JP2012247589A - Coloring composition for color filter, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition for a color filter having high contrast ratio and good heat resistance, and a color filter using it; and also a coloring composition for a color filter having an excellent balance in performance required for formation of good filter segments such as pattern shape and resolution when used as a photosensitive coloring composition, and a color filter using it having excellent contrast ratio and high definition.SOLUTION: The problems are solved by a coloring composition for a color filter containing a colorant, a binder resin and an organic solvent, which is characterized in that the colorant contains a phthalocyanine dye represented by the general formula (1) and in that the binder resin is a vinyl resin with an ethylenically unsaturated double bond introduced using an ethylenically unsaturated monomer having an epoxy group and also contains a vinyl resin [B1] comprising the following constitutional units (b1) and (b2).

Description

  The present invention relates to a color liquid crystal display device, a color composition for color filter used for manufacturing a color filter used for a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. It is.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. Therefore, liquid crystal display devices are being developed for use in televisions and personal computer monitors.

  Other typical liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and electrolysis is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) method for vertically aligning nematic liquid crystal with optical properties, and Optical Convencence Bend (OCB) method in which the optical axes of uniaxial retardation films are orthogonal to each other to perform optical compensation Etc., and each has been put to practical use.

  A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in In general, it is often formed from filter segments of three colors of red, green, and blue. Each of these segments is as fine as several microns to several hundreds of microns, and is neatly arranged in a predetermined arrangement for each hue. ing.

  The filter segments that make up the color filter are activated by proximity exposure (ultraviolet light source exposure) through a photomask for pixel formation after applying a photosensitive material on a glass substrate, drying and removing excess solvent. It is formed by irradiating energy rays, curing (negative type) or increasing alkali solubility (positive type), removing a portion that dissolves with an alkali solution, etc., and heating to 230 ° C. or more called post-baking. By repeating this for each color of red, green and blue, for example, a color filter is produced.

  In the production of a green filter, it is common to use various phthalocyanine compounds as a colorant, and many proposals for color filter compositions containing these compounds have been made.

  Patent Document 1 proposes a color filter composition using a halogenated phthalocyanine compound substituted with at least four halogen atoms as a green colorant.

  In Patent Document 2, as a green pigment, a halogenated copper phthalocyanine pigment and a central metal are selected from the group consisting of Mg, Al, Si, Ti, V, Mn, Fe, Co, Ni, Zn, Ge, and Sn. There has been proposed a color filter composition comprising a green colorant composed of at least one halogenated dissimilar metal phthalocyanine pigment.

  These phthalocyanine compounds are all materials for producing a high brightness color filter. However, in recent years, the demand for high brightness has been further increased, and the composition using these proposed colorants has a lightness. It is insufficient.

  Patent Document 3 discloses a pigment composition that maintains a clear hue, high light resistance, and high heat resistance by using a blue aluminum phthalocyanine pigment containing no halogen and a green pigment containing halogen. Yes.

  Regarding the coloring composition for the green color filter segment, Patent Document 4 uses an aluminum phthalocyanine pigment as a main pigment, and can achieve high brightness with high chromaticity even at a relatively small content, and achieve both color density and color purity. Disclosed techniques.

  Further, as an aluminum phthalocyanine pigment, in addition to the monomer aluminum phthalocyanine pigment described in Patent Document 4, in Patent Document 5, bis (phthalocyanylalumino) tetraphenyldimer obtained by dimerizing an aluminum phthalocyanine pigment with diphenylchlorosilane is used. Bis (phthalocyanylaluminum) phenylphosphonate pigments dimerized with siloxane pigments or phenylphosphonic acid are disclosed.

  In recent years, there has been a demand for higher density for color filters, and it is necessary to increase the colorant concentration in the color composition to be used. However, exposure sensitivity and development can be improved by increasing the colorant concentration of the color composition. Properties that contribute to image line formation, such as solubility at the time, are relatively lowered. As a result, the solubility of the non-image area during development deteriorates, and the colored composition of the non-image area remains undissolved during development, or remains on the substrate as a peeled piece with the resist not dissolved. May cause color misregistration. As a result, there is a problem that the quality of the color filter is deteriorated and the yield is reduced during production.

JP 2002-131521 A JP 2002-250812 A JP 2003-4930 A JP 2004-333817 A Japanese Unexamined Patent Publication No. 57-90058

  The problem to be solved by the present invention is to provide a coloring composition for a color filter having a high contrast ratio and good heat resistance, and a color filter using the same. In addition, when used as a photosensitive coloring composition, the color composition for color filters has an excellent balance of performance necessary for forming good filter segments, such as pattern shape and resolution, and contrast ratio using the same. The object is to provide an excellent, high-definition color filter.

  As a result of intensive studies, the present inventors have used a coloring composition containing a phthalocyanine dye having a specific structure and a binder resin having a specific structure, so that the coloring composition for a color filter solves the above-described problems. As a result, the present invention has been found.

[一般式（１）中、Ａ¹〜Ａ¹⁶は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、置換基を有してもよいアルキル基、または置換基を有してもよいアリール基を表す。
Ｒ¹およびＲ²は、それぞれ独立して、水素原子、ヒドロキシ基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、または−ＯＲ³を表し、Ｒ¹とＲ²とが互いに結合して環を形成しても良い。
Ｒ³は、置換基を有してもよいアルキル基、または置換基を有してもよいアリール基である。］

（ｂ１）；カルボキシル基を有する構成単位：
ビニル系樹脂［Ｂ１］の全構成単位の重量を基準として２〜６０重量％
（ｂ２）；一般式（２）または一般式（３）に示す芳香族環基を有する構成単位：
ビニル系樹脂［Ｂ１］の全構成単位の重量を基準として２〜８０重量％
一般式（２）：

一般式（３）：

[一般式（２）及び（３）中、Ｒ⁴は、水素原子、またはベンゼン環を有していてもよい炭素数１〜２０のアルキル基である。] That is, the present invention is a color filter coloring composition containing a colorant, a binder resin, and an organic solvent, wherein the colorant contains a phthalocyanine dye represented by the following general formula (1), A vinyl resin in which the binder resin is a vinyl resin in which an ethylenically unsaturated double bond is introduced using an ethylenically unsaturated monomer having an epoxy group, and includes the following structural units (b1) and (b2) The present invention relates to a coloring composition for a color filter, which contains a resin [B1].
General formula (1)

[In General Formula (1), A ^{1 to} A ¹⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, an alkyl group that may have a substituent, or an aryl that may have a substituent. Represents a group.
R ¹ and R ² are each independently hydrogen atom, hydroxy group, an optionally substituted alkyl group, an optionally substituted aryl group, or an -OR ^3, and R ¹ R ² may be bonded to each other to form a ring.
R ³ is an alkyl group which may have a substituent or an aryl group which may have a substituent. ]

(B1); a structural unit having a carboxyl group:
2 to 60% by weight based on the weight of all structural units of the vinyl resin [B1]
(B2): a structural unit having an aromatic ring group represented by the general formula (2) or the general formula (3):
2 to 80% by weight based on the weight of all structural units of the vinyl resin [B1]
General formula (2):

General formula (3):

[In General Formulas (2) and (3), R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

In the present invention, the vinyl resin [B1]
The precursor of the structural unit (b2) is reacted with an ethylenically unsaturated monomer having an epoxy group to obtain a copolymer (i1-1), and then the copolymer (i1-1) obtained ) And an unsaturated monobasic acid to obtain a copolymer (i1-2), and a resin obtained by reacting the obtained copolymer (i1-2) with a polybasic acid anhydride ,
Alternatively, the precursor of the structural unit (b1) and the precursor of the structural unit (b2) are reacted to obtain a copolymer (i2-1), and then the copolymer (i2-1) obtained The present invention relates to the coloring composition for a color filter, which is a resin obtained by reacting an ethylenically unsaturated monomer having an epoxy group.

