JP2013054339A - Color composition for color filters, and color filters - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color composition for a color filter which is excellent in the lightness, the contrast ratio and the tinctorial strength and satisfactory in other characteristics such as the heat resistance, the light resistance and the sensitivity when used for a color filter, and also provide a color filter based on the same.SOLUTION: A color composition for color filters comprises a colorant, a binder resin, and a solvent. The colorant contains one or more quinophthalone pigments [A] selected from those represented by the general formulas (1), (2) and (3), and a quinophthalone dye [B] represented by the general formula (4).

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 quality item required for the color filter is brightness. When a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights that are light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend.

  Furthermore, as described above, color liquid crystal devices are now used in televisions, personal computer monitors, etc., so that color filters have higher brightness, higher contrast, and higher reliability (heat resistance, light resistance). It is requested.

Examples of the yellow colorant for the color filter used for forming the green filter segment include C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment Yellow 185 or the like has been conventionally used. Among them, C.I. I. Pigment Yellow 138 is often used. However, C.I. I. Although pigment yellow 138 is relatively excellent in brightness, further improvement in brightness is desired. In addition, C.I. I. Pigment Yellow 138 has a problem of low contrast and low coloring power. Therefore, the conventional C.I. I. There is a need for a yellow colorant that is superior in lightness, contrast, and tinting strength to CI Pigment Yellow 138.

  Patent Document 1 discloses a quinophthalone pigment having a naphthalene ring for coloring a polymer material. However, all of the quinophthalone pigments obtained by the method of Patent Document 1 are for the purpose of coloring plastics, and there is no description about their suitability for color filter applications.

  Further, as colorants for color filters, quinophthalone dyes as shown in Patent Documents 2 and 3 have been proposed so far. However, since these dyes have a hydroxyl group in the quinoline ring, when the colored composition for color filter is prepared and applied to the substrate, the spectral shape of the coating film is poor and the lightness is not improved. Other quinophthalone dyes include C.I. I. Solvent Yellow 33 and C.I. I. Disperse Yellow 54 and 64 can be mentioned, but these dyes have no coloring power and have poor heat resistance and light resistance and cannot be used as colorants for color filters. Furthermore, when using dye for the photosensitive coloring composition containing components, such as a photoinitiator and a photopolymerizable monomer, there exists a problem that sufficient sensitivity cannot be obtained and pattern formation is difficult.

Japanese Unexamined Patent Publication No. 57-90058 JP-A-6-009891 JP 2006-091768 A

  The problem to be solved by the present invention is a color filter coloring composition that is excellent in brightness, contrast ratio, and coloring power when used in a color filter, and has other characteristics (heat resistance, light resistance, sensitivity), And providing a color filter using the same.

  As a result of intensive studies, the present inventors have found that the colorant contains a quinophthalone pigment [A] having a specific structure and a quinophthalone dye [B] having a specific structure, so that the color filter coloring composition is The present inventors have found that the above problems can be solved, and have reached the present invention.

[一般式（１）〜（３）中、Ｒ¹⁴〜Ｒ²⁸、Ｒ²⁹〜Ｒ⁴³、およびＲ⁴⁴〜Ｒ⁶⁰は、それぞれ独立して、水素原子、ハロゲン原子、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ルコキシル基、置換基を有してもよいアリール基、−ＳＯ₃Ｈ；−ＣＯＯＨ；およびこれら酸性基の１価〜３価の金属塩；アルキルアンモニウム塩、置換基を有してもよいフタルイミドメチル基、または置換基を有してもよいスルファモイル基を表す。］

[一般式（４）中、Ｒ⁴〜Ｒ⁹は、それぞれ独立に水素原子、ハロゲン原子、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ルケニル基、置換基を有してもよいアリール基、または−ＯＲ¹⁰を表す。
Ｒ¹⁰は、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ルケニル基、または置換基を有してもよいアリール基である。
ただし、Ｒ⁴〜Ｒ⁹が全て水素原子になる事はない。] That is, the present invention is a color filter coloring composition containing a colorant, a binder resin, and an organic solvent, and the colorant is represented by the following general formula (1), general formula (2), and general formula ( The present invention relates to a color filter coloring composition comprising one or more quinophthalone pigments [A] selected from 3) and a quinophthalone dye [B] represented by the following general formula (4).

