JP2019095548A - Color filter coloring composition and color filter - Google Patents

Abstract

To provide a color filter coloring composition which can be used to form a coating film that is superior in terms of not only dispersibility, such as contrast and storage stability, but also adhesion and developability, and to provide a color filter with high-quality filter segments, which solves the aforementioned problem, using such composition.SOLUTION: The above mentioned problem is solved by a color filter coloring composition containing a colorant, dispersant [A], binder resin, and organic solvent, where the dispersant [A] comprises a repeating unit represented by a general formula (1).SELECTED DRAWING: None

Description

  The present invention relates to a coloring composition and a photosensitive coloring composition used for producing a color filter used for a color liquid crystal display device, a color imaging tube device, an organic EL display device, an electronic paper, etc. The present invention relates to a color filter provided with a filter segment formed.

  Resin type dispersants are generally used in photosensitive compositions for color filters in order to keep the colorant dispersed well, and basic dispersants are used for pigments having an acidic surface. Depending on the structure, the properties of the colorant change significantly. In recent years, in the field of color filters used in color liquid crystal displays and the like, demands for high brightness, high contrast, thin films, fine patterns of patterns, etc. have been increasing. Accordingly, it is necessary to disperse the fine pigment with a limited amount of dispersant, and it is very difficult to achieve both the dispersibility and the required physical properties at the same time.

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

Japanese Patent Application Laid-Open No. 8-038875 Japanese Patent Application Laid-Open No. 8-143813 JP 2009-185277 publication Japanese Patent Application Laid-Open No. 2002-31713 Japanese Patent Application Laid-Open No. 2004-287366 Japanese Patent Application Laid-Open No. 2010-134419

An object of the present invention is to achieve the following objects.
That is, the object of the present invention is to provide a photosensitive coloring composition having not only good lightness, contrast, heat resistance and storage stability but also excellent adhesion and developability, and a color formed using the same. 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 a side chain. It is a block copolymer [A1] containing A block which has a repeating unit, and B block which does not have a repeating unit represented by General formula (1), It relates to the coloring composition for color filters characterized by the above-mentioned.
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 It 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。］ Moreover, this invention is a coloring composition for color filters whose X ^<+> in the said General formula (1) is a bivalent coupling group represented by following General formula (2) or 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 a bond to R ¹² and * ² represents a bond to 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 to R ¹² and * ² represents a bond to 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 each of R ³¹ and R ^{32 in} the general formula (3) is a monovalent aliphatic hydrocarbon group.

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 in the} general formula (1) is a combination of an alkanediyl group having 1 to 8 carbon atoms and -COO- or -CONRb- Related to things.
[Rb represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

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

  In the color filter according to the present invention, the content of the repeating unit represented by the general formula (1) is 50 to 100% by weight based on A block contained in the block copolymer [A1]. It relates to a coloring composition.

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

  In the color of the present invention, 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. The present invention relates to a coloring composition for a filter.

    The colorant further contains C.I. I. Pigment red 177, 254, C.I. I. Pigment yellow 138, 139, 185, 231, C.I. I. The present invention relates to the coloring composition for color filter described above, which comprises pigment green 58, 62, 63, pigment blue 15: 6 or pigment violet 23.

  Furthermore, 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 comprising a filter segment formed of the coloring composition for color filter.

The constituent features of the present invention will be described in detail below.
In the present application, when it is described as “(meth) acryloyl”, “(meth) acrylic”, “(meth) acrylic acid” or “(meth) acrylate”, unless otherwise described, Acryloyl and / or methacryloyl ”,“ acrylic and / or methacrylic ”,“ acrylic acid and / or methacrylic acid ”or“ acrylate and / or methacrylate ”. In addition, “CI” listed in the present specification means color index (CI).

<Colorant (a)>
The coloring composition for color filters of the present invention contains a colorant such as an organic pigment, an inorganic pigment, an organic dye, and an inorganic dye. These can be used alone or in combination of two or more. It is preferable to use an organic pigment for the coloring composition for color filters of the present invention, and for example, azo pigments (soluble azo lake pigments, insoluble azo pigments, condensation azo pigments, etc.), azomethine pigments, phthalocyanine pigments, quinacridone pigments Pigments, isoindolinone pigments, isoindoline pigments, quinophthalone pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, diketopyrrolopyrrole pigments, dye lake pigments, triarylmethane pigments, And squarylium pigments and the like. Among these, as a coloring agent used for the coloring composition for color filters of the present invention, from the viewpoint of color characteristics as a color filter, phthalocyanine pigments, diketopyrrolopyrrole pigments, quinophthalone pigments, isoindoline pigments It is preferable to use any one of an anthraquinone pigment, an azo pigment and a dioxazine pigment.
(Phthalocyanine pigment)
Examples of phthalocyanine pigments include copper phthalocyanines, metal-free phthalocyanines, zinc phthalocyanines, aluminum phthalocyanines, cobalt phthalocyanines, nickel phthalocyanines, iron phthalocyanines, and halogenated phthalocyanines 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, the patent 4893859, the Unexamined-Japanese-Patent 2016-57635, the pigment of Unexamined-Japanese-Patent 2016-153481, etc. are mentioned. Among them, zinc phthalocyanine and aluminum phthalocyanine are preferable from the viewpoint of lightness, and C.I. I. Pigment Green 58, Patents 4983859, and those disclosed in JP-A-2016-153481 are preferred.

(Diketopyrrolopyrrole pigment)
Examples of diketopyrrolopyrrole-based pigments include C.I. I. Pigment red 254, 255, 264, 270, 272, C.I. I. Pigment Orange 71, 73, 81, the pigment of Unexamined-Japanese-Patent No. 2012-21970 etc. is mentioned. Among them, from the viewpoint of lightness, C.I. I. Pygmen red 254 is preferred.

(Quinophthalone pigments)
Examples of quinophthalone pigments include C.I. I. Pigment Yellow 138, JP-A-6-9891, JP-A-499302, JP-A-2012-82337, International Publication 2013/081140, JP-A-2013-133448, etc. Among them, from the viewpoint of lightness and heat resistance, C.I. I. Pigment Yellow 138 and those described in Patent 4,993,026.

(Iso indoline pigment)
Examples of isoindoline-based pigments 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 the like. Among them, from the viewpoint of coloring power, C.I. I. Pigment yellow 139, 185 is preferable.

(Anthraquinone pigment)
Anthraquinone pigments collectively refer to pigments containing anthraquinone or anthrone which are quinones derived from anthracene in the structure, anthraquinone azo, amino anthraquinone, indanthrene, anthrapyrimidine, ansanthrone, flavanthrone, pyranthrone, isobiolance Ron and the like. 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, and the like. Among them, C.I. I. Pigment red 177 is preferred.

(Azo pigment)
The azo pigment is a generic term for pigments having an azo group (-N = N-), such as azo lake pigment, monoazo pigment, disazo pigment, benzimidazolone pigment, β-naphthol pigment, condensation azo pigment, azo metal complex pigment, etc. It can be mentioned. The following may be mentioned as representative ones.
Azo lake 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, 194, C.I. I. Pigment orange 36, 60.62, 64, 72, C.I. I. Pigment reds 171, 175, 176, 185, 208, C.I. I. Pigment violet 32, C.I. I. Pigment brown 25, 32
β-naphthol pigments: 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, 22, 31, 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, JP 2013-145321, C. 1; I. Pigment violet 13, 17, 50, C.I. I. Pigment blue 25, 26
Condensed azo pigments: 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 pigments: C.I. I. Pigment Yellow 150, JP-A-2014-12832, among them, C.I. I. Pigment red 242, C.I. I. Pigment Yellow 150 is desirable.
(Dioxazine pigment)
For example, C.I. I. Pigment violet 23, 34, 35, 37, C.I. I. Pigment blue 80 pigments.
(Other organic pigments)
As other organic pigments, any of known and commonly used pigments can be mentioned. For example, organic pigments such as quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, azomethine pigments, thioindigo pigments, metal complex pigments and the like 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. And pigments such as CI pigment orange 48 and 49.

(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 the like.

(Isoindolinone pigment)
C. I. Pigment yellow 109, 110, 173, 179, C.I. I. And pigments such as CI pigment orange 61.

(Metal complex pigment) azomethine 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 the like.
(Thioindigo pigment)
For example, C.I. I. Pigment red 88, 279, C.I. I. Pigment Violet 36, 38 and the like.

(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 acid dyes, direct dyes, basic dyes, salt forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, architectural dyes, sulfur dyes and the like can be used. In addition, these may be in the form of derivatives or laked lakes of dyes.

  Furthermore, acid dyes having an acidic group such as sulfonic acid and carboxylic acid, and in the case of direct dyes, inorganic salts of acid dyes, acid dyes and quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, Or a salt forming compound with a nitrogen-containing compound such as a primary amine compound, or using as a salt forming compound by using a resin component having these functional groups as a salt forming compound, or using it as a sulfone amide compound In order to be excellent in resistance, it is possible to make a coloring composition excellent in fastness, which is preferable. Further, a salt forming compound of an acid dye and a compound having an onium base is also preferable because it is excellent in fastness, and more preferably, the compound having an onium base is a resin having a cationic group in a side chain.

  In the case of the form of a basic dye, it can be used by using an organic acid or perchloric acid or a metal salt thereof to form a salt. Among them, a salt forming compound of a basic dye is preferable because it is resistant and excellent in the compatibility with the pigment, and the basic dye and organic sulfonic acid which is a counter component which works as a counter ion, organic sulfuric acid, fluorine group-containing phosphorus It is possible to use a salt-forming compound having formed a salt with an anion compound, a fluorine group-containing boron anion 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 acid dye. It is more preferable.

  Moreover, when it has a polymeric unsaturated group in pigment | dye frame | skeleton, it can be set as the dye excellent in tolerance, and it is preferable.

  The chemical structure of the dye includes, for example, azo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthraquinone dyes, Pyridone dyes, carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes Dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, Norin based dye include nitro dyes, nitroso dyes, and a dye structure derived from a dye selected from those metal complex dyes.

  Among these dye structures, azo dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone, from the viewpoint of color characteristics such as hue, color separation, and color unevenness. Dye structures derived from dyes selected from dyes, phthalocyanine dyes and subphthalocyanine dyes are preferable, and dyes selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes The pigment structure derived from is more preferable. Specific dye compounds that can form a dye structure are described in “New Dye Handbook” (Organic Synthetic Chemistry Association, edited by Maruzen, 1970), “The Society of Dyers and colourists”, “Dye Handbook” (Ogawara et al. Ed., Kodansha, 1986).