式（５）：

In addition, the present invention relates to the colored composition for color filters, wherein the vinyl resin [B1] further contains the following structural unit (b3).

(B3): a structural unit having an aliphatic cyclic group represented by formula (4) or formula (5):
2 to 60% by weight based on the weight of all structural units of the vinyl resin [B1]
Formula (4):

Formula (5):

  Further, the present invention relates to the color composition for color filters, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  The present invention also relates to a color filter comprising a filter segment formed on the substrate from the color filter coloring composition.

  The coloring composition for a color filter of the present invention has good patterning suitability in alkali development, and a color filter having a good pattern shape can be obtained. In addition, a color filter having a high contrast ratio and good heat resistance can be provided.

Hereinafter, the present invention will be described in detail.
In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is particularly described, Unless otherwise indicated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. It shall represent.
Further, “CI” mentioned in the present specification means a color index (CI).

  The present invention is a color filter coloring composition comprising a colorant, a binder resin, and an organic solvent, wherein the colorant contains a phthalocyanine dye represented by the general formula (1), and the binder resin , A vinyl resin in which an ethylenically unsaturated double bond is introduced using an ethylenically unsaturated monomer having an epoxy group, and a vinyl resin [B1] containing structural units (b1) and (b2) It is a coloring composition for color filters characterized by containing.

[一般式（１）中、Ａ¹〜Ａ¹⁶は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、置換基を有してもよいアルキル基、または置換基を有してもよいアリール基を表す。
Ｒ¹およびＲ²は、それぞれ独立して、水素原子、ヒドロキシ基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、または−ＯＲ³を表し、Ｒ¹とＲ²とが互いに結合して環を形成しても良い。
Ｒ³は、置換基を有してもよいアルキル基、または置換基を有してもよいアリール基である。］ <Colorant>
The coloring composition for a color filter of the present invention contains a phthalocyanine dye represented by the general formula (1) (hereinafter sometimes referred to as “specific phthalocyanine dye”) as a colorant.
(Phthalocyanine dye represented by the general formula (1))
General formula (1)

[In General Formula (1), A ^{1 to} A ¹⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, an alkyl group that may have a substituent, or an aryl that may have a substituent. Represents a group.
R ¹ and R ² are each independently hydrogen atom, hydroxy group, an optionally substituted alkyl group, an optionally substituted aryl group, or an -OR ^3, and R ¹ R ² may be bonded to each other to form a ring.
R ³ is an alkyl group which may have a substituent or an aryl group which may have a substituent. ]

Examples of the halogen atom in A ^{1 to} A ¹⁶ include fluorine, chlorine, bromine, and iodine.

Examples of the alkyl group which may have a substituent in A ^{1 to} A ¹⁶ and R ^{1 to} R ³ include a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms. . Examples of the “substituent” include halogen atoms such as chlorine, fluorine and bromine, alkoxy groups such as methoxy group, nitro groups and the like. Specific examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2,2,3,3-tetrafluoropropyl group, 2-nitropropyl group, Isopropyl group, isobutyl group, isopentyl group, 2-ethylhexyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl Group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4 It can be a decyl cyclohexyl group, but not limited thereto.

Examples of the aryl group which may have a substituent in A ^{1 to} A ¹⁶ and R ^{1 to} R ³ include a monocyclic or condensed polycyclic aromatic group having 6 to 18 carbon atoms. Examples of the “substituent” include halogen atoms such as chlorine, fluorine and bromine, alkoxy groups such as alkyl groups and methoxy groups, amino groups and nitro groups. Specific examples include phenyl group, naphthyl group, anthranyl group, p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2 -Aminoanthraquinonyl group and the like.

As the specific phthalocyanine dye that can be used in the colored composition for a color filter of the present invention, A ^{1 to} A ¹⁶ are preferably any one of a hydrogen atom, a halogen atom, and a methyl group from the viewpoint of dispersibility and color characteristics. More preferably, A ^{1 to} A ¹⁶ are all hydrogen atoms.

Furthermore, as the specific phthalocyanine dye that can be used in the coloring composition for a color filter of the present invention, at least one of R ¹ and R ² may have a substituent from the viewpoint of dispersibility and color characteristics. group or (in -OR ^3, R ³ is as an aryl group which may have a substituent) aryloxy group which may have a substituent, is preferably. More preferably, R ¹ and R ² may be an aryl group which may have a substituent, or an aryloxy group which may have a substituent (in —OR ³ , R ³ may have a substituent). It is preferable that R ¹ and R ² are a phenyl group or a phenoxy group because of excellent lightness.

  Specific examples of the specific phthalocyanine dye that can be used in the colored composition for a color filter of the present invention are given below, but the invention is not limited to these.

(Other colorants)
The coloring composition for a color filter of the present invention may contain a yellow pigment within a range not impairing the effects of the present invention, for example, in order to adjust chromaticity. The yellow pigment is not particularly limited, and generally includes a yellow dye or a yellow pigment.

  As yellow dye, azo dye, azo metal complex dye, anthraquinone dye, indigo dye, thioindigo dye, phthalocyanine dye, diphenylmethane dye, triphenylmethane dye, xanthene dye, thiazine dye, cationic dye, cyanine dye, nitro dye, quinoline dye , Naphthoquinone dyes and oxazine dyes.

  Therefore, specific examples of yellow dyes include C.I. I. Acid Yellow 2,3, 4, 5, 6, 7, 8, 9, 9: 1, 10, 11, 11: 1, 12, 13, 14, 15, 16, 17, 17: 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199 Etc.

  In addition, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 etc. are also mentioned.

  In addition, C.I. I. Basic Yellow 1, 2, 5, 11, 13, 14, 15, 19, 21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, 105, 106 and the like.

  In addition, C.I. I. Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64, 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186, 187, 188, 190, 191, 192, 194, 195 and the like are also included.

  In addition, C.I. I. Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184: 1, 202, 211, 229, 231, 232 233, 241, 245, 246, 247, 248, 249, 250, 251 and the like.

  As the yellow pigment, organic or inorganic pigments can be used alone or in admixture of two or more, and pigments having high color development properties and high heat resistance, particularly pigments having high heat decomposition resistance are preferred. Organic pigments are used. As the organic pigment, commercially available ones can be used, and natural pigments and inorganic pigments can be used in combination according to the desired hue of the filter segment.

Below, the specific example of the yellow organic pigment which can be used for the said coloring composition is shown. Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, Yellow pigments such as 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214 can be used. In particular, from the viewpoint of heat resistance, light resistance, and brightness of the filter segment, C.I. I. Pigment Yellow 138, 139, 150, and 185 are preferable.
These yellow pigments can be used alone or in combination of two or more depending on the desired color characteristics.

  Further, a green pigment can be added for the purpose of adjusting the hue. Examples of the green pigment include C.I. I. And green pigments such as CI Pigment Green 7, 10, 36, 37, and 58.

  In the present invention, when a green dye is used in combination with the phthalocyanine dye represented by the general formula (1), the weight ratio of the green dye / the phthalocyanine dye represented by the general formula (1) is 50/50 to 95 / The range of 5 is more preferable because the brightness and color reproducibility are good.

  When a yellow pigment is used in combination with the phthalocyanine pigment represented by the general formula (1), the weight ratio of the yellow pigment / the phthalocyanine pigment represented by the general formula (1) is in the range of 40/60 to 90/10. The brightness and the color reproducibility are preferable.

  The preferred colorant content in all the non-volatile components of the colored composition according to the present invention is 10 to 90% by weight, more preferably 15 to 85% by weight from the viewpoint of sufficient color reproducibility and stability. Most preferably, it is 20 to 80% by weight.