[In General Formulas (1) to (3), R ^{14 to} R ²⁸ , R ^{29 to} R ⁴³ , and R ^{44 to} R ⁶⁰ may each independently have a hydrogen atom, a halogen atom, or a substituent. A good alkyl group, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, —SO ₃ H; —COOH; and monovalent to trivalent metal salts of these acidic groups; It represents a salt, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent. ]

[In General Formula (4), R ^{4 to} R ⁹ each independently have a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. An aryl group which may be substituted, or —OR ¹⁰ ;
R ¹⁰ is an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent.
However, R ^{4 to} R ⁹ are not all hydrogen atoms. ]

Further, the present invention is characterized in that R ^{14 to} R ²⁸ , R ^{29 to} R ⁴³ , and R ^{44 to} R ⁶⁰ in the general formulas (1) to (3) are each independently a hydrogen atom or a halogen atom. The present invention relates to a coloring composition for a color filter.

In addition, the present invention relates to the coloring composition for a color filter, wherein at least one of R ^{4 to} R ⁹ in the general formula (4) is —OR ¹⁰ .

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.

  By using the coloring composition for a color filter of the present invention, it is possible to provide a color filter that is excellent in lightness, contrast ratio, and coloring power, and has good heat resistance and light resistance.

Hereinafter, the present invention will be described in detail.
Note that “CI” described below means a color index (CI).

  The present invention provides a color filter coloring composition containing a colorant, a binder resin, and an organic solvent, wherein the colorant is selected from the general formula (1), the general formula (2), and the general formula (3). The above quinophthalone pigment [A] (hereinafter sometimes referred to as “specific quinophthalone pigment”) and the quinophthalone dye [B] represented by the general formula (4) (hereinafter sometimes referred to as “specific quinophthalone dye”) And a coloring composition for a color filter. By using a specific quinophthalone pigment and a specific quinophthalone dye in combination, an effect excellent in lightness, contrast ratio, and coloring power is exhibited. Although the specific quinophthalone dye has a characteristic of high brightness, it has problems of low contrast ratio and low sensitivity. By using together with a specific quinophthalone pigment having a high contrast ratio, these problems can be solved while maintaining high brightness.

<Colorant>
The coloring composition for a color filter of the present invention includes, as a colorant, one or more quinophthalone pigments [A] selected from general formula (1), general formula (2), and general formula (3), and a general formula ( And a quinophthalone dye [B] represented by 4).

[一般式（１）〜（３）中、Ｒ¹⁴〜Ｒ²⁸、Ｒ²⁹〜Ｒ⁴³、およびＲ⁴⁴〜Ｒ⁶⁰は、それぞれ独立して、水素原子、ハロゲン原子、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ルコキシル基、置換基を有してもよいアリール基、−ＳＯ₃Ｈ；−ＣＯＯＨ；およびこれら酸性基の１価〜３価の金属塩；アルキルアンモニウム塩、置換基を有してもよいフタルイミドメチル基、または置換基を有してもよいスルファモイル基を示す。］ (Kinophthalone pigment [A])
The quinophthalone pigment [A] contains at least one pigment having a structure represented by the general formula (1), the general formula (2), and the general formula (3).

[In General Formulas (1) to (3), R ^{14 to} R ²⁸ , R ^{29 to} R ⁴³ , and R ^{44 to} R ⁶⁰ may each independently have a hydrogen atom, a halogen atom, or a substituent. A good alkyl group, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, —SO ₃ H; —COOH; and monovalent to trivalent metal salts of these acidic groups; A salt, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent is shown. ]

  Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

  Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a ptyl group, an isoptyl group, a tert-butyl group, a neopentyl group, an n-hexyl group and an n-octyl group. Group, stearyl group, linear or branched alkyl group such as 2-ethylhexyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, pendyl group, 4-methylpentyl group, 4-tert-butylbenzyl group, 4-methoxy Examples thereof include an alkyl group having a substituent such as a pendyl group, a 4-nitrobenzyl group, and a 2,4-dichlorobenzyl group.