<Finening of pigment>
When the coloring agent used for the coloring composition for color filters of this invention is a pigment, it is preferable to refine | miniaturize and use it from a viewpoint of contrast. The method of refining is not particularly limited, and any of wet grinding, dry grinding and solution precipitation methods can be used, for example, and as exemplified in the present invention, salt milling treatment by kneader method which is one of wet grinding Etc. to be miniaturized. The average primary particle size of the pigment determined by TEM (transmission electron microscopy) is preferably in the range of 5 to 90 nm. When it is smaller than 5 nm, dispersion in the organic solvent becomes difficult, and when it is larger than 90 nm, a sufficient contrast ratio may not be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling treatment is a batch type or continuous type of kneader, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. of a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent. After mechanically kneading while heating using a kneader, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and at the time of salt milling, the pigment is crushed using the hardness of the inorganic salt. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, 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 in terms of price. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight, based on 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet 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 is easily evaporated, 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, and most preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

  When the pigment is subjected to salt milling, a resin may be added as necessary. The type of resin to be 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, preferably 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 color filters of the present invention can contain any of various dye derivatives known in the prior art. Examples of dye derivatives include organic pigments, anthraquinones, acridones or triazines, compounds having a basic substituent, an acid substituent, or a phthalimidomethyl group which may have a substituent, for example, 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A 2001-335717, JP-A 2003- 128669, JP-A 2003-167112, JP-A 2004-091497, JP-A 2004-307854, JP-A 2007-156395, JP-A 2008-094873, JP-A 2008-094986 Publication No. 2008-095007 Publication No. 2008-19591 JP, but it is not limited to be used those described in Japanese Patent No. 4585781 Patent Publication. The pigment derivative may be added at the time of pigmentation such as salt milling, or may be added at the time of dispersion.

<Dispersant [A]>
The coloring composition for color filters of this invention makes a block copolymer [A1] mentioned later an essential component as a dispersing agent.

<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 site and an anionic site in the same side chain. It has a zwitterionic structure.
Yes the general formula X ⁺ is in (1), and A blocks having a structure represented by the following general formula (2) or the following general formula (3), the repeating structural unit represented by the general formula (1) It is a dispersing agent containing the block copolymer (B) which consists of not B blocks.
Due to the high polarity of the A block having the repeating structural unit represented by the general formula (1), not only can the pigment be miniaturized by strongly adhering (adsorbing) to the surface of the pigment or dye derivative, but also the developability and substrate adhesion Can be excellent. As for 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 to R ¹² and * ² represents a bond to R ¹³ . ]

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

As the divalent linking group which is R ¹² and R ¹³ in the general formula (1), a divalent hydrocarbon group, a divalent hydrocarbon group and a linking group containing atoms other than a carbon atom and a hydrogen atom are combined And groups in which some of the hydrogen atoms of these groups are substituted with halogen atoms. In addition, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
As such a divalent linking group, for example, 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 And at least one selected from an alkanediyl group and an arylene group having 6 to 20 carbon atoms, and -O-, -S-, -COO-, -CONRb- (wherein R b is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) And at least one selected from —SO ₂ — and the like.

  The alkanediyl group having 1 to 10 carbon atoms may be linear or branched and, for example, methylene group, ethylene group, ethane-1,1-diyl group, propane-1,1-diyl group, 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, decane-1,10- The C1-C10 alkanediyl groups, such as a diyl group, can be mentioned.

  As an arylene group, C6-C12 arylene groups, such as a phenylene group, a naphthylene group, a biphenylene group, an anthrylene group, can be mentioned.

  The arylenealkanediyl group is a divalent group formed by combining an arylene group and an alkanediyl group, and examples thereof include phenylenemethylene group, phenylenedimethylene group, phenylenetrimethylene group, phenylenetetramethylene group, and phenylenepentamethylene group. And phenylene C1-6 alkanediyl groups such as phenylene hexamethylene group.

In addition, 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 . indicates the number 1-8 alkyl group) and the -SO ₂ - is in combination with at least one group selected from the alkanediyl group and arylene group having 6 to 20 carbon atoms having 1 to 10 carbon atoms A group formed by combining 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 carbons and a 6 to 20 carbons are preferable. More preferred is a group formed by combining at least one selected from arylene groups and at least one selected from -O- and -SO _2- . Note that specific examples of the alkyl group having 1 to 8 carbon atoms according to R b include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, A hexyl group, a heptyl group, an octyl group etc. can be mentioned.

Among them, as the divalent linking group for R 12, an alkanediyl group having 1 to 10 carbons, an arylene group having 6 to 20 carbons, or an alkanediyl group having 1 to 10 carbons and an arylene having 6 to 20 carbons A group formed by combining at least one group selected from groups and at least one group selected from -O-, -S-, -COO-, -CONRb- and -SO _2- is preferable, and has 6 to 10 carbon atoms Or at least one selected from an arylene group, an alkanediyl 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- More preferred is a group formed by combining one species.
Incidentally, at least one selected from the arylene group having 6 to 20 alkanediyl group and the number of carbon atoms of 1 to 10 carbon atoms, -O -, - S -, - COO -, - CONRb- and -SO ₂ - selected from In a group formed by combining at least one of them, it is preferable that an alkanediyl group having 1 to 10 carbon atoms be 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.
As the divalent linking group for R ^13, an alkanediyl group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms or is arylene alkanediyl group having 7 to 20 carbon atoms is preferable, a carbon number 1 An alkanediyl group of 5 to 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 more preferable.

The cationic divalent linking group represented by 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) is there. Further, R ²¹ , R ²² , R ³¹ and R ³² are preferably monovalent aliphatic hydrocarbon groups, 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 according to the application. . 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 isomyristyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate;
Cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, tertiary butyl cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate;
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;
(Meth) 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 ester Such as polyethylene glycol (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, polyethylene glycol monostearyl ether (meth) acrylate, and octoxy polyethylene glycol-polypropylene glycol (meth) acrylate (Poly) alkylene glycol monoalkyl ether (meth) acrylates;
Phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, paracumyl phenoxyethyl (meth) acrylate, paraquat Mil phenoxy ethylene glycol (meth) acrylate, paracumyl phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polypropylene glycol (meth) acrylate, and nonyl phenoxy poly (ethylene glycol-propylene glycol) (meta) ) Having an aromatic ring such as acrylate (poly) Ruki glycol (meth) acrylates;
Alkyloxy such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane (Meth) acrylates having a silyl group;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
N-substituted (meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloyl morpholine; And nitriles such as (meth) acrylonitrile.

And styrenes such as styrene and 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.

  Furthermore, a carboxyl group-containing ethylenically unsaturated monomer may be used in combination, for example, (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, succinic acid mono [2- (meth) acrylic acid Unsaturated monocarboxylic acids such as leuoxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc .; maleic acid, maleic anhydride, fumaric acid, itaconic acid And unsaturated dicarboxylic acids such as itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid, or anhydrides thereof.

  In addition, 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- (Meth) acrylates having a tertiary amino group such as dimethylaminopropyl (meth) acrylate and N, N-diethylaminopropyl (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (Meth) acrylamides having a tertiary amino group such as (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide; and dimethylaminostyrene, diethylaminostyrene, etc. Can be mentioned. Among them, an ethylenically unsaturated monomer selected from the group consisting of benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and hydroxyethyl (meth) acrylate is preferable.

<Method of producing block copolymer [A1]>
The block copolymer [A1] used in the present invention may be any copolymer consisting of the A block and the B block as described above, and it may be an AB block, a BAB block, or an AB- A is preferable, and A-B block and B-A-B block can be more preferably used. Such block copolymers are prepared, for example, by the living polymerization method described below. Here, the living polymerization is a polymerization method for easily synthesizing a block polymer and a resin having a uniform molecular weight, because side reactions which occur in general radical polymerization are suppressed, and further, polymerization growth occurs uniformly. The molecular weight of the polymer and the ratio of block copolymerized monomers can be freely controlled by the preparation ratio of the polymerization initiator and the vinyl monomer added at the time of polymerization, and block polymer, gradient polymer, star polymer, comb polymer, and further Can be used to produce end-functionalized 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 are developed, and research and development are widely performed. Nitroxide method (Nitroxide mediated polymerization: NMP method) using dissociation and coupling of amine oxide radical (refer to Reference 1 and Reference 2). Atom transfer radical polymerization (ATRP method) in which a halogen compound is polymerized as an initiation compound using a heavy metal such as copper, ruthenium, nickel, or iron and a ligand that forms a complex therewith (Reference 2) See references 3 and 4). Reversible addition-fragmentation chain transfer (RAFT method) in which a dithiocarboxylic acid ester or a xanthate compound is used as an initiating compound to polymerize using an addition polymerizable monomer and a radical initiator (Reference: RAFT method) 5) and Macromolecular Designvia Interchange of Xanthate (MADIX method) (see reference 6). Methods using heavy metals such as organic tellurium, organic bismuth, organic antimony, antimony antimony, organic germanium, germanium germanium and the like (Degenerative transfer: DT method) (see Reference 7 and Reference 8), etc. may be mentioned. It is not limited to these.

(Reference 1) Chemical Review (2001) 101, 3661
(Reference 2) Macromolecules, 1994, 27, 7228
(Reference 3) JP-A 2000-500516 (Ref. 4) JP-2000-514479 (Ref. 5) Chemical Review (2001) 101, 3689
(Reference 6) JP-A-2000-515181 (Reference 7) International Publication WO 1999-05099 Reference (Reference 8) JP 2007-277533 (Reference 9) Journal of American Chemical Society (2002) ) 124 2874

  Among these radical living polymerization methods, atom transfer radical polymerization method (ATRP method) and nitroxide method (NMP method) can be applied not only to control of molecular weight and molecular weight distribution of polymer but also to a wide range of monomers It is preferable at the point which can adopt the polymerization temperature applicable to the point and the existing equipment, and further, the nitroxide method (NMP method) is more preferable at the point which does not use the transition metal etc. which may become causes, such as coloring.

[Atom transfer radical polymerization method (ATRP method)]
The atom transfer radical polymerization method is carried out using a transition metal complex such as copper, ruthenium, iron or nickel as a redox polymerization catalyst. Specific examples of transition metal complexes include low valence transition metal halides such as copper (I) chloride copper (I) bromide.

  An organic ligand is used for the transition metal complex. Organic ligands are used to enable solubility in the polymerization solvent and reversible conversion of the redox polymerization catalyst. As a coordination atom of the transition metal, a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom and the like can be mentioned.

  As the initiator used for the atomic radical polymerization method, known ones can be used, but mainly organic halides having high reactivity carbon halogen bond, halogenated sulfonyl compounds and the like are used. Specific examples thereof include ethyl bromoisobutyrate, ethyl bromobutyrate, ethyl chloroisobutyrate, ethyl chlorobutyrate, paratoluenesulfonic acid chloride, 1-bromoethylbenzene, chloroethylbenzene and the like. These are used alone or in combination.