(Miniaturization of pigment)
When the colorant used in the coloring composition of the present invention is a pigment, it can be refined by a salt milling process or the like. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. When the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult. When the thickness is larger than 90 nm, a sufficient contrast ratio cannot be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. 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 both the processing efficiency and the 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 to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. 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, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, 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.

一般式（３）：

[一般式（２）及び（３）中、Ｒ⁴は、水素原子、またはベンゼン環を有していてもよい炭素数１〜２０のアルキル基である。] <Binder resin>
(Vinyl resin [B1])
The binder resin contained in the colored composition of the present invention is a vinyl resin in which an ethylenically unsaturated double bond is introduced using an ethylenically unsaturated monomer having an epoxy group, and the following structural unit (b1) ) And (b2) containing vinyl resin [B1].
(B1); a structural unit having a carboxyl group:
2 to 60% by weight based on the weight of all structural units of the vinyl resin [B1]
(B2): a structural unit having an aromatic ring group represented by the general formula (2) or the general formula (3):
2 to 80% by weight based on the weight of all structural units of the vinyl resin [B1]
General formula (2):

General formula (3):

[In General Formulas (2) and (3), R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

Hereinafter, the structural unit (b1), the structural unit (b2), other structural units, and a method of introducing an ethylenically unsaturated double bond using an ethylenically unsaturated monomer having an epoxy group in order. explain.
In the present specification, the content% by weight of each structural unit is the weight% of the precursor that brings each structural unit to the vinyl resin [B1].

[Structural unit (b1)]
The structural unit (b1) has a carboxyl group and functions as an alkali-soluble site during development. Based on the weight of all the structural units of the vinyl resin [B1], the structural unit (b1) is 2 to 60% by weight from the viewpoint of developability. If it is less than 2% by weight, the removability of the unexposed portion by the alkaline developer becomes insufficient, and if it exceeds 60% by weight, the dissolution rate in the alkali developer is increased and the exposed portion is dissolved.

  The structural unit (b1) corresponds to a carboxyl group that is not used for an addition reaction with an epoxy group by a method using a precursor of the structural unit (b1) having a carboxyl group and a method (i-1) described later. The unit may be the structural unit (b1) in the vinyl resin.

  Examples of the precursor of the structural unit (b1) having a carboxyl group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, or α-chloroacrylic acid, and unsaturated dicarboxylic acids such as maleic acid or fumaric acid. And compounds containing a carboxyl group such as an acid and having an ethylenically unsaturated double bond. Moreover, what half-esterified the anhydride of unsaturated dicarboxylic acid, such as maleic anhydride, with the (meth) acrylic compound which has hydroxyl groups, such as hydroxyalkyl (meth) acrylate, can also be used. Among these, (meth) acrylic acid is more preferable, and methacrylic acid is most preferable from the viewpoint of polymerizability (ease of control of molecular weight and the like). These can be used alone or in combination of two or more.

一般式（３）：

[一般式（２）及び（３）中、Ｒ⁴は、水素原子、またはベンゼン環を有していてもよい炭素数１〜２０のアルキル基である。] [Structural unit (b2)]
The structural unit (b2) has a cyclic structure with an aromatic ring group represented by the general formula (2) and the general formula (3), and functions as an affinity site for a pigment or a pigment composition comprising a pigment and a dispersant. To do. Based on the weight of all structural units of the vinyl resin [B1], the structural unit (b2) is 2 to 80% by weight from the viewpoints of developability, dispersion stability, and chemical resistance. If it is less than 2% by weight, the developability, dispersion stability and chemical resistance are lowered. If it exceeds 80% by weight, the dissolution rate in an alkaline developer is slowed, the development time is long, and the productivity is deteriorated. .
(B2): a structural unit having an aromatic ring group represented by the general formula (2) or the general formula (3):
2 to 80% by weight based on the weight of all structural units of the vinyl resin [B1]
General formula (2):

General formula (3):

[In General Formulas (2) and (3), R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

  As the precursor of the structural unit (b2), styrene, α-methylstyrene, divinylbenzene, indene, acetylnaphthene, benzyl acrylate, benzyl methacrylate, bisphenol A diglycidyl ether di (meth) acrylate, (meth) of methylolated melamine Examples thereof include monomers and oligomers such as acrylate esters, and ethylenically unsaturated monomers represented by the general formula (6).

[一般式（６）中、Ｒ₆は、水素原子、またはメチル基であり、Ｒ₇は、炭素数２若しくは３のアルキレン基であり、Ｒ₈は、ベンゼン環を有していてもよい炭素数１〜２０のアルキル基であり、ｎは、１〜１５の整数である。] General formula (6):

[In General Formula (6), R ₆ is a hydrogen atom or a methyl group, R ₇ is an alkylene group having 2 or 3 carbon atoms, and R ₈ is a carbon that may have a benzene ring. It is a C1-C20 alkyl group, and n is an integer of 1-15. ]

As the ethylenically unsaturated monomer represented by the general formula (6), for example,
New Frontier CEA [EO-modified cresol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : methyl group, n = 1 or 2], NP-2 [n-nonylphenoxy polyethylene] Glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n = 2], N-177E [n-nonylphenoxypolyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene Group, R ₈ : n-nonyl group, n = 16 to 17], or PHE [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1],
Daicel, IRR169 [ethoxylated phenyl acrylate (EO 1 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], or Ebecryl 110 [ethoxylated phenyl acrylate (EO 2 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 2],
Aronix M-101A manufactured by Toagosei Co., Ltd. [phenol EO modified (n≈2) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈2], M-102 [phenol EO modified ( n≈4) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈4], M-110 [paracumylphenol EO modified (n≈1) acrylate, R ₆ : hydrogen atom , R _7: an ethylene group, R _8: Parakumiru, n ≒ 1], M-111 [n- nonylphenol EO-modified (n ≒ 1) acrylate, R _6: a hydrogen atom, R _7: an ethylene group, R _8: n- Nonyl group, n≈1], M-113 [n-nonylphenol EO-modified (n≈4) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n≈4], or M-117 [n-nonyl Phenol PO modified (n≈2.5) acrylate, R ₆ : hydrogen atom, R ₇ : propylene group, R ₈ : n-nonyl group, n≈2.5],
Kyoeisha light acrylate PO-A [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], P-200A [phenoxypolyethylene glycol acrylate, R ₆ : hydrogen atom, R _7: an ethylene group, R _8: a hydrogen atom, n ≒ 2], NP-4EA [nonylphenol EO adduct acrylate, R _6: a hydrogen atom, R _7: an ethylene group, R _8: n-nonyl group, n ≒ 4 ], Or NP-8EA [[nonylphenol EO adduct acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n≈8], or light ester PO [phenoxyethyl methacrylate, R ₆ : Methyl group, R ₇ : propylene group, R ₈ : hydrogen atom, n = 1],
Manufactured by NOF Corporation Blemmer ANE-300 [nonylphenoxy polyethylene glycol acrylate, R _6: a hydrogen atom, R _7: an ethylene group, R _8: - nonyl group, n ≒ 5], ANP-300 [nonylphenoxy polypropylene glycol acrylate, R _6: a hydrogen atom, R _7: a propylene group, R _8: n-nonyl group, n ≒ 5], 43ANEP-500 [nonylphenoxy - polyethylene glycol - polypropylene glycol - acrylate, R _6: a hydrogen atom, R _7: an ethylene group And propylene group, R ₈ : -nonyl group, n≈5 + 5], 70ANEP-550 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group and propylene group, R ₈ : n -Nonyl group, n≈9 + 3], 75AN EP-600 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group and propylene group, R ₈ : n-nonyl group, n≈5 + 2], AAE-50 [phenoxypolyethylene glycol Acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], AAE-300 [phenoxypolyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen Atom, n≈5.5], PAE-50 [phenoxypolyethylene glycol methacrylate, R ₆ : methyl group, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], PAE-100 [phenoxypolyethylene glycol methacrylate, R _6: a methyl group, R _7: an ethylene group, R _8: a hydrogen atom, n = ], Or 43PAPE-600B [phenoxy - polyethylene glycol - polypropylene glycol - methacrylate, R _6: a methyl group, R _7: an ethylene group and a propylene group, R _8: a hydrogen atom, n ≒ 6 + 6],
Shin-Nakamura Chemical Co., Ltd. NK ESTER AMP-10G [phenoxy ethyleneglycol acrylate (EO1mol), R _6: a hydrogen atom, R _7: an ethylene group, R _8: a hydrogen atom, n = 1], AMP-20G [phenoxy ethyleneglycol acrylate (EO 2 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈2], AMP-60G [phenoxyethylene glycol acrylate (EO ₆ mol), R ₆ : hydrogen atom, R ₇ : ethylene group , R ₈ : hydrogen atom, n≈6], PHE-1G [phenoxyethylene glycol methacrylate (EO 1 mol), R ₆ : methyl group, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1],
Biscoat # 192 manufactured by Osaka Organic Chemical Co., Ltd. [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], or
Nippon Kayaku SR-339A [2-phenoxy ethyleneglycol acrylate, R _6: a hydrogen atom, R _7: an ethylene group, R _8: a hydrogen atom, n = 1], or SR-504 (ethoxylated nonylphenol acrylate, R ₆ : Hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group] and the like, but not limited thereto, two or more kinds may be used in combination.