  Examples of the alkoxyl group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isoptyloxy group, a tert-butyloxy group, a neopentyloxy group, 2, In addition to linear or branched alkoxyl groups such as 3-dimethyl-3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitro Examples include an alkoxyl group having a substituent such as a propoxy group and a benzyloxy group.

  In addition, examples of the aryl group which may have a substituent include an aryl group such as a phenyl group, a naphthyl group, an anthranyl group, a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p- Methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4 , 5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group and other aryl groups having a substituent.

Examples of acidic groups include —SO ₃ H and —COOH, and monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, and aluminum salts. Etc. In addition, as the alkyl ammonium salt of acidic group, quaternary alkyl such as ammonium salt of long-chain monoalkylamine such as octylamine, laurylamine, stearylamine, palmityltrimethylammonium, dilauryldimethylammonium, distearyldimethylammonium salt, etc. An ammonium salt is mentioned.

The “substituent” in the phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —) which may have a substituent and the sulfamoyl group (H ₂ NSO ₂ —) which may have a substituent "Includes the above halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, and the like.

Furthermore, the quinophthalone pigment [A] used in the coloring composition for a color filter of the present invention includes R ^{14 to} R ²⁸ , R ^{29 to} R ⁴³ , and R ^{44 to} R ^{60 in} the general formulas (1) to (3). From the viewpoints of brightness and contrast ratio, a hydrogen atom or a halogen atom is preferable.

  The quinophthalone pigment [A] that can be used in the colored composition of the present invention may contain two or more quinophthalone pigments. At this time, quinophthalone pigments produced separately may be mixed together, or two or more quinophthalone pigments may be produced simultaneously by a cosynthesis method. When these separately prepared quinophthalone pigments are used, they may be simply mixed before the two types of pigments are dispersed, or may be pulverized and mixed by a salt milling process.

  Moreover, although it is essential that the coloring composition of this invention contains at least 1 or more types of pigment represented by General formula (1)-(3) as quinophthalone pigment [A], quinophthalone pigment [A] Other pigments may be included. Examples of pigments other than the quinophthalone pigment [A] include C.I. having the same quinophthalone skeleton. I. Pigment Yellow 138 is preferably used in terms of contrast ratio. This is because the quinophthalone pigment [A] has a skeleton similar to that of C.I. I. This is because Pigment Yellow 138 is effective.

  Specific examples of the quinophthalone pigment [A] that can be used in the colored composition for a color filter of the present invention are shown below, but are not limited thereto.

[一般式（４）中、Ｒ⁴〜Ｒ⁹は、それぞれ独立に水素原子、ハロゲン原子、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ルケニル基、置換基を有してもよいアリール基、または−ＯＲ¹⁰を表す。
Ｒ¹⁰は、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ルケニル基、または置換基を有してもよいアリール基である。
ただし、Ｒ⁴〜Ｒ⁹が全て水素原子になる事はない。] (Kinophthalone dye [B])
The quinophthalone dye [B] is a dye having a structure represented by the general formula (4).

[In General Formula (4), R ^{4 to} R ⁹ each independently have a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. An aryl group which may be substituted, or —OR ¹⁰ ;
R ¹⁰ is an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent.
However, R ^{4 to} R ⁹ are not all hydrogen atoms. ]

The alkyl group which may have a substituent in R ^{4 to} R ¹⁰ is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms, or a case having 2 to 30 carbon atoms. Includes a linear, branched, monocyclic or condensed polycyclic alkyl group containing one or more ester bonds (—COO—) and one or more ether bonds (—O—). Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, trifluoromethyl group, isopropyl group, isobutyl group, isopentyl group, 2-ethylhexyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert- A pentyl group, a tert-octyl group, a neopentyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, a 4-decylcyclohexyl group, and the like can be mentioned. It is not something.

Specific examples of the linear or branched alkyl group having 2 to 30 carbon atoms and optionally including one or more ester bonds include —CH ₂ —CH ₂ —CH ₂ —COO—CH ₂ —CH ₃ , _{-CH 2 -CH (-CH 3) -CH} 2 -COO-CH 2 -CH 3, -CH 2 -CH 2 -CH 2 -OCO-CH 2 -CH 3, -CH 2 -CH 2 -CH 2 - _{CH 2 -COO-CH 2 -CH (} -CH 2 -CH 3) -CH 2 -CH 2 -CH 2 -CH 3, - (CH 2) 5 -COO- (CH 2) 11 -CH 3, -CH _{2 -CH 2 -CH 2 -CH (-COO} -CH 2 -CH 3) can be exemplified _2, etc., but is not limited thereto.