[Nitroxide method (NMP method)]
The nitroxide-mediated living radical polymerization method is carried out using a stable nitroxy free radical (= N-O.) As a radical capping agent. The stable nitroxy free radical is not particularly limited. 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 And 3,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamine oxy radical and the like. Instead of the nitroxy free radical, a stable free radical such as galvinoxyl free radical may be used.

  The radical capping agent is used in combination with a radical polymerization initiator. Although the combined use ratio of both is not specifically limited, 0.1-10 mol of radical initiators are suitable with respect to 1 mol of radical capping agents.

  Although the said radical polymerization initiator is suitably selected according to the weight average molecular weight (Mw) of resin synthesize | combined, (meth) acryloyl group in the monomer used when synthesize | combining copolymer [A1] It is used in a ratio of 0.0001 to 1 mole, preferably 0.001 to 0.1 mole, per 1 mole.

Although a well-known thing can be used as a radical polymerization initiator, If it is a compound which can generate | occur | produce a radical on polymerization temperature conditions, there will be no restriction | limiting in particular. For example, di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-di (t) -Dialkylperoxides such as butylperoxy) hexin-3;
peroxy esters such as t-butyl peroxybenzoate, t-butyl peroxy acetate, 2,5-dimethyl-2,5-di (benzoyl peroxy) 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- Peroxyketals such as butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) barate, etc .;
Hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylcyclohexane-2,5-dihydroperoxide;
Diacyl peroxides such as benzoyl peroxide, decanoyl peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide;
Organic peroxides such as peroxydicarbonates such as bis (t-butylcyclohexyl) peroxydicarbonate, or mixtures thereof.

  Moreover, an azo compound can also be used as a radical polymerization initiator. For example, 2,2′-azobisbutyronitriles such as 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis (2-methylbutyronitrile), 2, 2, 2,2′-azobisvaleronitriles such as 2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 ′ 2,2'-azobispropionitriles such as -azobis (2-hydroxymethylpropionitrile), 1,1'-azobis-1- such as 1,1'-azobis (cyclohexane-1-carbonitrile) and the like Alkane nitriles can be used.

  Furthermore, as reported in Macromolecules 1995, 28, 2993, instead of using a radical capping agent and the above-mentioned radical polymerization initiator in combination, an alkoxyamine compound represented by the following compounds (N-1 to 4) is started You may use as an agent.

  In the process for producing a block copolymer and / or a B-A-B block copolymer comprising an A block having a zwitterionic structure in a side chain and a B block having no zwitterionic structure according to the present invention, Solventless or optionally solvent can be used. As a solvent, for example, 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, ethylene Although glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, or diethylene glycol monobutyl ether acetate is used, it is not particularly limited thereto. These polymerization solvents may be used as a mixture of two or more.

[Method of producing polymer (A)]
The polymer (A) containing the repeating unit represented by General formula (1) can be obtained using a well-known synthesis method, and a manufacturing method is not specifically limited. The following method (i
) (Ii).
<Manufacturing method (i)>
The method of polymerizing the ethylenically unsaturated monomer (b1) which is a precursor of the repeating unit represented by General formula (1), and another ethylenically unsaturated monomer (b3) by well-known polymerization reaction.
<Manufacturing method (ii)>

Into an intermediate polymer (a) obtained by a known polymerization method, an ethylenically unsaturated monomer (b2) capable of reacting with the modified species (b4) and another ethylenically unsaturated monomer (b3), A method of reacting modified species (b4).

«Production method (i)»
As an ethylenically unsaturated monomer (b1) which is a precursor of the repeating unit represented by General formula (1), the monomer represented by the following general formula (4) is mentioned.
(Ethylenically 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 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 a bond with R ^42, and * ² represents a bond with R ⁴³ .

[In the general formula (6), R ⁶¹ and R ⁶² each independently represent a monovalent organic group.
* ¹ represents a bond with R ^42, and * ² represents a 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。 As a compound represented by General formula (4), the compound like the following (4-1 to 4-16) is mentioned, for example.

Among them, compounds (4-1), (4-2), (4-5), (4-6), (4-9), (4-10), (4-13) and (4-14) are compounds. Preferably, compounds (4-1), (4-5), (4-9), (4-10), (4-13), (4-14) are more preferable, and still more preferably (4-4). 9), (4-10), (4-13), (4-14), and most preferably (4-9).

(Other ethylenic unsaturated monomers (b3))
As another ethylenic unsaturated monomer (b3), an acrylic monomer and monomers other than an acrylic monomer are mentioned.
As an 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 ethyl hexyl (meth) acrylate, stearyl (meth) acrylate, and lauryl (meth) acrylate;
Alicyclic resins such as cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl oxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate Formula alkyl (meth) acrylates;
(Meth) acrylates having a heterocyclic substituent such as tetrahydrofurfuryl (meth) acrylate and 3-methyl oxetanyl (meth) acrylate;
(Meth) acrylates having an aromatic substituent such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethylene oxide modified (meth) acrylate, and paracumylphenoxyethylene oxide modified (meth) acrylate;
Methoxypolypropylene glycol (meth) acrylate, and alkoxypolyalkylene glycol (meth) acrylates such as ethoxy polyethylene glycol (meth) acrylate; and
(Meth) acrylamide (In addition, when it describes as "(meth) acrylamide", acrylamide and / or methacrylamide shall be shown. The following is the same.), N, N- dimethyl (meth) acrylamide, N, N -(Meth) acrylamides, such as -diethyl (meth) acrylamide, N- isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloyl morpholine, etc. are mentioned.

Moreover, as monomers other than the said 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 said monomers other than an acrylic monomer can also be used together with the said acrylic monomer.

  Moreover, a carboxyl group-containing ethylenically unsaturated monomer can be used alone or in combination with the above-mentioned monomer.

As a carboxyl group-containing ethylenic unsaturated monomer, for example,
It is possible to select one or two or more species from acrylic acid, methacrylic acid, ε-caparolactone-added acrylic acid, ε-couplerolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc. .

«Production method (ii)»
Examples of the ethylenically unsaturated monomer (b2) capable of reacting with the modified species (b4) described later include monomers represented by the following general formula (7), and the like.

〔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 formula (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 ), or —P (R ⁷⁵ ) (R ⁷⁶ ), or the following general formula (8), and R ^{73 to} R ⁷⁶ are each independently And 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 for R ⁷² in the general formula (7) has the same meaning as the divalent linking group for R ¹² in the general formula (1).
The monovalent organic group in R ^{73 to} R ⁷⁶ in the general formula (7) has the same meaning as the monovalent organic group in the general formulas (2) and (3).
The monovalent organic group in R ⁸¹ and R ⁸² in the general formula (8) has the same ^{meaning as} the monovalent organic group in R ³¹ and R ³² of the general formula (3).

Specific examples of the ethylenically unsaturated monomer (b2) represented by the general formula (7) are
N, N-Dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, 2,2,2, (Meth) acrylates having a secondary or tertiary amino group such as 6,6-tetramethyl piperidyl methacrylate, 1,2,2,6,6-pentamethyl piperidyl methacrylate;
Tertiary such as N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide (Meth) acrylamides having an amino group;
And the like, and preferably, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (methacrylate), N, N-dimethylaminopropyl (meth) acrylamide, 1,2,2,6, 6-pentamethyl piperidyl methacrylate, particularly preferably 1,2,2,6,6-pentamethyl piperidyl methacrylate.

(Other ethylenic unsaturated monomers (b3))
The other ethylenically unsaturated monomer (b3) is the same as the ethylenically unsaturated monomer (b3) in the production method (i).

(Denatured species (b4))
As the modified species (b4), it is possible to react with Z in the general formula (7) which is a constituent unit of the polymerization intermediate polymer (a), and after the reaction, it is particularly preferable to give the structure of the general formula (1) There is no limitation, and examples thereof include a compound represented by the following general formula (9), a compound represented by the following general formula (10), and the like.

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 Formula (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, fluoroacetic acid, bromoacetic acid, iodoacetic acid, chloropropionic acid, fluoropropionic acid, bromopropionic acid, iodopropionic acid, chlorobutanoic acid, fluorobutanoic acid Bromobutanoic acid, iodobutanoic acid chloromethanesulfonic acid, fluoromethylsulfonic acid, bromomethanesulfonic acid, iodomethanesulfonic acid, chloropropanesulfonic acid, fluorinated propanesulfonic acid, bromopropanesulfonic acid, iodopropanesulfonic acid, chlorobutanesulfone acid Acid, fluorinated butanesulfonic acid, bromobutanesulfonic acid, iodobutanesulfonic acid chloromethanephosphonic acid, fluorinated methylphosphonic acid, bromomethanephosphonic acid, iodomethanephosphonic acid, chloropropanephosphonic acid, fluorinated propanephos acid Phosphate, bromopropane phosphonic acid, iodopropane acid, chloro butanoic acid, fluoride Butanhosuhon acid, bromo butanoic acid, but such iodo butane phosphonic acid,
Bromoacetic acid, chloropropionic acid and chloroacetic acid are preferred, among which chloroacetic acid is particularly preferred.

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

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

  The amount of the solvent to be used is preferably 10 to 300 parts by weight, and more preferably 50 to 100 parts by weight with respect to 100 parts by weight of the monomer consisting of A block and B block. The solvent used may be removed after completion of the reaction by an operation such as distillation, or may be used as it is as part of the product of the composition.

  The content of the block A (a block containing a partial structure having an amphoteric ion structure represented by the general formula (1)) is preferably 1% by weight to 99% by weight based on the solid content of the block copolymer [A1]. Furthermore, it is preferable to contain 20 weight%-80 weight%, and it is preferable to contain 20 weight%-50 weight% especially. 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, when the B block is compatible with the solvent which is the dispersion medium, the pigment can be stably present in the dispersion medium. Furthermore, 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, whereby the dispersion stability is further improved.

The content of the repeating unit represented by the general formula (1) is preferably 1 to 100% by weight, more preferably 20 to 100% by weight, based on A block (100% by weight) contained in the block copolymer [A1]. It is preferable to contain by weight to 100% by weight, and it is particularly preferable to contain 50 to 100% by weight. Since the repeating unit represented by the general formula (1) acts as a pigment adsorptive group, the dispersibility is improved by the content ratio as described above. Further, the remaining 0 to 50% by weight of the monomer in the A block is preferably an ethylenically unsaturated monomer having an amino group, but the ethylenically unsaturated monomer having no amino group is preferred. It is possible to copolymerize even a monomer.

  In addition, the molecular weight of the block copolymer [A1] of the present invention is preferably in the range of usually 3,000 or more and 20,000 or less, more preferably 5,000 or more and 15,000 or less in terms of weight average in terms of polystyrene. A range of 7,000 or more and 12,000 or less is particularly preferable. When the molecular weight of the block copolymer is less than 3,000, the dispersion stability tends to decrease, and when 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. If the blending 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 the amount is more than 50 parts by weight, the alkali developability may be lowered when using a pigment dispersion resist containing the pigment dispersion composition and forming a pixel pattern of a color filter by photolithography.