In the ethylenically unsaturated monomer represented by the general formula (6), the alkyl group represented by R ₈ has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group includes not only a linear alkyl group but also a branched alkyl group and an alkyl group having a benzene ring as a substituent. When the carbon number of the alkyl group of R ₈ is 1 to 10, the alkyl group becomes an obstacle and the penetration of ITO etching solution, metal etching solution, etc. is suppressed and the chemical resistance is increased. However, when the carbon number exceeds 10, the alkyl group The steric hindrance effect increases, and the adhesion with the base material tends to be hindered. This tendency becomes more prominent as the carbon chain length of the alkyl group of R ₈ becomes longer. When the carbon number exceeds 20, the adhesion with the substrate is extremely lowered. Examples of the alkyl group having a benzene ring represented by R ₈ include a benzyl group and a 2-phenyl (iso) propyl group. By adding one side chain benzene ring, chemical resistance is further improved and developability is also improved.

  In the ethylenically unsaturated monomer represented by the general formula (6), n is preferably an integer of 1 to 15. When n exceeds 15, the hydrophilicity increases and the effect of solvation decreases, and the viscosity of the vinyl resin [B1] increases, and the viscosity of the photosensitive composition using the same increases, thereby improving the fluidity. May have an effect. From the viewpoint of solvation, n is particularly preferably 1 to 4.

  As the precursor of the structural unit (b2), styrene, α-methylstyrene, benzyl acrylate, benzyl methacrylate, or the general formula (6) from the viewpoints of copolymerization with other precursors and chemical resistance. The ethylenically unsaturated monomer shown by these is preferable. These are particularly preferable because a benzene ring can be introduced into the side chain of the vinyl resin [B1]. By introducing a benzene ring into the side chain of the vinyl resin, the side chain benzene ring is oriented to the pigment, so that the resin adsorption to the pigment is promoted and the pigment aggregation is also suppressed. Furthermore, benzyl acrylate and / or benzyl methacrylate are most preferred from the viewpoints of developability and dispersion stability.

[Other structural units]
Vinyl-type resin [B1] may have structural units other than a structural unit (b1) and a structural unit (b2) as another structural unit. However, since the main function of the other structural unit is to provide developability, a small structure is formed with respect to the ring structure having a relatively large side chain of the structural unit (b2) having a chemical resistance function. It is preferable to take. Thereby, it is considered that developability can be imparted while maintaining the characteristics of the structural unit (b2) having a large side chain having chemical resistance.

  Moreover, it is preferable that vinyl-type resin [B1] of this invention further contains the structural unit (b3) which has a cyclic structure by the aliphatic cyclic group shown to Formula (4) and Formula (5). The structural unit (b3) has a cyclic structure with an aliphatic ring group represented by the formula (4) and the formula (5), and serves as an affinity site for a pigment or a pigment composition comprising a pigment and a dispersant, and the like. Functions as a hydrophobic site for the alkaline developer.

Examples of other structural unit precursors include:
Methyl (meth) methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (Meth) acrylate, pentyl (meth) acrylate, isopentyl acrylate, neopentyl (meth) acrylate, t-pentyl (meth) acrylate, 1-methylbutyl (meth) acrylate, hexyl (meth) acrylate, hepta (meth) acrylate, octyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, Alkyl or alkenyl (meth) acrylates such as rohexyl (meth) acrylate, allyl (meth) acrylate, or oleyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (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 (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di Various acrylic and methacrylic esters such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isobornyl (meth) acrylate, ester acrylate, epoxy (meth) acrylate, urethane acrylate, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol Divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl- 2,2 '-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'-[oxybis (methylene)] bis-2- Examples of monomers and oligomers such as propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate include, but are not limited to, other ethylenically unsaturated monomers. Can be selected, and two or more types can be used in combination. As described above, methyl (meth) acryl methacrylate or ethyl (meth) acrylate is preferably used from the viewpoint of developability.

Examples of other ethylenically unsaturated monomers include:
(Meth) acrylates having a heterocyclic substituent such as tetrahydrofurfuryl (meth) acrylate or 3-methyloxetanyl (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate or ethoxypolyethylene glycol (meth) acrylate; or
(Meth) acrylamide (in the case of “(meth) acrylamide”, it means acrylamide and / or methacrylamide; the same shall apply hereinafter), N, N-dimethyl (meth) acrylamide, N, N -(Meth) acrylamides such as diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine.

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

(Structural unit (b3))
The structural unit (b3) has 2 to 60% by weight from the viewpoint of developing property, dispersion stability, and chemical resistance, based on the weight (100% by weight) of all the structural units of the vinyl resin [B1]. Is preferred. When the content is 2% by weight or more, the affinity site for the pigment or the pigment composition composed of the pigment and the dispersant is sufficient, and a high-quality color filter can be obtained, or the storage stability of the color filter coloring composition can be improved. It is preferable because it becomes good. Further, it is favorable without causing a problem of pattern peeling or chipping in the pixel portion. The amount of 60% by weight or less is preferable because the dissolution rate in an alkali developer is fast, the development time is short, and the productivity of the color filter is improved.

Formula (4):

Formula (5):

Examples of the precursor of the structural unit (b3) include an ethylenically unsaturated monomer represented by the general formula (7), an ethylenically unsaturated monomer represented by the general formula (8), and the like.
General formula (7):

[一般式（７）、一般式（８）中、Ｒ₉は、水素原子、またはメチル基であり、Ｒ₁₀は、炭素数２若しくは３のアルキレン基であり、ｍは、１〜１５の整数である。] General formula (8):

[In General Formula (7) and General Formula (8), R ₉ is a hydrogen atom or a methyl group, R ₁₀ is an alkylene group having 2 or 3 carbon atoms, and m is an integer of 1 to 15. It is. ]

Examples of the ethylenically unsaturated monomer represented by the general formula (7) include:
FANCLIL FA-513A [dicyclopentanyl acrylate, R ₉ : hydrogen atom, R ₁₀ : none, m = 0], or FA-513M [dicyclopentanyl methacrylate, R ₉ : methyl, R ₁₀ manufactured by Hitachi Chemical Co., Ltd. : None, m = 0] and the like, but not limited thereto, two or more kinds can be used in combination.

