 to 100% by weight with respect to the A block contained in the block copolymer [A1]. The coloring composition for a color filter according to the above. The coloring composition for a color filter according to any one of claims 1 to 6 , further comprising a dispersant [B] having an aromatic carboxyl group. Claim 1 is characterized in that the colorant is any one of a phthalocyanine pigment, a diketopyrrolopyrrole pigment, a quinophthalone pigment, an isoindoline pigment, an anthraquinone pigment, an azo pigment, and a dioxazine pigment. a color filter for coloring composition according to any one of claims 1-7. The colorant further comprises C.I. I. Pigment Red 177, 254, C.I. I. Pigment Yellow 138, 139, 185, 231, C.I. I. The coloring composition for a color filter according to any one of claims 1 to 8, which comprises Pigment Green 58, 62, 63, Pigment Blue 15: 6, or Pigment Violet 23. The coloring composition for a color filter according to any one of claims 1 to 9, further comprising at least one selected from the group consisting of a photopolymerizable monomer and a photopolymerization initiator. A color filter comprising a filter segment formed from the coloring composition for a color filter according to any one of claims 1 to 10 on a substrate.