<Dispersants other than block copolymer [A1]>
In the coloring composition for color filters in the present invention, dispersants other than the block copolymer [A1] can be used in combination. It has a colorant affinity site that has the property of adsorbing to the added colorant, and a site that is compatible with the colorant carrier, and functions to be adsorbed to the added colorant and stabilize the dispersion in the colorant carrier It is a thing. Specific examples of the dispersant include dispersants having an aromatic carboxyl group, polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts , Polycarboxylic acid alkylamine salt, polysiloxane, long chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, and reaction of poly (lower alkyleneimine) with polyester having free carboxyl group Oil-based 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 And water soluble resins such as polyvinyl pyrrolidone and water soluble polymers , Polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, phosphates, etc., which may be used alone or in combination of two or more, but are not necessarily limited thereto. It is not a thing.

  Examples of commercially available dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 154, 161, 162, 163, 164, 165, 166, 167, 168 manufactured by Big Chemie Japan. , 170, 171, 174, 180, 181, 182, 183, 185, 190, 2000, 2001, 2020, 2025, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-TeRRa-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen et al., SOLSPERSE-3000, 9000, 11200, 13000, 1 manufactured by Japan Lubrizol Corporation. 240, 13650, 13940, 16000, 17000, 18000, 20000, 20000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 3300, 32500, 34750, 35100, 35200, 36500, 37500, 38500, 38500, 38500 39000, 41000, 41090, 53095, 56000, 55000, 7100, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080 , 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5066, 5070, 7500, 7554, 1101, 150, 1501, 1502, 1503, etc. Ajinomoto Fine Techno Co., Ltd. Ajispar PA111, PB711, PB821, PB822 , PB 824 and the like.

<Binder resin>
The binder resin is one in which a coloring agent is dispersed, or one in which a salt-forming compound is dyed and permeated, and examples thereof include a thermoplastic resin and a thermosetting resin.

  As a thermoplastic resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin And polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin modified maleic resin, rosin modified fumaric 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 range of 400 to 700 nm in the visible light range. Moreover, since the coloring composition for color filters of this invention is a form of alkali development type coloring resist material, it is preferable to use the alkali-soluble vinyl-type resin which copolymerized the acidic group containing ethylenic unsaturated monomer.

  As alkali-soluble resin which copolymerized the acidic group containing ethylenic unsaturated monomer, resin which has acidic groups, such as a carboxyl group and a sulfone group, is mentioned, for example. Specifically as an alkali-soluble resin, an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or An isobutylene / (anhydride) maleic acid copolymer etc. are mentioned. Among them, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, in particular an acrylic resin having an acidic group, is preferably used because it has high heat resistance and transparency.

  In order to improve the photosensitivity of an alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenic non-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, since this has the effect of improving the solvent resistance of the resist material.

  As active energy ray curable resin which has an ethylenically unsaturated double bond, resin which introduce | transduced the unsaturated ethylenic double bond by the method of (a)-and (c) shown below, for example is mentioned.

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

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

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano-substituted, etc. Monocarboxylic acids and the like can be mentioned, and these may be used alone or in combination of two or more.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, which may be used alone or in combination of two or more. I do not mind. The remaining anhydride is obtained by using tricarboxylic acid anhydride such as trimellitic acid anhydride or using tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride, if necessary, such as increasing the number of carboxyl groups. It is also possible to hydrolyze the group. In addition, when tetrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as a polybasic acid anhydride, the unsaturated ethylenic double bond can be further increased.

[Method (b)]
As a similar method of method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added 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 the unsaturated ethylenic monomer having an epoxy group are generated as compared with the method (a). When the resin having a cationic group in the side chain, which is used when obtaining the salt forming compound of the present invention, contains oxetanyl group or t-butyl group as a thermally crosslinkable functional group, the method is used as a binder resin ( Use of the resin obtained by b) is preferable because it exhibits higher heat resistance.

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

  As the unsaturated ethylenic monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol (Meth) acrylates or hydroxyalkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate may be mentioned, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and / or butylene oxide etc. to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) ester mono (meth) acrylates to which (poly) 12-hydroxystearic acid or the like is added can also be used. From the viewpoint of coating foreign matter suppression, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferred.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethylisocyanate or 1,1-bis [(meth) acryloyloxy] ethylisocyanate, but are not limited thereto. Alternatively, two or more types can be used in combination.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, and more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. 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 using binder resin as a photosensitive composition, it is preferable to use resin of an acid value of 20-300 mgKOH / g from a dispersibility of a pigment and a salt-forming compound, permeability, developability, and a heat resistance viewpoint. If the acid value is less than 20 mg KOH / g, the solubility in a developer is poor, and it is difficult to form a fine pattern. If it exceeds 300 mg KOH / g, fine patterns may not be left.

  The binder resin is preferably used in an amount of 30% by weight or more based on the total weight of the coloring agent (100% by weight) because the film forming property and the various resistances are good, and the coloring agent concentration is high and good. It is preferable to use it in an amount of 500% by weight or less because it can exhibit color characteristics.

(Thermosetting compound)
In the present invention, a thermosetting compound may be further included in combination with the thermoplastic resin which is a binder resin. As a thermosetting compound, for example, an epoxy compound and / or a resin, an oxetane compound and / or a resin, a benzoguanamine compound and / or a resin, a rosin modified maleic acid compound and / or a resin, a rosin modified fumaric acid compound and / or a resin Although a melamine compound and / or resin, a urea compound and / or resin, a phenol compound and / or resin are mentioned, this invention is not limited to this.

<Organic solvent>
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and infiltrated into the coloring agent carrier, and the coloring film is coated by applying a dry film thickness of 0.2 to 5 μm on a substrate such as a glass substrate. An organic solvent is included to facilitate formation. The organic solvent is selected in consideration of the solubility of each component of the coloring composition as well as the safety, as well as the application property of the coloring composition is good.

  As an organic solvent, for example, ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl- 1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-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-butyl Benzene, n-propyl acetate, 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 monotertiary 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, 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 monomethyl ether Chill 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, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, Acetic acid Propyl, and dibasic acid esters. These solvents may be used alone or in combination of two or more at an arbitrary ratio as needed.

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

  In addition, the organic solvent is used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the coloring agent because it can adjust the coloring composition to an appropriate viscosity and form a colored film having an intended uniform film thickness. Is preferred.

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

  Examples of monomers and oligomers that cure by ultraviolet light and heat to form a transparent resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 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, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglyci Ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca (Meth) acrylates, ester acrylates, (meth) acrylic esters of methylolated melamine, epoxy (meth) acrylates, urethane acrylates and other various acrylic esters and methacrylic esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, rh (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. These photopolymerizable compounds can be used alone or in combination of two or more at an arbitrary ratio as needed.

  The compounding 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 It is more preferable that

<Photoinitiator>
The color composition for color filters of the present invention is a solvent-developable or alkali-developable colored resist material to which a photopolymerization initiator or the like is added when the composition is cured by ultraviolet irradiation to form a filter segment by photolithography. It can be prepared in the form of The compounding amount when using the photopolymerization initiator is preferably 5 to 200% by weight based on the total amount of the colorant (100% by weight), and 10 to 150% by weight from the viewpoint of photocurability and developability More preferably, it is%.

  As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-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) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or ben Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropyl thioxanthone, or 2,4-diethyl thioxanthone Thioxanthone compounds of the formula: 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-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- (4 Triazine compounds such as' -methoxystyryl) -6-triazine; 1- (N-4-benzoylphenyl-carbazol-3-yl) -butane-1,2-dione-2-oxy -O-acetate, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl]-, 1- (0-acetyloxime), or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxyl Oxime ester compounds such as amines; phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide or 2,4,6-trimethylbenzoyl diphenyl phosphine oxide; 9,10-phenanthrenequinone Quinone compounds such as camphor quinone and ethyl anthraquinone; borate compounds; carbazole compounds; A zole-based compound; or a titanocene-based compound or the like is used.

  These photopolymerization initiators can be used alone or in combination of two or more at an arbitrary ratio as required. The content of these photopolymerization initiators is preferably 5 to 200% by weight based on the total amount (100% by weight) of the colorant in the coloring composition for color filter, and from the viewpoint of photocurability and developability, 10 It is more preferable that it is -150 weight%.

<Sensitizer>
Furthermore, the coloring composition for color filters of the present invention can contain a sensitizer. As sensitizers, unsaturated ketones represented by chalcone derivatives, dibenzalacetone etc., 1,2-diketone derivatives represented by benzyl and camphorquinone etc., benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapyrazino porphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalylo porphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrilium derivative, tetraphyrin derivative, anurene derivative, spiropyran derivative, spirooxazine Derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester, acyl phosphine oxide, methylphenyl glyoxylate, benzyl, 9, 10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone , 4,4'-diethylaminobenzophenone and the like.

  More specifically, edited by Ogawara Shin et al., "Dye Handbook" (1986, Kodansha), edited by Ogawara Shin et al., "Chemicals of functional dyes" (1981, CMC), edited by Ikemori Tadajiro et al. Specific examples thereof include, but are not limited to, the sensitizers described in “Specially functional materials” (1986, CMC). In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be contained.

  Two or more types of sensitizers may be used at an arbitrary ratio as needed. The compounding amount at the time of using the sensitizer is preferably 3 to 60% by weight based on the total weight (100% by weight) of the photopolymerization initiator contained in the coloring composition, and photocurable, The content is more preferably 5 to 50% by weight from the viewpoint of developability.

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

  As such an amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethyl paratoluidine etc. are mentioned.

<Leveling agent>
It is preferable to add a leveling agent to the colored composition of the present invention in order to improve the leveling properties of the composition on a transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by BYK Chemie, and the like. As a specific example of dimethylsiloxane which has a polyester structure in a principal chain, BYK-310 by BYK-Chemie company, BYK-370, etc. are mentioned. The dimethylsiloxane having a polyether structure in the main chain and the dimethylsiloxane having a polyester structure in the main chain can also be used in combination. In general, the content of the leveling agent is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a low solubility in water while having a hydrophilic group, and when it is added to a coloring composition, It is characterized by low surface tension reduction ability, and in addition to low surface tension reduction ability, it is useful that the wettability to the glass plate is good, and the addition amount at which defects of the coating film due to foaming do not appear. Those which can sufficiently suppress the chargeability can be preferably used. As a leveling agent which has such a preferable characteristic, dimethylpolysiloxane which has a polyalkylene oxide unit can use it preferably. The polyalkylene oxide unit may be a polyethylene oxide unit or a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit to dimethylpolysiloxane is a pendent type in which the polyalkylene oxide unit is bonded to a repeating unit of dimethylpolysiloxane, a terminal-modified type bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane It may be any of linear block copolymer types alternately and repeatedly bonded. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2203. -2-207, but not limited thereto.