  Specific examples of the linear or branched alkyl group having 2 to 30 carbon atoms and optionally including one or more ether bonds include —CH 2 —O—CH 3, —CH 2 —CH 2 —O—CH 2 —. CH3, -CH2-CH2-CH2-O-CH2-CH3,-(CH2-CH2-O) n-CH3 (where n is 1 to 8),-(CH2-CH2-CH2-O) m- CH3 (where m is 1 to 5), -CH2-CH (CH3) -O-CH2-CH3-, -CH2-CH- (OCH3) 2, and the like can be mentioned, but are not limited thereto. It is not a thing.

Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 30 carbon atoms and optionally including one or more ether bonds include the following, but are not limited thereto. Absent.

Furthermore, specific examples of linear, branched, and alkyl groups having 3 to 30 carbon atoms and including one or more ester bonds (—COO—) and ether bonds (—O—) include —CH ₂ —. _{CH 2 -COO-CH 2 -CH 2} -O-CH 2 -CH (CH 2 -CH 3) -CH 2 -CH 2 -CH 2 -CH 3, -CH 2 -CH 2 -COO-CH 2 -CH _{2 -O-CH 2 -CH 2 -O} -CH 2 -CH (CH 2 -CH 3) can be exemplified _{-CH 2 -CH 2 -CH 2 -CH 3} , but the invention is not limited to .

Examples of the alkenyl group which may have a substituent in R ^{4 to} R ¹⁰ include linear, branched, monocyclic or condensed polycyclic alkenyl groups having 1 to 30 carbon atoms. They may have a plurality of carbon-carbon double bonds in the structure. Specific examples include vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4- Pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group, cyclopenta Although a dienyl group etc. can be mentioned, it is not limited to these.

The aryl group which may have a substituent in R ^{4 to} R ¹⁰ is a substituted or unsubstituted monocyclic or condensed polycyclic aromatic group having 6 to 18 carbon atoms, such as a phenyl group, 1- Naphthyl group, 2-naphthyl group, p-biphenyl group, m-biphenyl group, 2-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2-fluorenyl group, 3- Fluorenyl group, 9-fluorenyl group, 1-pyrenyl group, 2-pyrenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 4-methylbiphenyl group, terphenyl group, 4- Methyl-1-naphthyl group, 4-tert-butyl-1-naphthyl group, 4-naphthyl-1-naphthyl group, 6-phenyl-2-naphthyl group, 10-phenyl-9-an Lil group, spirofluorenyl group, 4-maleimidyl phenyl group, such as 2-benzocyclobutenyl group.

Furthermore, the quinophthalone dye [B] used in the coloring composition for a color filter of the present invention is such that at least one of R ^{4 to} R ⁹ in the general formula (4) is —OR ^10. From the viewpoints of light resistance and light resistance.

  The quinophthalone dye [B] can be obtained by reacting the corresponding 2-methylquinoline and naphthalenedicarboxylic anhydride in benzoic acid at a high temperature as shown in the following reaction formula.

  Specific examples of the quinophthalone dye [B] that can be used in the colored composition for a color filter of the present invention are shown below, but are not limited thereto.

  The content of the quinophthalone pigment [A] and the quinophthalone dye [B] is preferably in the range of 10 to 1500 parts by weight of the quinophthalone dye [B] with respect to 100 parts by weight of the quinophthalone pigment [A]. More preferably, it is the range of 100-1200 weight part. When the amount of the quinophthalone dye [B] is more than 10 parts by weight, the effect of improving the brightness can be exhibited. Moreover, when it is less than 1500 parts by weight, the contrast ratio and sensitivity when used as a photosensitive coloring composition are preferable.

(Other colorants)
The coloring composition of the present invention may use a colorant other than the quinophthalone pigment [A] and the quinophthalone dye [B] in order to form a green filter segment, a red filter segment, or a yellow filter segment. In particular, the colored composition of the present invention is very excellent in forming a green filter segment having high brightness by using a green colorant and / or a blue colorant in combination. In addition, a yellow colorant other than the quinophthalone pigment [A] and the quinophthalone dye [B] can be used in combination as long as the effects of the present invention are not impaired.