As an unsaturated ethylene monomer represented by the general formula (8), for example,
FANCLIL FA-511A [dicyclopentenyl acrylate, R ₉ : hydrogen atom, R ₁₀ : none, m = 0], FA-512A [dicyclopentenyloxyethyl acrylate, R ₉ : hydrogen atom, R ₁₀ : Ethylene group, m = 1], FA-512M [dicyclopentenyloxyethyl methacrylate, R ₉ : methyl group, R ₁₀ : ethylene group, m = 1], or FA-512MT [dicyclopentenyloxyethyl methacrylate, R _9: methyl group, R _10: an ethylene group, m = 1] and the like but can be exemplified, without limitation, can be used in combination of two or more kinds.

[Introduction of ethylenically unsaturated double bond]
In addition, the vinyl resin [B1] of the present invention is a structural unit having an ethylenically unsaturated double bond in which an ethylenically unsaturated double bond is introduced using an ethylenically unsaturated monomer having an epoxy group ( It is a vinyl resin having b4).
The vinyl resin [B1] has a double bond group and functions as a site that improves the pattern shape. The structural unit (b4) having an ethylenically unsaturated double bond is 2 to 60% by weight from the viewpoint of the pattern shape based on the weight of all the structural units of the vinyl resin [B1] (100% by weight). preferable. When it is 2% by weight or more, the pattern shape is good, and when it is 60% by weight or less, the resolution is good, which is preferable.
As a method for introducing an ethylenically unsaturated double bond using an ethylenically unsaturated monomer having an epoxy group, an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having an epoxy group can be used. Examples thereof include a method in which an ethylenically unsaturated double bond is introduced using a monomer to form a photosensitive resin, and a method (i1) or a method (i2) shown below is exemplified.

[Method (i1)]
Examples of a method for introducing an ethylenically unsaturated double bond using an ethylenically unsaturated monomer having an epoxy group include an ethylenically unsaturated monomer having an epoxy group and one or more other types of ethylene. A carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is added to the side chain epoxy group of the copolymer obtained by copolymerizing with the polymerizable unsaturated monomer, There is a method (i1) in which a polybasic acid anhydride is reacted with the generated hydroxyl group, an ethylenically unsaturated double bond is introduced to give the function of a photosensitive resin, and a carboxyl group having an alkali-soluble function is introduced. .

  That is, in the present invention, a copolymer (i1-1) was obtained by reacting a precursor of the structural unit (b2) with an ethylenically unsaturated monomer having an epoxy group, and then obtained. A copolymer (i1-2) and an unsaturated monobasic acid are reacted to obtain a copolymer (i1-2). Further, the obtained copolymer (i1-2), a polybasic acid anhydride, A resin obtained by reacting is preferable because the pattern shape is good.

  Moreover, since the carboxyl group of the unsaturated monobasic acid used in this method (i1) forms an ester bond after the addition reaction to the epoxy group, the structural unit (b1) of the vinyl resin [B1] in this specification Since the polybasic acid anhydride forms a carboxyl group after reaction with a hydroxyl group, it corresponds to the structural unit (b1) of the vinyl resin [B1] in this specification.

[Method (i2)]
Alternatively, a part of the side chain carboxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other ethylenically unsaturated monomers. And the method (i2) of introducing an ethylenically unsaturated double bond and a carboxyl group by addition reaction of an ethylenically unsaturated monomer having an epoxy group.

  That is, in the present invention, the precursor of the structural unit (b1) and the precursor of the structural unit (b2) are reacted to obtain a copolymer (i2-1), and then the copolymer obtained A resin obtained by reacting (i2-1) with an ethylenically unsaturated monomer having an epoxy group is preferable because of excellent heat resistance.

  In this case, only the structural unit corresponding to the carboxyl group that is not used for the addition reaction with the epoxy group corresponds to the structural unit (b1) of the vinyl resin [B1] in the present specification.

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

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, P-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano-substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together. Of these, (meth) acrylic acid is preferred.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Further, when etrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

The weight average molecular weight (Mw) of the vinyl resin [B1] is preferably in the range of 5,000 to 100,000, more preferably in the range of 5,000 to 80,000, still more preferably 5,000 to 30. , 000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.
When the weight average molecular weight (Mw) of the vinyl resin [B1] exceeds 100,000, the interaction between the resins becomes strong, and the viscosity of the photosensitive resin composition becomes high, so that the handling tends to be difficult. Further, if the weight average molecular weight (Mw) is less than 5,000, problems may occur in developability and adhesion to a substrate such as glass.

  The weight average molecular weight (Mw) of the vinyl resin [B1] is preferably in the range of 5,000 to 80,000, more preferably in the range of 7,000 to 50,000 in order to disperse the colorant preferably. is there. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are HLC-8220GPC (manufactured by Tosoh Corporation) as a device, and TSK-GEL SUPER HZM-N is connected in series as a column. Is a molecular weight in terms of polystyrene measured using THF.

  When the vinyl resin [B1] is used as a coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent. The balance between the group and the aromatic group is important for the dispersibility, penetrability, developability, and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern does not remain by development.

  The vinyl resin [B1] is preferably used in an amount of 20 to 500 parts by weight with respect to 100 parts by weight of the colorant. If it is less than 20 parts by weight, the film formability and various resistances are insufficient, and if it is more than 500 parts by weight, the concentration of the colorant becomes low and color characteristics cannot be expressed.

(Other resins)
The photosensitive resin composition of the present invention may further contain other resins other than the vinyl resin [B1]. The other resin is preferably a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Other resins include thermoplastic resins, thermosetting resins, and photosensitive resins, and these can be used alone or in admixture of two or more.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 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, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, 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 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, 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, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  In addition, the organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the colored composition can be adjusted to an appropriate viscosity to form a filter segment having a desired uniform film thickness. Is preferred.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether 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 Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate 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, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability. .

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

Examples of the photopolymerization initiator include 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 Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) Nyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -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- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] Or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound or the like is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

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

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Antioxidant>
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  As the hindered phenol-based antioxidant, 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- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2'-thio- Su- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2′thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) ) -Propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro Cinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Examples of hindered amine-based antioxidants include 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-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) 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 oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl 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, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) 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 (diphenoxyphosphonoxy) -ben Zen, ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As sulfur-based antioxidants, 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 and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2 -Hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2, -Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Examples of the salicylate ester 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 singly or in combination of two or more at any ratio as required.

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the photosensitive coloring composition for a color filter because the brightness and sensitivity are good.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

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

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content 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, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene 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 stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. 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- Til-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. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include 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 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

<Method for producing colored composition>
The coloring composition of the present invention contains a coloring agent in a dye carrier such as a binder resin and / or a solvent, preferably together with a dispersion aid, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical It can be produced by finely dispersing (pigment dispersion) using various dispersing means such as a type sand mill, an annular type bead mill, or an attritor. At this time, the specific aluminum phthalocyanine dye and other colorants may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. In addition, when the colorant has high solubility, specifically, it is highly soluble in the solvent to be used, and if it is dissolved by stirring and no foreign matter is confirmed, it is necessary to manufacture by finely dispersing as described above. There is no.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition includes the pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, additives, and the like. Can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a large effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 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-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazettes, Japanese Patent No. 4585781 etc. can be used. These may be used alone or in combination of two or more. When a pigment derivative is used, one having a quinophthalone skeleton is preferable from the viewpoint of brightness.

  The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

  The resin-type dispersant has a colorant-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. -EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7 54,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene 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 stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When a resin-type dispersant and a surfactant are added, the amount 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. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. 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, and the green filter segment is formed from the colored composition of the present invention. The color filter may further comprise a magenta filter segment, a cyan filter segment, and a yellow filter segment, and the cyan filter segment is formed from the colored composition of the present invention. It may be.