  The leveling agent may be supplemented with an anionic, cationic, nonionic or amphoteric surfactant. The surfactant may be used as a mixture of two or more.

  Examples of anionic surfactants to be added to leveling agents include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphoric acid Ester etc. are mentioned.

  Examples of the cationic surfactant added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. As a nonionic surfactant which is added to the leveling agent as auxiliaries, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate And alkylbetaines such as alkyldimethylaminoacetic acid betaines; amphoteric surfactants such as alkylimidazolines; and fluorine-based 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.

  As an epoxy compound, phenol novolac epoxy resin, cresol novolac epoxy resin, trishydroxyphenylmethane epoxy resin, dicyclopentadiene phenol epoxy resin, bisphenol-A epoxy resin, bisphenol-F epoxy resin, biphenol epoxy Resin, bisphenol-A novolac epoxy resin, naphthalene skeleton-containing epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin and the like can be mentioned.

  Specific examples of the phenol novolac epoxy resin include, for example, Epiclon N-740, Epiclon N-770, Epiclon N-775 manufactured by DIC Corporation, D.C. E. N438, RE-306 manufactured by Nippon Kayaku Co., Ltd., jER152 manufactured by Mitsubishi Chemical Corporation, jER154 and the like.

  Specific examples of the cresol novolac epoxy resin include Epiclon N-660, Epiclon N-665, Epiclon N-670, Epiclon N-673, Epiclon N-680, Epiclon N-695, Epiclon N-665, manufactured by DIC Corporation. EXP, Epiclon N-672-EXP, Nippon Kayaku Co., Ltd. EOCN-102S, EOCN-103S, EOCN-104S, Union Carbide Co., Ltd. UVR-6650, Sumitomo Chemical Co., Ltd. ESCN-195 etc. are mentioned.

  Specific examples of trishydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H, manufactured by Nippon Kayaku Co., Ltd., TACTIX-742, manufactured by Dow Chemical Co., jER E1032H60, manufactured by Mitsubishi Chemical Co., Ltd., etc. It can be mentioned.

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

  Specific examples of the bisphenol-type epoxy resin include jER 828 and jER 1001 manufactured by Mitsubishi Chemical Co., Ltd., UVR-6410 manufactured by Union Carbide Co., Ltd., D. E. R-331, bisphenol-A type epoxy resin such as YD-8125 manufactured by Nippon Steel Epoxy Co., Ltd., UVR-6490 manufactured by Union Carbide Corporation, bisphenol-F type such as YDF-8170 manufactured by Nippon Steel Epoxy Manufacturing Co., Ltd. An epoxy resin etc. are mentioned.

  Specific examples of the biphenol type epoxy resin include biphenol type epoxy resins such as Nippon Kayaku Co., Ltd. NC-3000, NC-3000H, and bixylenol type epoxy resins such as jER YX-4000, jER YL-6121 etc. Resin etc. are mentioned.

  Specific examples of the bisphenol A novolac epoxy resin include Epiclon 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. and EXA-4750 manufactured by DIC Corporation.

  As a specific example of an alicyclic epoxy resin, Daicel Co., Ltd. make Sekicide 2021P, 2081, 2000, Epolide PB3600, PB4700, GT401, EHPE-3150, cyclomer M100 grade | etc., Etc. are mentioned.

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

  These epoxy compounds may be used alone or in combination of two or more at an arbitrary ratio as needed.

  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 is 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 one having a monofunctional oxetane group, one having a bifunctional oxetane group, and one having a bifunctional or more oxetane group.

As the monofunctional oxetane group, (3-ethyl oxetan-3-yl) methyl acrylate, (3-ethyl oxetan-3-yl) methyl methacrylate, 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl- 3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-methacryloxymethyl) oxetane, 3-ethyl-3-{[3- (3- Triethoxysilyl) propoxy] methyl} oxetane etc. are mentioned.
As a specific example, OXE-10 by Osaka Organic Chemical Industry Co., Ltd., OXE-30 OXT-101, 212 etc. by Toagosei Co., Ltd. are mentioned.

When the oxetane group is bifunctional, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl), 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-hydroxymethyl oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3,7-bis (3-) Oxetanyl) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ene Ethyl-3-oxetanylmethoxy) methyl] propane, ethyleneglycose bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis (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 bis Henol 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) And EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether and the like.
As a specific example, Ube Industries, Ltd. make, OXBP, OXTP, Toagosei Co., Ltd. make OXT-121, OXT-221 grade | etc., Is mentioned.

As the oxetane group having two or more functional groups,
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-oxetanylmethyl) ether, caprolactone modified di Pentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, oxe Resin (e.g., Patent No. 3,783,462 No. oxetane-modified phenol novolak resin according) containing Tan group or above, such as OXE-30 (meth) polymers obtained by the acrylic monomer by radical polymerization. Such polymers can be obtained using known polymerization methods.

  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, in 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 is obtained, which is preferable.

<Hardening agent, hardening accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening agent, the hardening accelerator, etc. as needed. As a curing agent, a phenolic resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound and the like are effective, but not particularly limited thereto, a thermosetting resin Any curing agent may be used as long as it can react with it. Among these, a compound having two or more phenolic hydroxyl groups in one molecule, and an amine curing agent are preferably mentioned. Examples of the curing accelerator include amine compounds (for example, 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 amidine compounds and salts thereof (eg, Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- The -4- methylimidazole etc., phosphorus compounds (eg triphenylphosphine etc.), guanamine compounds (eg melamine, guanamine, acetoguanamine, benzoguanamine etc.), s-triazine derivatives (eg 2,4-diamino-6) -Methacryloyloxyethyl-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>
In addition, 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 in 100% by weight of the total of the photopolymerization initiator and the ultraviolet absorber. When the content of the ultraviolet absorber is less than the above, the effect of the ultraviolet absorber is small and the resolution can not be ensured, and when the content is more than the above, the sensitivity is low and the pixel peeling and the hole diameter are larger than the design values May cause problems such as

  At this time, when the photosensitive coloring composition contains a sensitizer, the content of the photopolymerization initiator is determined to include the content of the sensitizer.

  The total content of the photopolymerization initiator and the ultraviolet light absorber is preferably 1 to 20% by weight in 100% by weight of the solid content of the photosensitive coloring composition. When the total content of the photopolymerization initiator and the ultraviolet light absorber is less than the above, the adhesion is weakened to cause peeling of the pixel. When the total content 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 is determined to include the content of the sensitizer.

  2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, octyl-3 [3-tert-butyl as a benzotriazole type organic compound -4-Hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H -Benzotriazol-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 of 2-methoxy-1-methylethyl acetate and 95% by weight of benzenepropanoic acid, 3- ( 2H-benzotriazol-2-yl)-(1,1-dimethylethyl) -4-hydroxy, compound of C7-9 side chain and linear alkyl esters, 2- (2H-benzotriazol-2-yl) -4 , 6-Bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3) , 3- tetramethylbutyl) phenol.

  More specifically, BASF "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. Be

  Examples of triazine organic compounds include 2- [4,6-di (2,4-xylyl) -1,3,5-triazin-2-yl] -5-octyloxyphenol and 2- [4,6-bis (2,4-Dimethylphenyl) -1,3,5-triazin-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-glycidic ester, 2,4-bis "2-hydroxy-4-butoxyphenyl" -6- (2,4-dibutoxyphenyl) -1,3-5-triazine and the like.

  More specifically, "KEMISORB 102" manufactured by Chemi-Pro Chemical, "TINUVIN 400" manufactured by BASF, "TINUVIN 405", "TINUVIN 460", "TINUVIN 477-DW", "TINUVIN 479", "TINUVIN 1577", "ADEKA STAB LA-46" and "ADEKA STAB LA-F70" by ADEKA, "CYASORB UV-1164" by Sun Chemical Co., etc. are mentioned.

Examples of benzophenone organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n- Examples include octoxybenzophenone, 2,2-dihydroxy-4-methoxybenzophenone and the like.

  More specifically, “KEMISORB 10”, “KEMISORB 11”, “KEMISORB 11S”, “KEMISORB 12”, “KEMISORB 111” manufactured by Chemi-Pro Chemical, “SEESORB 101”, “SEESORB 107” manufactured by Shipro Chemicals, Company-made "Adeka stub 1413" etc. is mentioned.

<Thiol chain transfer agent>
The coloring composition of the present invention may optionally contain a thiol chain transfer agent. By using a thiol-based chain transfer agent together with a photopolymerization initiator, in the radical polymerization process after light irradiation, it acts as a chain transfer agent and generates a thiyl radical which is less susceptible to inhibition of polymerization by oxygen, so the resulting colored composition It becomes high sensitivity.

  In addition, polyfunctional aliphatic thiols bonded to an aliphatic group such as methylene or ethylene having two or more SH groups are preferable. More preferably, they are polyfunctional aliphatic thiols having 4 or more SH groups. By increasing the number of functional groups, the polymerization initiation function is improved, and the surface of the pattern can be cured to near the substrate.

  As polyfunctional thiols, for example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bis thiopropio , Trimethylolpropane tristhioglycollate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethyl mercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dib Examples thereof include ethylamino) -4,6-dimercapto-s-triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

  These thiol chain transfer agents can be used alone or in combination of two or more.

  In addition, the content of the thiol chain transfer agent is preferably 1 to 10% by weight, and more preferably 2.0 to 8.0% by weight in the total solid content (100% by weight) of the photosensitive composition. is there. In this range, the effect of the chain transfer agent is increased, and the sensitivity, the tapered shape, the wrinkles, the film shrinkage ratio, etc. become good.

<Antioxidant>
The coloring composition of the present invention can contain an antioxidant. The antioxidant can increase the transmittance of the coating film because it prevents the composition contained in the coloring composition from being oxidized and yellowed due to a heat step during heat curing or ITO annealing. In particular, when the coloring agent concentration of the photosensitive coloring composition is high, the amount of the film crosslinking component decreases, and the yellowing of the heat process is strong to cope with the use of a highly sensitive crosslinking component and the increase of the photopolymerization initiator. Phenomenon is seen.
Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation in the heating step and to obtain a high transmittance of the coating film.

  In the present invention, the "antioxidant" may be a compound having an ultraviolet absorbing function, a radical trapping function, or a peroxide decomposing function, and specifically, hindered phenol type or hindered amine type as an antioxidant. And phosphorus, sulfur, benzotriazole, benzophenone, hydroxylamine, salicylic acid ester, and triazine compounds, and known ultraviolet light absorbers, antioxidants and the like can be used. Further, the antioxidant used in the present invention is preferably one containing no halogen atom.