  Examples of the green colorant that can be used in combination with the green filter segment include C.I. I. Examples thereof include, but are not limited to, green pigments such as CI Pigment Green 7, 10, 36, 37, and 58. Preferred green colorants to be used in combination are C.I. I. Pigment green 36 and 58.

  Examples of blue colorants that can be used in combination with the green filter segment include C.I. I. Pigment Blue 15: 3, 15: 4, and aluminum phthalocyanine pigments may be mentioned, but are not limited thereto. A preferable blue colorant to be used in combination is an aluminum phthalocyanine pigment from the viewpoint of brightness. The aluminum phthalocyanine pigment is not particularly limited as long as it has a structure in which trivalent aluminum is coordinated at the center of the phthalocyanine ring.

Examples of the red colorant that can be used in combination for forming the red filter segment 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, 149, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 242, 246, 254, 255, 264, 270, 272, 273, 274 Mention may be made of red pigments such as 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286 or 287. Further, red dyes such as xanthene, azo, disazo, and anthraquinone can also be mentioned. Specifically, C.I. I. Examples thereof include salt-forming dyes of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338, and oil-soluble dyes which are sulfonamidated.
Examples of orange colorants that can be used in combination include C.I. I. Mention may be made of orange pigments such as CI Pigment Orange 38, 43, 71, or 73.

  Examples of yellow colorants that can be used in combination with green filter segment formation, red filter segment formation, and yellow filter segment formation 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, 82,185,187,188,193,194,198,199,213,214,218,219,220, or include yellow pigments 221, such as, but not limited thereto. Preferred yellow pigments to be used in combination are C.I. I. Pigment Yellow 138, 139, 150, 185. A yellow dye may be used in combination, and specific examples include azo dyes, azo metal complex dyes, anthraquinone dyes, xanthene dyes, cyanine dyes, quinoline dyes, naphthoquinone dyes, and the like.

(Miniaturization of pigment)
When the colorant used in the coloring composition of the present invention is a pigment, it is preferably used after being refined. There are no particular limitations on the method of miniaturization. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As exemplified in the present invention, salt milling treatment by a kneader method, which is one type of wet grinding. Etc. can be made finer. 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 batch or continuous type of mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent, such as a kneader, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. In this process, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a kneader. 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 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.

<Binder resin>
The binder resin contained in the colored composition of the present invention is one that disperses or dyes or penetrates a colorant, and includes conventionally known thermoplastic resins and thermosetting resins. The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

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

Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.
In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the colorant is fixed, heat resistance is improved, and fading (lightness reduction) due to heat of the colorant can be suppressed. In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development process.

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

  Energy ray curable resins having an ethylenically unsaturated active double bond include polymers having reactive substituents such as hydroxy groups, carboxyl groups, amino groups, and reactive groups such as isocyanate groups, aldehyde groups, and epoxy groups. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a substituent or cinnamic acid is used. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferred as the color filter coloring composition.

The following are mentioned as a monomer which comprises the said thermoplastic resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypoly Ji glycol (meth) acrylate of (meth) acrylates,
Alternatively, (meth) acrylamide (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, etc. Acrylamides, styrene, styrene such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, fatty acid vinyl such as vinyl acetate, or vinyl propionate Kind.

  Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4- Phenylene dimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-sc N-imidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide and 9-maleimide acridine.

  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. Especially, an epoxy resin and a melamine resin are used more suitably from a viewpoint of heat resistance improvement.

  The weight average molecular weight (Mw) of the binder resin 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. 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 connected to four separation columns in series in the gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corporation. This is a polystyrene equivalent molecular weight measured using “TSK-GEL SUPER H5000”, “H4000”, “H3000”, and “H2000” manufactured by the company and using tetrahydrofuran as the mobile phase.

  When the binder resin 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, and an aromatic group The balance of groups 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 binder resin is preferably used in an amount of 20 to 700 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 700 parts by weight, the concentration of the colorant becomes low and color characteristics cannot be expressed.