  The red filter segment can be formed using a normal red coloring composition comprising a red pigment and a colorant carrier. Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, Mention may be made of red pigments such as 280, 281, 282, 283, 284, 285, 286 or 287. Also, red dyes such as xanthene, azo, disazo, and anthraquinone can be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  In addition, red coloring compositions include C.I. I. Pigment orange 43, 71, or 73, and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,193,194,198,199,213,214,218,219,220, or may be used in combination of a yellow pigment 221, and the like. Also, orange dyes and / or yellow dyes such as quinoline, azo, disazo, and methine dyes can be used.

  The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a colorant carrier. Examples of blue pigments include C.I. I. Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. A purple pigment can be used in combination with the blue coloring composition. Examples of purple pigments that can be used in combination include C.I. I. And violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50. In addition, a basic dye or a salt-forming compound of an acid dye exhibiting blue or purple can be used. When the dye is used, a triarylmethane dye or a xanthene dye is preferable in terms of lightness.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, 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 UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

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

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. “PGMAC” means propylene glycol monomethyl ether acetate.

  The average primary particle diameter of the pigment and the weight average molecular weight (Mw) of the resin are as follows.

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

(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin was measured using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, TSK-GEL SUPER HZM-N connected in series as a column, and THF as a solvent. The molecular weight in terms of polystyrene.

  First, the colorant used in the examples and comparative examples and the method for producing the binder resin solution will be described.

<Method for producing colorant>
(Production of hydroxyaluminum phthalocyanine 1)
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-amyl alcohol and stirred. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of hydroxyaluminum phthalocyanine 1 represented by the following formula (9).

Formula (9)

(Production of hydroxyaluminum phthalocyanine 2)
In the production of hydroxyaluminum phthalocyanine 1, hydroxyaluminum phthalocyanine 2 represented by the following formula (10) was obtained by the same production method except that 250 parts of 4-methylphthalodinitrile was used instead of phthalodinitrile. .

Formula (10)

(Production of blue colorant (A-1))
In a reaction vessel, 100 parts of methanol, 100 parts of hydroxyaluminum phthalocyanine 1 and 49.5 parts of diphenyl phosphate were added, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of a specific phthalocyanine dye represented by formula (1-1).

  Subsequently, a salt milling process was performed. 100 parts of the specific phthalocyanine dye represented by the formula (1-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of colorant (A-1) were obtained. The average primary particle size was 31.2 nm.

(Production of blue colorant (A-2))
In a reaction vessel, 100 parts of hydroxyaluminum phthalocyanine 1 and 43.2 parts of diphenylphosphinic acid 1 were added to 1000 parts of methanol, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain 112 parts of a specific phthalocyanine dye represented by formula (1-2).
The specific phthalocyanine dye represented by the formula (1-2) thus obtained was subjected to a salt milling method similar to that for the blue colorant (A-1) to obtain a blue colorant (A-2). The average primary particle size was 29.5 nm.

(Production of blue colorant (A-3))
100 parts of hydroxyaluminum phthalocyanine 2 and 28.0 parts of phenylphosphinic acid were added to 1000 parts of methanol in a reaction vessel, heated to 40 ° C. and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain 102 parts of a specific phthalocyanine dye represented by formula (1-3).
A blue colorant (A-3) was produced from the obtained specific phthalocyanine dye represented by the formula (1-3) by the same salt milling method as that for the blue colorant (A-1). The average primary particle size was 33.1 nm.

(Production of yellow colorant (Y-1))
C. I. 100 parts of Pigment Yellow 138 (trade name Paliotor Yellow K0961HD, manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of colorant (Y-1) were obtained. The average primary particle size was 35.5 nm.

<Method for producing binder resin solution>
[Resin solution (B1-1)]
(Stage 1: Polymerization of resin main chain)
Place 100 parts of propylene glycol monomethyl ether acetate (PGMAC) in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. At the same temperature, 16.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and azobisisobutyronitrile 1 as a catalyst required for the reaction of the precursor at this stage 0.0 part of the mixture was added dropwise over 2.5 hours to carry out the polymerization reaction.

(Step 2: Reaction to epoxy group)
Next, the inside of the flask was purged with air, and 17.0 parts of acrylic acid and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, Reaction was performed for 5 hours, and the resin solution whose weight average molecular weight is about 12000 (measurement by GPC) was obtained. The added acrylic acid is ester-bonded to the end of the epoxy group of the glycidyl methacrylate structural unit, so that no carboxyl group is generated in the resin structure.

(Step 3: Reaction to hydroxyl group)
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine as a catalyst required for the reaction of the precursor at this stage were added and reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of two carboxyl groups generated by cleavage of the carboxylic anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxyl group terminal.

(Step 4: Adjustment of nonvolatile content)
Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 40% to obtain a resin solution (B1-1).

  The weight ratio of the structural unit in the resin solution (B1-1) is as follows: tetrahydrophthalic anhydride as the structural unit (b1); 21.7% by weight, styrene as the structural unit (b2); 11.6% by weight, structural unit (b3 ) As dicyclopentanyl methacrylate; 29.3% by weight; as the structural unit (b4), the total of glycidyl methacrylate and acrylic acid ester-bonded to the glycidyl terminal; 37.4% by weight.

[Resin solutions (B1-2 to 3 and B2-1)]
Resin solutions (B1-2) to (B1-3) and (B2-1) were obtained in the same manner as the resin solution (B1-1). That is, in the manufacturing method of the resin solution (B1-1), the precursors corresponding to the structural units (b1) to (b4) and other structural units were replaced according to Table 1. The number of catalyst parts required for each stage was mixed in proportion to the total number of precursors mixed in each stage.

[Resin solution (B1-4 to 5)]
Resin solutions (B1-4) to (B1-5) were obtained in the same manner as in steps 1, 2, and 4 of resin solution (B1-1). That is, in the manufacturing method of the resin solution (B1-1), the precursors corresponding to the structural units (b1) to (b4) and other structural units were replaced according to Table 1. The precursor corresponding to MAA (methacrylic acid) in the structural units (b1) to (b3) and the structural unit (b4) is mixed to carry out stage 1 of production, and then GMA (glycidyl methacrylate) is used as the precursor. In addition, stage 2 of the production was carried out and stage 4 was further carried out. The number of catalyst parts required for each stage was mixed in proportion to the total number of precursors mixed in each stage.

[Resin solution (B2-2)]
The resin solution (B2-2) was prepared in the same manner as in Step 1, Step 2, and Step 4 of the resin solution (B1-1). That is, in the manufacturing method of the resin solution (B1-1), the precursors corresponding to the structural units (b1) to (b4) and other structural units were replaced according to Table 1. GMA (glycidyl methacrylate) in the structural unit (b2), the structural unit (b4), and other precursors corresponding to the other structural units are mixed to perform Step 1 of production, and then AA (acrylic acid) is the precursor. In addition, stage 2 of the manufacturing was carried out and stage 4 was further carried out. The number of catalyst parts required for each stage was mixed in proportion to the total number of precursors mixed in each stage.

  Table 1 shows the compositions and weight ratios of the obtained resin solutions (B1-1 to 5) and resin solutions (B2-1 to 2). The value in parentheses represents the weight ratio (% by weight) of the constituent unit in the resin solid content.