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

Examples of hindered phenolic antioxidants include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di) -Tert-Butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-tert-butyl-4-4 Nonylphenol, 2,2'-Isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-Butylidene-bis- (2-t-butyl-5-methylphenol), 2,2'-thio- S- (6-t-Butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'-thiodiethyl bis- (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-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydro) And the like. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.
Specific examples include Adekastab AO-20, AO-30, AO-40, AO50, AO60, AO320 manufactured by ADEKA, KEMINOX 101, 179, 76, 9425 manufactured by Chemipro, IRGANOX 1010, 1035, 1076, 1098 manufactured by BASF. 1135, 1330, 1726, 1425 WL, 1520 L, 245, 259, 3114, 5057, 565, and sianox CY-1790 and CY-2777 manufactured by Sun Chemical Co., Ltd., and the like.

As the hindered amine antioxidant, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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-butane tetracarboxylate, 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-triazine-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)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-Pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomeric types having a hindered amine structure And poly Mar-type compounds can also be used.
Specifically, Adekastab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-82, LA-87, LA manufactured by ADEKA Corporation. -402F, LA-502XP, KAMISTAB 29, 62, 77, 29, 94, manufactured by Chemi-Pro Chemical, Tinuvin 249, TINUVIN 111 FDL, 123, 144, 292, 5100, manufactured by BASF, Siersorb UV-3346, manufactured by Sun Chemical Co., UV-3529, UV-3853 grade | etc., Is mention | raise | lifted.

As a phosphorus antioxidant, tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 'isopropylidene diphenol alkyl phosphite, tris nonyl phenyl phosphite, tris dinonyl phenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-Di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidene bis (3-methyl-) 6-t-Butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxy phosphonyloxy)-Ben Zen, ethyl phosphite bis (2,4-di-tert-butyl-6-methylphenyl) and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.
Specific examples thereof include Adekastab PEP-36, PEP-8, HP-10, Adekastab 2112, 1178, 1500, C, 3013, TPP, BASF IRGAFOS 168, Clariant Chemicals Hostanox P-EPQ, etc. .

As a sulfur-based antioxidant, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 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 thereof include Adekastab AO-412S and AO-503 manufactured by ADEKA, and KEMINOXPLS manufactured by Chemi-Pro Chemical.

As the benzotriazole-based antioxidant, compounds of oligomer type and polymer type having a benzotriazole structure can be used.
Specific examples thereof include Adekastab LA-29, LA-31 RG, LA-32, LA-36, -412S manufactured by ADEKA, KEMISORB 71, 73, 74, 79, 279 manufactured by Chemi-Pro Chemical, TINUVIN PS manufactured by BASF, 99- 2, 384-2, 900, 928, 1130 and the like.

Examples of benzophenone antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4. Octadecyloxy benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy- 4-methoxy-5 sulfo benzophenone, 2-hydroxy-4-methoxy-2'- carboxy benzophenone, etc. are mentioned. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.
Specific examples thereof include Adekastab 1413 manufactured by ADEKA Corporation, KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemi-Pro Chemical, UV-12 and UV-329 manufactured by Sun Chemical Co., and the like.

As a triazine type antioxidant, a 2, 4- bis (allyl) 6- (2-hydroxyphenyl) 1, 3, 5- triazine etc. are mentioned. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.
Specific examples thereof include Adekastab LA-46 and F70 manufactured by ADEKA, KEMISORB 102 manufactured by Chemi-Pro Chemical, TINUVIN 400, 405, 460, 477 and 479 manufactured by BASF, and Sieasorb UV-1164 manufactured by Sun Chemical Co., Ltd.

  Examples of the salicylate-based antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate and the like. In addition, oligomer type and polymer type compounds having a salicylate structure can also be used.

  These antioxidants can be used alone or in combination of two or more at an arbitrary ratio as required.

  The content of the antioxidant is more preferably 0.5 to 5.0% by weight in 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 can contain a storage stabilizer in order to stabilize the viscosity over time of the composition. Further, in order to enhance the adhesion to the transparent substrate, an adhesion improver such as a silane coupling agent may be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butyl pyrocatechol, tetraethyl phosphine, tetraphenyl phosphine and the like. Organic phosphine, phosphite and the like can be mentioned. Storage stabilizers can be used in amounts of 0.1 to 10% by weight, based on the total amount of colorant (100% by weight).

  Adhesion improvers include vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinylsilanes such as vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3,3, 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-aminopropyl trie Xysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and 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).

<Method of producing coloring composition>
The coloring composition of the present invention comprises three colorants, a dispersant, a colorant such as a binder resin, and / or a solvent, preferably a kneader together with a dispersion aid (a pigment derivative or a surfactant). It can be finely dispersed and manufactured using various dispersing means such as a roll mill, a two-roll mill, a ball mill, a sand mill, an annular type bead mill, or an attritor (colorant dispersion resistance). The colored composition of the present invention can also be produced by mixing pigments, salt-forming compounds, other colorants and the like separately dispersed in a colorant carrier. When the solubility of the coloring agent such as dye is high, specifically, the solubility in the solvent used is high, and if it is in a state where it is not dissolved by stirring and no foreign matter is confirmed, the finely dispersing step as described above is performed. It does not have to be.

  Moreover, when using as a photosensitive coloring composition for color filters (resist material), it can prepare as a solvent development type or an alkali development type coloring composition. The solvent-developable or alkali-developable coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, another dispersion aid, and an additive. 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, dispersion aids such as dye derivatives, dispersants, surfactants and the like can be suitably contained. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the coloring composition formed by dispersing the colorant in the colorant carrier using the dispersion aid has brightness, contrast and storage stability. Sex is good. The dye derivative and the dispersant are as described above.

<Surfactant>
As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; alkyl dimethylamino There may be mentioned amphoteric surfactants such as alkyl betaines such as betaine acetate and alkyl imidazolines, which may be used alone or in combination of two or more, but it is not necessarily limited thereto.

  When a surfactant is added, it is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. If the content of the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect, and if the content is more than 55 parts by weight, the dispersion may be influenced by the excess dispersant. .

<Removal of coarse particles>
The coloring composition of the present invention may be coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, by means of centrifugation, filtration with a sintered filter or membrane filter, and the like. It is preferable to carry out the removal of the mixed dust. Thus, the coloring composition preferably contains substantially no particles of 0.5 μm or more. More preferably, it is 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 comprises a red filter segment, a green filter segment, and a blue filter segment. Also, the color filter may further include a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment. In the color filter of the present invention, at least one of the red filter segment, the green filter segment, and the 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.

<Method of manufacturing color filter>
The color filter can be manufactured by a printing method or a photolithography method. Since formation of the filter segment by the printing method can be patterned only by repeating printing and drying of the coloring composition prepared as printing ink, it is excellent in mass productivity at low cost as a method of manufacturing a color filter. Furthermore, with the development of printing technology, printing of fine patterns having high dimensional accuracy and smoothness can be performed. In order to print, it is preferable to set it as a composition which an ink does not dry and solidify on the printing plate or on a blanket. In addition, it is important to control the flowability of the ink on the printing press, and the viscosity of the ink can be adjusted by a dispersant or an extender pigment.

  When a filter segment is formed by photolithography, the coloring composition prepared as the above-mentioned solvent development type or alkali development type coloring resist material is coated on a transparent substrate by spray coating, spin coating, slit coating, roll coating, etc. The dry film is applied to a thickness of 0.2 to 5 μm by a method. The film dried if necessary is exposed (irradiated) through a mask having a predetermined pattern provided in contact or non-contact with the film. Thereafter, the uncured area is removed by immersion in a solvent or an alkaline developer or by spraying the developer to remove a non-cured portion to form a desired pattern, and then the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate | stimulate superposition | polymerization of a coloring resist material, heating can also be given as needed. According to the photolithography method, it is possible to manufacture a color filter with higher accuracy than the above-mentioned printing method.

In the development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the exposure sensitivity, after applying and drying the colored resist, applying and drying a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin 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, etc. in addition to the above method, but 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. . In the transfer method, filter segments are formed in advance on the surface of a peelable transfer base sheet, and the filter segments are transferred to a desired substrate.

  Before forming the color filter segments on a transparent substrate or a reflective substrate, a black matrix can be formed in advance. As the black matrix, although 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, it is not limited thereto. Alternatively, thin film transistors (TFTs) may be formed in advance on the above-described transparent substrate or reflective substrate, and then the color filter segments may be formed. Moreover, an overcoat film, a transparent conductive film, etc. are formed on the color filter of this invention as needed.

  The color filter of the present invention is bonded to the opposite substrate using a sealing agent, and after injecting liquid crystal from the injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or retardation film is used as a substrate if necessary. The color liquid crystal display device is manufactured by bonding to the outer side of. This color liquid crystal display device can be twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), critically aligned (VA), optically convensend bend (OCB) Etc.) can be used in a liquid crystal display mode in which coloring is performed.

  The color filter of the present invention can also be used for producing a color imaging device, an organic EL display device, an electronic paper, etc. in addition to the color liquid crystal display device.

 Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereby. In the following description, "parts" and "%" mean "parts by weight" and "% by weight" unless otherwise specified.

(Average primary particle size of pigment)
The average primary particle size of the pigment was measured by direct measurement of the primary particle size from an electron micrograph using a transmission (TEM) electron microscope. 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 diameter of the primary pigment particles. Next, with respect to 100 or more pigment particles, the volume (weight) of each particle is determined by approximating to the cube of the determined particle diameter, and the volume average particle diameter is made the average primary particle diameter.

(Weight average molecular weight of binder resin)
The weight average molecular weight (Mw) of the resin was measured using a TSK gel column (manufactured by Tosoh Corporation) and a GPC equipped with a RI detector (HLC-8120GPC manufactured by Tosoh Corporation), using polystyrene as the developing solvent and polystyrene conversion It is a 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 (mg KOH / g) to 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))
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the basic resin type dispersant are measured using HLC-8320GPC (manufactured by Tosoh Corporation) as an apparatus, using SUPER-AW 3000 as a column, and 30 mM triethylamine as an eluent. And polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) measured using a 10 mM LiBr solution in N, N-dimethylformamide.

(Amine value of block copolymer [A1] and intermediate polymer (a))
The amine value of the basic resin type dispersant is a value obtained by converting the total amine number (mg KOH / g) measured in solid content in accordance with the method of ASTM D 2074.

  Then, the manufacturing method of the binder resin solution used in the Example and the comparative example, a block copolymer solution, a pigment, a pigment derivative, the coloring composition for color filters, and the photosensitive coloring composition is demonstrated.