<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 alkyl lactates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate It is preferable to use glycol acetates such as ethylene glycol monoethyl 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 developing type or alkaline developing type photosensitive coloring composition is added. It can be prepared in the form of a product.

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, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, biimidazole derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, or 4,4′-tetra (t-butylperoxyca Rubonyl) benzophenone, 4,4′-diethylaminobenzophenone and the like.
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

<Multifunctional thiol>
The coloring composition of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene,
2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

  The content of the polyfunctional thiol is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight based on the weight (100% by weight) of the total solid content of the color filter coloring composition. . If the content of the polyfunctional thiol is less than 0.1% by weight, the effect of adding the polyfunctional thiol is insufficient, and if it exceeds 30% by weight, the sensitivity is too high and the resolution is lowered.

<Antioxidant>
The coloring composition 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.

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

  When the content of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the color filter coloring composition (100% by weight), brightness and sensitivity are more preferable.

<Amine compound>
The coloring composition of the present invention can contain an amine compound that functions to reduce 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 comprises a coloring agent in a coloring agent 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, It can be produced by finely dispersing (pigment dispersion) using various dispersing means such as a vertical sand mill, an annular bead mill, or an attritor. At this time, the quinophthalone pigment [A], the quinophthalone dye [B], 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 is prepared by mixing the pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, a binder resin, and an additive. Can be 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 re-aggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has brightness, contrast ratio, and Viscosity stability is improved.

  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 dye derivative is used, those having a quinophthalone skeleton and an azo skeleton are preferable from the viewpoint of lightness.

  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, 167 manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti -Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324, 21407, 21715 or Lactimon, Lactimon-WS or Bykumen, etc., Japan Lubrizol SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, manufactured by Ciba Japan , 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 45 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajimoto Fine Techno Co., Ltd. PB821, PB822, PB824, etc. are mentioned.

  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 includes a red filter segment, a green filter segment, and a blue filter segment. The color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment. In the color filter of the present invention, at least one of a red filter segment, a green filter segment, and a yellow filter segment is formed from the colored composition of the present invention. In particular, it is preferable that the green filter segment is formed from the colored composition of the present invention.

  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, 1: 2, 9, 14, 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. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 27, 29, 30, 31, 32, Mention may be made of purple pigments such as 37, 39, 40, 42, 44, 47, 49 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.

  Moreover, the measuring method of the average primary particle diameter of a pigment, the identification method of a coloring agent, and the measuring method of the weight average molecular weight (Mw) of resin are as follows.

(Measurement method of 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.

(Colorant identification method)
The colorant (quinophthalone pigment and quinophthalone dye) used in the coloring composition of the present invention was identified by using a MALDI mass spectrometer autoflex II (hereinafter referred to as TOF-MS) manufactured by Bruker Daltonics, Inc., and obtained mass spectrum. The molecular ion peak was identified with the mass number obtained by calculation.

(Measurement method of weight average molecular weight (Mw) of resin)
The weight average molecular weight (Mw) of the resin was measured in terms of polystyrene measured using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using THF as a developing solvent. It is a weight average molecular weight (Mw).

  Then, the manufacturing method of the binder resin solution, pigment | dye derivative, colorant, green coloring composition, and blue coloring composition which were used by the Example and the comparative example is demonstrated.

<Method for producing binder resin solution>
(Preparation of acrylic resin solution 1)
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. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Was added to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
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 dropping, 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 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 20% by mass. Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

<Method for producing pigment derivative>
(Production of pigment derivative 1)
According to the synthesis method described in Japanese Patent No. 4585781, a pigment derivative (1) was obtained.

<Method for producing colorant>
(Production of quinophthalone compound (1))
A quinophthalone compound (1) was obtained according to the synthesis method described in JP-A-2008-81566. As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (1).

(Production of quinophthalone compound (2))
To 200 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 150 parts of 2,3-naphthalenedicarboxylic anhydride and 154 parts of benzoic acid were added, heated to 180 ° C., and stirred for 4 hours. Further, after cooling to room temperature, the reaction mixture was added to 5440 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 116 parts of a specific quinophthalone pigment represented by the formula (A-3). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone pigment of the formula (A-3).
Subsequently, using the quinophthalone pigment of the formula (A-3) as a raw material, the quinophthalone compound (2) is obtained by the same method as the synthesis of the quinophthalone compound (1) according to the synthesis method described in JP-A-2008-81666. It was. As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (2).