The precursors of the structural units and the abbreviations of the structural units in Table 1 are described below.
MAA: methacrylic acid THPA: tetrahydrophthalic anhydride (4-cyclohexene-1,2-dicarboxylic anhydride)
BzMA: Benzyl methacrylate St: Styrene DCPMA: Dicyclopentanyl methacrylate GMA: Glycidyl methacrylate GMA-AA: A structure in which acrylic acid is added to the structural unit GMA and bonded MMA-GMA: GMA is added in the structural unit to the methacrylic acid and bonded BMA: n-butyl methacrylate HEMA: 2-hydroxyethyl methacrylate

[Resin solution (B2-3)]
70.0 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen Thereafter, a mixture of 67.2 parts of benzyl methacrylate, 18.4 parts of methacrylic acid, 14.4 parts of dicyclopentanyl methacrylate, and 0.4 parts of 2,2′-azobisisobutyronitrile was added from the dropping tube over 2 hours. The solution was added dropwise to carry out a polymerization reaction. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a solid content of 50% by weight.
After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl was added to the previously synthesized resin solution so that the nonvolatile content was 40% by weight. Ether acetate was added to prepare a resin solution (B2-3). The weight average molecular weight was 22000.

[Resin solution (B2-4)]
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, and the temperature was raised to 80 ° C. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample about 2 parts of the resin solution, heat dry at 180 ° C for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 40 wt% Thus, a resin solution (B2-4) was prepared. The weight average molecular weight (Mw) was 18000.

[Resin solution (B2-5)]
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. Was added to prepare a resin solution (B2-5). The weight average molecular weight (Mw) was 26000.

[Example 1]
(Green coloring composition (DG-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. It filtered with a 0.0 micrometer filter and produced the green coloring composition (DP-1). At this time, when the coated substrate is used, the blue colorant (A-1) and the yellow colorant (Y-1) are matched with the C light source so that the chromaticity is x = 0.290 and y = 0.600. The ratio was selected.

Blue colorant (A-1) 3.4 parts Yellow colorant (Y-1) 7.6 parts Resin-type dispersant ("BYK-LPN6919" manufactured by Big Chemie) 5.5 parts Acrylic resin solution (B1-1) 14.25 parts PGMAC 53.25 parts cyclohexanone 16.0 parts

[Example 2]
(Green coloring composition (DG-2))
A green colored composition (DG-2) was obtained in the same manner as the green colored composition (DG-1) except that the blue colorant (A-1) was changed to the blue colorant (A-2).

[Example 3]
(Green coloring composition (DG-3))
A green colored composition (DG-3) was obtained in the same manner as the green colored composition (DG-1) except that the blue colorant (A-1) was changed to the blue colorant (A-3).

[Examples 4 to 8, Comparative Examples 1 to 5]
(Green coloring composition (DG-4 to 13))
Except having changed the resin solution (B1-1) into the resin solution shown in Table 2, it carried out similarly to the green coloring composition (DG-1), and obtained the green coloring composition (DG-4-13).

<Coating preparation and evaluation>
The contrast ratio (CR) of the green coating film produced using the obtained green coloring composition (DG-1-13) and heat resistance evaluation were performed by the following method. Table 2 shows the evaluation results.

(Evaluation of contrast ratio (CR) of coating film)
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the coating film of the colored composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the colored composition, scattering or the like occurs by the colorant particles, and when a part of the polarization plane is displaced, the polarizing plate is transmitted in parallel. When the polarizing plate is orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plates were parallel and the luminance when they were orthogonal was calculated as the contrast ratio.

(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)

Therefore, when scattering occurs due to the colorant in the coating film, the luminance when parallel is reduced and the luminance when orthogonal is increased, the contrast ratio becomes low.

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

The green coloring composition (DG-1 to 13) was applied on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 30 minutes. A coated substrate was prepared by heating and cooling for a minute. The contrast ratio (CR) of the obtained coated substrate was measured. The prepared coated substrate was adjusted to a chromaticity of y = 0.600 with a C light source after heat treatment at 220 ° C.
The contrast ratio was determined according to the following criteria.
○: 4000 or more Δ: 3500 or more and less than 4000 ×: less than 3500

(Evaluation of heat resistance of coating film)
The green coloring composition (DG-1 to 13) was applied on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 30 minutes. A coated substrate was prepared by heating and cooling for a minute. The prepared coated substrate was adjusted to a chromaticity of y = 0.600 with a C light source after heat treatment at 220 ° C. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following four stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
◎: ΔEab * is less than 3.0 ○: ΔEab * is less than 5.0 Δ: ΔEab * is 5.0 or more and less than 10.0 ×: ΔEab * is 10.0 or more

  As shown in Table 2, the coloring composition for a color filter of the present invention containing a phthalocyanine dye having a specific structure and a binder resin having a specific structure has a high contrast ratio and extremely excellent heat resistance. Met.

<Method for producing green photosensitive coloring composition>
[Example 9]
(Green photosensitive coloring composition (RG-1))
A mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain a green photosensitive coloring composition (RG-1).

Green coloring composition (DG-1) 55.0 parts Acrylic resin solution (B1-1) 9.2 parts Photopolymerizable monomer (“Aronix M402” manufactured by Toagosei Co., Ltd. 3.8 parts Photopolymerization initiator (Ciba -"Irgacure 907" manufactured by Japan Co., Ltd.) 1.9 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.3 parts PGMAC 19.8 parts Cyclohexanone 10.0 parts

[Example 10]
(Green photosensitive coloring composition (RG-2))
A green photosensitive coloring composition (RG-2) was obtained in the same manner as in Example 9 except that the green coloring composition (DG-1) was changed to the green coloring composition (DG-2).

[Example 11]
(Green photosensitive coloring composition (RG-3))
A green photosensitive coloring composition (RG-3) was obtained in the same manner as in Example 9 except that the green coloring composition (DG-1) was changed to the green coloring composition (DG-3).

[Examples 12 to 17, Comparative Examples 6 to 11]
(Green photosensitive coloring composition (RG-4 to 15))
Green photosensitive coloring compositions (RG-4 to 15) were obtained in the same manner as in Example 9 except that the acrylic resin solution (B1-1) was changed to the acrylic resin solution shown in Table 3.

<Coating preparation and evaluation>
The following methods evaluated the contrast ratio, heat resistance, developability, pattern shape, and resolution of the green coating film produced using the obtained green photosensitive coloring composition (RG-1-15). Table 3 shows the evaluation results.

(Evaluation of contrast ratio of coating film)
The green photosensitive coloring composition (RG-1 to 15) was applied on a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, and then dried at 70 ° C. for 20 minutes. Using a lamp, UV exposure was performed with an integrated light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. to obtain a coated substrate. Then, after heating at 220 ° C. for 30 minutes and allowing to cool, the contrast ratio (CR) of the obtained coating film substrate was measured by the same method as the evaluation of the colored composition. The prepared coated substrate was adjusted to a chromaticity of y = 0.600 with a C light source after heat treatment at 220 ° C. The alkali developer was 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of an anionic surfactant (“Perex NBL” manufactured by Kao Corporation), and 90% by weight of water. The thing which consists of was used.
The contrast ratio was determined according to the following criteria.
○: 4000 or more Δ: 3500 or more and less than 4000 ×: less than 3500

(Evaluation of heat resistance of coating film)
The green photosensitive coloring composition (RG-1 to 15) was applied on a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, and then dried at 70 ° C. for 20 minutes. Using a lamp, UV exposure was performed with an integrated light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. Subsequently, it was heated at 220 ° C. for 30 minutes and allowed to cool to obtain a coated substrate. The prepared coated substrate was adjusted to a chromaticity of y = 0.600 with a C light source after heat treatment at 220 ° C. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following four stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
A: ΔEab * is less than 3.0 ○: ΔEab * is less than 5.0 Δ: ΔEab * is 5.0 or more and less than 10.0 X: ΔEab * is 10.0 or more

(Developability evaluation)
A substrate in which a green photosensitive coloring composition (RG-1 to 15) is applied on a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater at a rotation speed of 2 μm after drying. After drying at 70 ° C. for 20 minutes, spray development was performed using a sodium carbonate aqueous solution at 23 ° C., and the developability was evaluated in four stages. The alkali developer was 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of an anionic surfactant (“Perex NBL” manufactured by Kao Corporation), and 90% by weight of water. The thing which consists of was used.
◎: Can be completely removed within 30 seconds ○: Over 30 seconds but completely removed within 33 seconds Δ: Over 33 seconds but completely removed within 36 seconds ×: Over 36 seconds Can not be completely removed