<Method of producing binder resin solution>
(Preparation of Acrylic Resin Solution 1)
Add 100 parts of propylene glycol monomethyl ether acetate to a reaction vessel equipped with a separable 4-neck flask, a thermometer, a condenser, a nitrogen gas inlet pipe, and a stirrer, and heat it at 120 ° C while injecting nitrogen gas into the vessel. 16.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 25.0 parts of dicyclopentanyl methacrylate, 16 parts of methyl methacrylate and azobisisobutyro as a catalyst required for the reaction of the precursor at this stage from the dropping tube at a 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 is replaced with air, and 17.0 parts of acrylic acid and 0.3 parts of trisdimethylaminomethylphenol as a catalyst required for the reaction of the precursor at this stage and 0.3 parts of hydroquinone are charged, 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). The introduced acrylic acid is ester-bonded to the epoxy group terminal of the glycidyl methacrylate structural unit, so that no carboxyl group is generated in the resin structure. Further, 0.5 parts of triethylamine was added as a catalyst required for the reaction of 30.4 parts of tetrahydrophthalic anhydride and the precursor in this stage, and the reaction was carried out at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of the two carboxyl groups formed by cleavage of the carboxylic acid anhydride is ester-linked to the hydroxyl group in the resin structure, and the other produces a carboxyl group end. Propylene glycol monomethyl ether acetate was added to a nonvolatile content of 40% to obtain an acrylic resin solution 1.

<Production of block copolymer [A1]>
Production Example 1: Block Copolymer Solution (A1-1)
23 parts of methyl methacrylate, 13 parts of n-butyl methacrylate, 8 parts of n-butyl acrylate, 8 parts of t-butyl acrylate, in a reactor equipped with a gas feed pipe, a condenser, a stirring blade, and a thermometer Propylene glycol monomethyl ether acetate 100: 8 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 The system was purged with nitrogen by dissolving in a portion and bubbling nitrogen for 30 minutes. Thereafter, the mixture was gently stirred, and was stirred at 60 ° C. for 24 hours while flowing 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 added for 30 minutes. The solution subjected to substitution was added to the above reaction solution, and living radical polymerization was performed 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 by converting from the non-volatile content. Thereafter, propylene glycol monomethyl ether acetate was added so as to have a volatile content of 40% to obtain a block copolymer fluid (A1-1) having no ionic group. As a result of molecular weight measurement, it was Mw 9000.

Preparation Example 2 Preparation of Polymer A1-2
25 parts of methyl methacrylate, 15 parts of n-butyl methacrylate, 10 parts of n-butyl acrylate, 10 parts of t-butyl methacrylate, in a reaction apparatus equipped with a gas feed pipe, a condenser, a stirring blade and a thermometer Propylene glycol monomethyl ether acetate 100: 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 The system was purged with nitrogen by dissolving in a portion and bubbling nitrogen for 30 minutes. Thereafter, the mixture was gently stirred, and was stirred at 60 ° C. for 24 hours while flowing 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-pentamethyl piperidyl methacrylate ("ADEKA STAB LA 82" manufactured by ADEKA) in 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 for 24 hours at 60 ° C. The polymerization solution was sampled to measure the solid content, converted to non-volatile content It was confirmed that the polymerization conversion was 97% or more, and a solution of the intermediate polymer (a-1) was obtained, and then 17.1 parts of chloroacetic acid and 100 parts of propylene glycol monomethyl ether acetate were charged into the above container The reaction was continued for 7 hours at 100 ° C., and the reaction was terminated when the solid content amine value disappeared. About 2 g of the solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether acetate is added to the previously synthesized resin solution so that the non-volatile content is 40% by weight. (A1-2) was prepared.

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

Preparation Example 12 Preparation of Polymer A1-10
A reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 25 parts of methyl methacrylate, 15 parts of n-butyl methacrylate, 10 parts of n-butyl acrylate, 10 parts of t-butyl methacrylate, methacrylic acid Propylene glycol monomethyl ether acetate 100: 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 The system was purged with nitrogen by dissolving in a portion and bubbling nitrogen for 30 minutes. Thereafter, the mixture was gently stirred, and was stirred at 60 ° C. for 24 hours while flowing 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-pentamethyl piperidyl methacrylate ("ADEKA STAB LA 82" manufactured by ADEKA) in 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 for 24 hours at 60 ° C. The polymerization solution was sampled to measure the solid content, converted to non-volatile content It was confirmed that the polymerization conversion was 97% or more, and a solution of the intermediate polymer (a-1) was obtained, followed by charging 8.5 parts of chloroacetic acid and 100 parts of propylene glycol monomethyl ether acetate into the above container The reaction was continued for 7 hours at 100 ° C., and the reaction was terminated when the solid content amine number reached 35.2 KOH mg / g. After cooling by about 2g, sample about 2g of resin solution, heat to dryness at 180 ° C for 20 minutes, measure the non volatile matter and measure propylene glycol monomethyl ether acetate so that the non volatile matter becomes 40 wt% in the resin solution synthesized earlier. Was added to prepare a polymer (A1-10).

The abbreviations in Table 1 are as follows.
MMA: methyl methacrylate nBMA: methacrylic acid n-butyl nBA: acrylic acid n-butyl tBA: acrylic acid t-butyl HEMA: methacrylic acid 2-hydroxyethyl LA 82: 1, 2, 2, 6, 6-pentamethyl piperidyl methacrylate DMAEMA : Dimethylaminoethyl methacrylate DMAPMA: 2- (dimethylamino) propyl methacrylate

<Production Example of Block Copolymer (A2-1), (A2-2)>
Production Example 12 Preparation of Block Copolymer Solution (A2-1)
A reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 25 parts of methyl methacrylate, 15 parts of n-butyl methacrylate, 10 parts of n-butyl acrylate, 10 parts of t-butyl acrylate, and methacrylate Propylene glycol monomethyl ether acetate 100: 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 The system was purged with nitrogen by dissolving in a portion and bubbling nitrogen for 30 minutes. Thereafter, the mixture was gently stirred, and was stirred at 60 ° C. for 24 hours while flowing 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-pentamethyl piperidyl methacrylate ("ADEKA STAB LA 82" manufactured by ADEKA) with 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 for 24 hours at 60 ° C. The polymerization solution was sampled to measure the solid content, converted to non-volatile content After that, it was confirmed that propylene glycol monomethyl ether acetate was added so that the volatile content would be 40%, and a block copolymer fluid having no ionic group (A2-1). As a result of molecular weight measurement, it was Mw 9000, and the amine value per solid content was 70.4 mg KOH / g. .

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

The abbreviations in Table 2 are as follows.
DMC: dimethylaminoethyl methacrylate methyl chloride salt

<Method of producing pigment>
(Method of producing aluminum phthalocyanine pigment 1)
In 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. The reaction solution was poured into 4000 parts of water after cooling to room temperature. The product was filtered, washed with methanol and dried to obtain aluminum phthalocyanine pigment 1.

(Production method of aluminum phthalocyanine pigment 2)
In 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 and stirred, and reacted at 20 ° C. for 3 hours. Thereafter, the reaction mixture was poured into 5,000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. In a beaker, 500 parts of 2.5% aqueous sodium hydroxide solution and the collected residue were added and stirred at 80 ° C. for 1 hour. Thereafter, the 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 a crude halogenated aluminum phthalocyanine pigment, and 18.2 parts of diphenyl phosphate were added to a 3-neck flask, and the mixture was heated to 90 ° C. and reacted for 8 hours. The reaction solution was poured into 4000 parts of water after cooling to room temperature. The product was filtered, washed with methanol and dried to obtain aluminum phthalocyanine pigment 2.

(Method for producing quinophthalone pigment 1)
100 parts of compound (A), 108 parts of tetrachlorophthalic anhydride and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, heated to 180 ° C., and reacted for 4 hours. Further, after cooling to room temperature, the reaction mixture was poured into 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)

<Method of producing finely divided pigment>
(Production of micronized 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 Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , To obtain a finely divided green pigment P-1.

(Production of micronized 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 Co., Ltd.) and kneaded at 80 ° C. for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , To obtain a finely divided green pigment P-2.

(Production of micronized 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 Co., Ltd.) and kneaded at 80 ° C. for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , To obtain a finely divided green pigment P-3.

(Production of micronized yellow pigment P-4)
Quinophthalone yellow pigment C.I. I. Pigment Yellow 138 ("Paliotol Yellow L 0962 HD" manufactured by BASF Corporation), 200 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , To obtain a finely divided yellow pigment P-4.

(Production of micronized 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 Co., Ltd.) and kneaded at 80 ° C. for 6 hours. Next, this kneaded material is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , To obtain a finely divided yellow pigment P-5.

(Production of micronized yellow pigment P-6)
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 ("Paliotol Yellow D 1819" manufactured by BASF Corporation), 200 parts, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. The kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and dried at 85 ° C. overnight. Yellow pigment P-6 is obtained.

(Production of micronized yellow pigment P-7)
Isoindoline yellow pigment C.I. I. 200 parts of CI Pigment Yellow 185 ("Paliotol Yellow D 1155" manufactured by BASF Corp.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. The kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and dried at 85 ° C. overnight. Yellowish pigment P-7 was obtained.

(Production of micronized yellow pigment P-8)
Azo yellow pigments C.I. I. 200 parts of C.I. Pigment Yellow 150 ("E4GNGT" manufactured by Lanxess 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 Co., Ltd.) and kneaded at 80.degree. Next, this kneaded material is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , To obtain a finely divided yellow pigment P-8.

(Production of micronized red pigment P-9)
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of CI Pigment Red 254 ("B-CF" manufactured by BASF 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 Co., Ltd.) and kneaded at 80C for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , 190 parts of a finely divided diketopyrrolopyrrole pigment P-9.

(Production of micronized red pigment P-10)
Anthraquinone red pigment C.I. I. Pigment Red 177 ("Chromophthal Red A2B" manufactured by BASF Corporation), 200 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , Anthraquinone fined red pigment P-10 was obtained.

(Production of micronized 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, sodium chloride 1400 parts, and diethylene glycol 360 parts are charged in a stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.) It knead | mixed for 6 hours at 80 degreeC. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. And finely divided blue pigment P-11 were obtained.

(Production of micronized purple pigment P-12)
Dioxazine purple pigment C.I. I. Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Color Corp.), 200 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material was introduced into 8000 parts of hot water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered, sodium chloride and diethylene glycol were removed by repeated washing with water, and then dried overnight at 85 ° C. to obtain a finely divided purple pigment P-12.

<Method of Producing Colored 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 for 3 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads of 0.5 mm in diameter, 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.

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

<Evaluation of pigment dispersion>
The following evaluation was performed about the pigment dispersions (GP-1)-(GP-57) obtained by the Example and the comparative example. The results are shown in Table 4.

(Contrast ratio (CR) evaluation of coating film)
The light emitted from the liquid crystal display backlight unit is polarized through the polarizing plate, passes through the coating of the coloring composition applied on the glass substrate, and reaches the other polarizing plate. At this time, light passes through the polarizing plate if the polarizing planes of the polarizing plate and the polarizing plate are parallel, but light is blocked by the polarizing plate if the polarization planes are orthogonal to each other. However, when light polarized by the polarizing plate passes through the coating film of the coloring composition, the colorant particles cause scattering or the like, and when deviation occurs in part of the polarization plane, transmission occurs when the polarizing plates are parallel. The amount of light to be reduced decreases, and when the polarizing plates are orthogonal, some light is transmitted. The transmitted light was measured as the brightness on the polarizing plate, and the ratio of the brightness when the polarizing plates were parallel to the brightness when the polarizing plates were orthogonal was calculated as the contrast ratio.
(Contrast ratio) = (brightness in parallel) / (brightness in orthogonal)
Therefore, when scattering occurs due to the colorant in the coating, the brightness in parallel decreases and the brightness in orthogonal increases, so the contrast ratio decreases.