(Production of quinophthalone compound (3))
20 parts of 8-hydroxy-2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It was dried overnight in a vacuum dryer (40 ° C.) to obtain 37 parts of quinophthalone compound (3). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (3).

(Production of yellow colorant (YA-1))
To 300 parts of methyl benzoate, 100 parts of quinophthalone compound (1), 70 parts of 2,3-naphthalenedicarboxylic anhydride and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. The formation of the specific quinophthalone pigment represented by the formula (A-1) and the disappearance of the raw material quinophthalone compound (1) were confirmed by TOF-MS. Further, after cooling to room temperature, the reaction mixture was added to 3130 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol and dried to obtain 120 parts of a specific quinophthalone pigment represented by the formula (A-1). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone pigment of the formula (A-1).
Subsequently, 100 parts of the quinophthalone pigment of the formula (A-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 60 ° C. for 6 hours. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of a yellow colorant (YA-1) were obtained. The average primary particle size was 31.3 nm.

(Production of yellow colorant (YA-2))
50 parts of a quinophthalone pigment of the formula (A-1), C.I. I. 50 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 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 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of a yellow colorant (YA-2) were obtained. The average primary particle size was 30.2 nm.

(Production of yellow colorant (YA-3))
To 300 parts of methyl benzoate, 100 parts of quinophthalone compound (2), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. Furthermore, after cooling to room temperature, the reaction mixture was added to 3510 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 118 parts of a specific quinophthalone pigment represented by the formula (A-2). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone pigment of the formula (A-2).
Subsequently, 100 parts of the quinophthalone pigment of the formula (A-2), 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 60 ° C. for 6 hours. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of a yellow colorant (YA-3) were obtained. The average primary particle size was 31.1 nm.

(Production of yellow colorant (YA-4))
50 parts of a quinophthalone pigment of the formula (A-2), C.I. I. 50 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 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 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of a yellow colorant (YA-4) were obtained. The average primary particle size was 30.2 nm.

(Production of yellow colorant (YA-5))
20 parts of a quinophthalone pigment of the formula (A-2), C.I. I. 80 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 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 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 96 parts of a yellow colorant (YA-5) were obtained. The average primary particle size was 29.7 nm.

(Production of yellow colorant (YA-6))
100 parts of the quinophthalone pigment of the formula (A-3), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of a yellow colorant (YA-6) were obtained. The average primary particle size was 34.1 nm.

(Production of yellow colorant (YA-7))
To 300 parts of methyl benzoate, 100 parts of quinophthalone compound (2), 176 parts of tetrabromophthalic anhydride, and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 6 hours. Furthermore, after cooling to room temperature, the reaction mixture was added to 7190 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 138 parts of a specific quinophthalone pigment represented by the formula (A-5). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone pigment of the formula (A-5).
Subsequently, 100 parts of the quinophthalone pigment of the formula (A-5), 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 60 ° C. for 8 hours. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of a yellow colorant (YA-7) were obtained. The average primary particle size was 28.3 nm.

(Production of yellow colorant (YA-8))
50 parts of a quinophthalone pigment of the formula (A-5), C.I. I. 50 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 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 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of yellow colorant (YA-8) were obtained. The average primary particle size was 28.1 nm.

(Production of yellow colorant (YB-1))
29 parts of 6-hexyl-2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and 42 parts of specific quinophthalone dyes (yellow coloring agent (YB-1)) represented by Formula (B-1) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-1).

(Production of yellow colorant (YB-2))
34 parts of 8- (2-ethylhexyloxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained 50 parts of specific quinophthalone dye (yellow colorant (YB-2)) represented by Formula (B-5). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-5).

(Production of yellow colorant (YB-3))
44 parts of 8- (2-ethylhexyloxy) -5-phenyl-2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. This was dried overnight in a vacuum dryer (40 ° C.) to obtain 57 parts of a specific quinophthalone dye (yellow colorant (YB-3)) represented by the formula (B-6). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-6).

(Production of yellow colorant (YB-4))
46 parts of 8-dodecoxy-5-bromo-2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained 46 parts of specific quinophthalone dyes (yellow colorant (YB-4)) represented by Formula (B-8). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-8).