(Pattern shape, resolution evaluation)
After coating the green photosensitive coloring composition (RG-1 to 15) on a 100 mm × 100 mm, 1.1 mm thick glass substrate, the solvent was removed by heating at 70 ° C. for 20 minutes in a clean oven, A coating film of about 2 μm was obtained. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) using an ultrahigh pressure mercury lamp. Thereafter, this substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 230 ° C. for 330 minutes in a clean oven. The spray development was performed in the shortest time during which a pattern can be formed without any development remaining on the coating film of each photosensitive coloring composition, and this was set as an appropriate development time. The alkali developer was 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of an anionic surfactant (“Perex NBL” manufactured by Kao Corporation), and 90% by weight of water. The thing which consists of was used.
The film thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

((Pattern shape evaluation))
A 100 μm photomask portion of the filter segment formed by the above method was cut into a 1 cm square glass and subjected to Pt / Pd vapor deposition with a Hitachi sputtering apparatus (E-1030), and then a Hitachi SEM (S-4300). ), The cross-sectional pattern shape of the filter segment was observed at an acceleration voltage of 15 kV and an observation magnification of 10,000 times, and was evaluated in four stages according to the angle (θ degrees) formed between the glass substrate and the edge portion of the cross section of the filter segment.
◎: θ <20 degrees, forward tapered shape ○: 20 degrees ≦ θ ≦ 45 degrees, forward tapered shape Δ: 45 degrees <θ ≦ 80 degrees, forward tapered shape ×: θ> 80 degrees, sharp forward taper to overhang

((Resolution evaluation))
The pattern in the 25 μm photomask portion of the filter segment formed by the above method was evaluated by observing with an optical microscope. The rank of evaluation is as follows. The poor resolution means that adjacent stripe patterns are connected or chipped. The resolution evaluation was determined according to the following criteria.
◎: Good resolution and linearity ○: Slightly inferior in linearity but good resolution △: Partially poor resolution ×: Poor resolution

  As shown in Table 3, the coloring composition for a color filter of the present invention containing a phthalocyanine dye having a specific structure and a binder resin having a specific structure obtained high-level evaluation results in all evaluations.

  That is, in the combination with the phthalocyanine dye having a specific structure, the development property is improved in the structure containing a large amount of the structural unit (b1) of the resin (B1), and the contrast ratio is improved in the structure containing a large amount of the structural unit (b2). In addition, the composition containing a large amount of the structural unit (b3) tends to have an effect of suppressing the resolution, and is a colored composition having high performance.

<Production of color filter>
First, the red photosensitive coloring composition and the blue photosensitive coloring composition used for preparation of a color filter were produced.

(Preparation of red photosensitive coloring composition (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. It filtered with a 0.0 micrometer filter, and produced the red coloring composition (DR-1).

Red pigment (CI Pigment Red 254) 9.6 parts Red Pigment (CI Pigment Red 177) 2.4 parts Resin-type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Resin solution (B2-5) 17.5 parts 69.5 parts propylene glycol monomethyl ether acetate

Subsequently, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a red photosensitive coloring composition (RR-1).

Red coloring composition (DR-1) 42.0 parts Resin solution (B2-4) 6.6 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (Ciba・ "Irgacure 907" manufactured by Japan Co., Ltd.) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 46.2 parts ethylene glycol monomethyl ether acetate

(Preparation of blue photosensitive coloring composition (RB-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. It filtered with a 0.0 micrometer filter, and produced blue coloring composition (DB-1).

Blue pigment (CI Pigment Blue 15: 6) 7.2 parts Purple Pigment (CI Pigment Violet 23) 4.8 parts Resin Type Dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Resin solution (B2-5) 17.5 parts Propylene glycol monomethyl ether acetate 69.5 parts

Then, after stirring and mixing the mixture of the following composition so that it might become uniform, it filtered with a 1.0 micrometer filter, and produced blue photosensitive coloring composition 1 (RB-1).

Blue coloring composition 1 (DB-1) 34.0 parts Resin solution (B2-4) 7.6 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator ( "Irgacure 907" manufactured by Ciba Japan Co., Ltd.) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 52.7 parts ethylene glycol monomethyl ether acetate

(Production of color filter)
A black matrix is patterned on a glass substrate, and the red photosensitive coloring composition (RR-1) is applied to the substrate with a spin coater in a C light source (hereinafter also used for green and blue) x = 0.640, y = 0.330 was applied to form a colored film. The film was irradiated with ultraviolet rays of 150 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 220 ° C. for 20 minutes to obtain a red filter segment Formed. By using the same method, the blue photosensitive coloring composition (RB-1) was prepared so that x = 0.290 and y = 0.600 using the green photosensitive coloring composition (RG-1) of the present invention. A green filter segment and a blue filter segment were formed so that x = 0.150 and y = 0.060 were used to obtain a color filter.

  By using the green photosensitive coloring composition (RG-1) of the present invention, the color filter can be made to have a high CR, and other physical properties can be suitably used without any problem.

Claims (5)

A color filter coloring composition comprising a colorant, a binder resin, and an organic solvent, wherein the colorant contains a phthalocyanine dye represented by the following general formula (1), and the binder resin is an epoxy group A vinyl resin into which an ethylenically unsaturated double bond has been introduced using an ethylenically unsaturated monomer having the following structure, and contains a vinyl resin [B1] containing the following structural units (b1) and (b2) A colored composition for a color filter.
General formula (1)

[In General Formula (1), A ^{1 to} A ¹⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, an alkyl group that may have a substituent, or an aryl that may have a substituent. Represents a group.
R ¹ and R ² are each independently hydrogen atom, hydroxy group, an optionally substituted alkyl group, an optionally substituted aryl group, or an -OR ^3, and R ¹ R ² may be bonded to each other to form a ring.
R ³ is an alkyl group which may have a substituent or an aryl group which may have a substituent. ]

(B1); a structural unit having a carboxyl group:
2 to 60% by weight based on the weight of all structural units of the vinyl resin [B1]
(B2): a structural unit having an aromatic ring group represented by the general formula (2) or the general formula (3):
2 to 80% by weight based on the weight of all structural units of the vinyl resin [B1]
General formula (2):

General formula (3):

[In General Formulas (2) and (3), R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ] Vinyl resin [B1]
The precursor of the structural unit (b2) is reacted with an ethylenically unsaturated monomer having an epoxy group to obtain a copolymer (i1-1), and then the copolymer (i1-1) obtained ) And an unsaturated monobasic acid to obtain a copolymer (i1-2), and a resin obtained by reacting the obtained copolymer (i1-2) with a polybasic acid anhydride ,
Alternatively, the precursor of the structural unit (b1) and the precursor of the structural unit (b2) are reacted to obtain a copolymer (i2-1), and then the copolymer (i2-1) obtained The colored composition for a color filter according to claim 1, which is a resin obtained by reacting an ethylenically unsaturated monomer having an epoxy group. The colored composition for a color filter according to claim 1 or 2, wherein the vinyl resin [B1] further contains the following structural unit (b3).

(B3): a structural unit having an aliphatic cyclic group represented by formula (4) or formula (5):
2 to 60% by weight based on the weight of all structural units of the vinyl resin [B1]
Formula (4):

Formula (5):

  Furthermore, the coloring composition for color filters of any one of Claim 1 thru | or 3 containing a photopolymerizable monomer and / or a photoinitiator.   A color filter comprising a filter segment formed from the colored composition for a color filter according to claim 1 on a substrate.