  A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as a luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as a polarizing plate. In the measurement, it measured through the black mask which opened the 1-cm square hole in the measurement part.

First, the pigment dispersion is applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and then heated at 230 ° C. for 60 minutes, allowed to cool By doing this, a coated substrate was produced. The contrast ratio (CR) of the obtained coated substrate was measured. The prepared coated 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.

:: over 9000: extremely good ○: over 6000 to less than 9000: good Δ: over 3000 to less than 6000: practicable ×: less than 3000: defective

(Viscosity evaluation (dispersion stability))
The initial viscosity at 25 ° C. was measured for the viscosity of the pigment dispersion 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. Dispersion stability was evaluated on the basis of the following by viscosity change rate = (initial viscosity-viscosity over time) / initial viscosity x 100 (%). Evaluation criteria are shown below.

○ (Good for practical use): When the viscosity change rate is within ± 10% and no sediment is generated.
Δ (practical possibility): When the viscosity change rate is ± 10% to 20% and the sediment is not generated.
X (not practical): When the rate of viscosity change exceeds ± 20%, or when the rate of viscosity change is within ± 20%, a precipitate is produced.

(Foreign body evaluation)
The evaluation of the generation of foreign matter is carried out by applying the pigment dispersion to a transparent substrate so that the dried coating film is about 1.5 μm, heating in an oven at 250 ° C. for 60 minutes, and leaving it to cool. The number of foreign objects in it was counted. The surface was observed using a metallurgical microscope "BX60" manufactured by Olympus Systems Corporation. The magnification was set to 500 times, and the number of foreign substances observable in any five fields of view was measured in transmission.

:: number of foreign matter less than 3: extremely good ○: number of foreign matter is 3 or more and less than 20: good Δ: number of foreign matter is 21 or more and less than 100: practicable ×: number of foreign matter is 100 Pieces or more: Defective

As shown in Table 4, by using the block copolymer of the present invention, a dispersion excellent in contrast ratio, viscosity stability, and foreign matter with respect to various coloring materials could be formed.

<Production of Photosensitive Colored Composition for Color Filter>
[Example 38] (Green photosensitive coloring composition (R-1))
After stirring and mixing the mixture of the following composition so that it might become uniform, it filtered with a filter with a hole diameter of 1 micrometer, and produced photosensitive coloring composition (R-1).

PG 58 · Pigment dispersion (GP-1): 38.0 parts PY 138 · Pigment dispersion (GP-20): 12.0 parts Acrylic resin solution 1: 10.0 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd. "Alonics M-402": 2.0 parts Photopolymerization initiator ("IRGACURE 907" manufactured by BASF Corporation): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.): 0. 3 parts cyclohexanone: 36.7 parts

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

<Evaluation of photosensitive coloring composition>
The heat resistance, the developability, and the adhesion were evaluated for the obtained photosensitive coloring composition. 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 is formed in advance by a spin coating method, and then dried in a clean oven at 70 ° C. for 20 minutes. Then, the substrate was cooled to room temperature and then exposed to ultraviolet light through a photomask using an extra-high pressure mercury lamp. Thereafter, the substrate was spray developed for 30 seconds with a 0.2% by weight aqueous solution of sodium carbonate at 23 ° C., 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 stripe-like colored pixel layer on the substrate. The prepared colored pixel layer was adjusted to have a film thickness of 2.0 μm after heat treatment at 230 ° C. [L * (1), a * (1), b * (1)] was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) of the obtained coating film. 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 equation. 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 = 1 less than: extremely good ○: ΔE * ab = 1 or more and less than 3: good Δ: ΔE * ab = 3 or more and less than 5: practicable x: ΔE * ab = 5 or more: defective

(Evaluation of developability)
Using the photosensitive coloring composition thus obtained, a spin coater is used to apply a film thickness of 2.0 μm on a 100 mm × 100 mm, 1.1 mm thick glass substrate, and the film thickness is made to be 2.0 μm. It dried and produced the coating film board | substrate. The substrate was spray developed with a 0.2% by weight aqueous solution of sodium carbonate at 23 ° C., and the time (development time) in which development was performed until the coating film was completely eliminated was calculated to evaluate the developability. The judgment criteria are shown below.

:: Less than 20 seconds ○: More than 20 seconds and less than 30 seconds :: More than 30 seconds and less than 40 seconds ×: More than 40 seconds ... Unavailable level

(Evaluation of adhesion)
The substrate coated with the photosensitive coloring composition on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater at a rotational speed of 2 μm after drying is dried at 70 ° C. for 20 minutes An ultraviolet light of 150 mJ / cm 2 was irradiated using a super high pressure mercury lamp through a photomask having 100 openings of 10 μm × 10 μm. Next, after spray development was carried out with an alkaline developing solution consisting of a 0.2% by weight aqueous solution of sodium carbonate to remove an unexposed part, washing was carried out with ion exchanged water. At this time, the adhesion was evaluated based on how many 10 μm × 10 μm patterns remain. Further, the evaluation of developability was judged according to the following criteria. X is a difficult level to use.

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

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

<Preparation of color filter>
The photosensitive coloring composition of the present invention was used to prepare a color filter. The red and blue photosensitive coloring compositions used were prepared as follows.

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

PR 254 · pigment dispersion (GP-30): 30.0 parts PR 177 · pigment dispersion (GP-32): 20.0 parts Acrylic resin solution 1: 10.0 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd. "Alonics M-402": 2.0 parts Photopolymerization initiator ("IRGACURE 907" manufactured by BASF Corporation): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.): 0. 3 parts cyclohexanone: 36.7 parts

(Red photosensitive coloring composition (R-27))
(R-26) except that (GP-30) was changed to (GP-46) and (GP-32) was changed to (GP-47) in the preparation of the red photosensitive coloring composition (R-26) In the same manner, a red photosensitive coloring composition (R-27) was prepared.

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

PB 15: 6 pigment dispersion (GP-34): 28.1 parts PV 23 pigment dispersion (GP-36): 3.1 parts acrylic resin solution 1: 6.3 parts photopolymerizable monomer (Toago synthesis "Alonics M-402" manufactured by Co., Ltd .: 4.0 parts Photopolymerization initiator ("IRGACURE 907" manufactured by BASF Corp.): 2.0 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.): 0.3 parts cyclohexanone: 56.2 parts

(Blue photosensitive coloring composition (R-29))
(R-25) except that (GP-34) was changed to (GP-48) and (GP-36) to (GP-49) in the preparation of the red photosensitive coloring composition (R-28) A blue photosensitive coloring composition (R-29) was produced in the same manner as in

Example 60 (Color Filter (CF-1))
The red photosensitive coloring composition (R-26) was applied to a glass substrate on which a black matrix is formed in advance by a spin coating method, and then dried in a clean oven at 70 ° C. for 20 minutes. The substrate was then cooled to room temperature, and then exposed to ultraviolet light through a photomask using an extra-high pressure mercury lamp.
Thereafter, the substrate was spray developed for 30 seconds with a 0.2% by weight aqueous solution of sodium carbonate at 23 ° C., 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 stripe-like colored pixel layer on the substrate.
Next, using the green-sensitive colored composition (R-1) of the present invention, a green-colored pixel layer was formed in the same manner as the red-colored pixel layer. Furthermore, the blue photosensitive pixel composition was similarly formed using a blue photosensitive coloring composition (R-28), and the color filter (CF-1) was obtained. The formed film thickness of each colored pixel layer was 2.0 μm.
Comparative Example 27 (Color Filter (CF-2))
In the preparation of the color filter (CF-1), the photosensitive coloring composition used is a red-sensitive coloring composition (R-27) and a green-sensitive coloring composition (R-23) blue-sensitive Color filter (CF-2) was prepared in the same manner as (CF-1) except that the colored coloring composition (R-29) was used. .0 μm.

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

Claims (13)

It is a coloring composition for color filters which contains a coloring agent, dispersing agent [A], binder resin, and a solvent, and this dispersing agent [A] has an A block which has a repeating unit represented by the following general formula (1). The coloring composition for color filters which is a block copolymer [A1] which contains and B block which does not have a repeating unit represented by 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 It represents, Y ^- represents a monovalent anionic group. ] In the general formula (1) contained in the A block of the block copolymer [A1], X ⁺ is a divalent linking group represented by the following general formula (2) or the following general formula (3) The coloring composition for color filters as described in 1.
General formula (2)

[In the general formula (2), R ²¹ and R ²² each independently represent a monovalent organic group.
* ¹ represents a bond to R ¹² and * ² represents a bond to 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 to R ¹² and * ² represents a bond to R ¹³ . ] The coloring composition for color filters according to claim 2, wherein X ⁺ in the general formula (1) is a divalent linking group represented by the general formula (3). R ³¹ and R ³² are monovalent color filter coloring composition according to claim 2 or 3 is an aliphatic hydrocarbon radical of the general formula (3). Wherein Y in the general formula (1) ^- is, -CO ₂ ^- or -SO ₃ ^- color filter coloring composition according to any one of claims 1 to 4 is. The group according to any one of claims 1 to 5, wherein R ^{12 in the} general formula (1) is a combination of an alkanediyl group having 1 to 8 carbon atoms and -COO- or -CONRb-. Colored composition for color filter.
[Rb represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ] Wherein R ¹³ in the general formula (1) is a color filter for coloring composition according to any one of claims 1 to 6 alkanediyl group having 1 to 5 carbon atoms.  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 color filters as described.   Furthermore, the dispersing agent [B] which has an aromatic carboxyl group is contained, The coloring composition for color filters of any one of the Claims 1-8 characterized by the above-mentioned.  The coloring agent is any one of a phthalocyanine based pigment, a diketopyrrolopyrrole based pigment, a quinophthalone based pigment, an isoindoline based pigment, an anthraquinone based pigment, an azo based pigment, and a dioxazine based pigment. The coloring composition for color filters of any one of -9.   The colorant further contains C.I. I. Pigment red 177, 254, C.I. I. Pigment yellow 138, 139, 185, 231, C.I. I. The coloring composition for color filters according to any one of claims 1 to 10, comprising pigment green 58, 62, 63, pigment blue 15: 6 or pigment violet 23.   The coloring composition for color filters according to any one of claims 1 to 11, 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 of the coloring composition for color filter according to any one of claims 1 to 12 on a substrate.