(Production of yellow colorant (YB-5))
34 parts of 6- (2-ethylhexyloxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. This was dried overnight in a vacuum dryer (40 ° C.) to obtain 43 parts of a specific quinophthalone dye (yellow colorant (YB-5)) represented by the formula (B-10). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-10).

(Production of yellow colorant (YB-6))
29 parts of 6- (2-ethoxyethoxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained 39 parts of specific quinophthalone dye (yellow colorant (YB-6)) represented by Formula (B-11). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-11).

(Production of yellow colorant (YB-7))
34 parts of 6- (2- (1,3-dioxan-2-yl) ethoxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained 33 parts of specific quinophthalone dye (yellow colorant (YB-7)) represented by Formula (B-12). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-12).

(Production of yellow colorant (YB-8))
34 parts of 4- (2-ethylhexyloxy) -2-methylquinoline, 25 parts of naphthalenedicarboxylic anhydride and 300 parts of benzoic acid were mixed and stirred at 200 ° C. for 7 hours. After allowing to cool, 1000 parts of methanol was added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put in 2000 parts of methanol, stirred for 1 hour, and then collected by suction filtration. This was dried overnight in a vacuum dryer (40 ° C.) to obtain 42 parts of a specific quinophthalone dye (yellow colorant (YB-8)) represented by the formula (B-13). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-13).

(Production of yellow colorant (YB-9))
20 parts of quinophthalone compound (3) was mixed with 200 parts of N, N-dimethylacetamide, 3 parts of sodium hydroxide and 18 parts of 2-ethylhexyl-4-bromobutyric acid were further mixed, and the mixture was stirred at 90 ° C. for 1 hour. After allowing to cool, 1000 parts of methanol and 1000 parts of water were added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 1000 parts of methanol and stirred for 1 hour, and then the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained 16 parts of specific quinophthalone dye (yellow colorant (YB-9)) represented by Formula (B-27). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-27).

(Production of yellow colorant (YB-10))
200 parts of N, N-dimethylacetamide was mixed with 20 parts of quinophthalone compound (3), 3 parts of sodium hydroxide and 19 parts of 2-ethylhexyl-5-bromovaleric acid were further mixed, and the mixture was stirred at 90 ° C. for 1 hour. . After allowing to cool, 1000 parts of methanol and 1000 parts of water were added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 1000 parts of methanol and stirred for 1 hour, and then the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained 20 parts of specific quinophthalone dye (yellow colorant (YB-10)) represented by Formula (B-28). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-28).

(Production of yellow colorant (YB-11))
To 200 parts of N, N-dimethylacetamide, commercially available C.I. I. Disperse Yellow 160 (20 parts) was mixed, sodium hydroxide (3 parts) and 2-ethylhexyl-4-bromobutyric acid (18 parts) were further mixed, and the mixture was stirred at 90 ° C. for 1 hour. After allowing to cool, 1000 parts of methanol and 1000 parts of water were added and stirred for 1 hour. The precipitated solid was collected by suction filtration. Further, the solid was put into 1000 parts of methanol and stirred for 1 hour, and then the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained 20 parts of specific quinophthalone dye (yellow colorant (YB-11)) represented by Formula (B-30). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone dye of the formula (B-30).

(Production of yellow colorant (YB-12))
20 parts of quinophthalone compound (3) is mixed with 200 parts of N, N-dimethylacetamide, 3 parts of sodium hydroxide, 24 parts of 2- (2- (2-ethylhexyloxy) ethoxy) ethyl-2-bromobutanoate Were further mixed and stirred at 100 ° C. for 2 hours. After allowing to cool, the reaction solution was added to 500 parts of water, and 1000 parts of chloroform was further added to extract the organic layer. Magnesium sulfate was added to the organic layer, dried, filtered and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)), and the specific quinophthalone dye represented by formula (B-41) (yellow colorant (YB-12) )) 28 parts were obtained. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 626 (molecular weight 625.8).

(Production of yellow colorant (YB-13))
20 parts of quinophthalone compound (3) is mixed with 200 parts of N, N-dimethylacetamide, 3 parts of sodium hydroxide, 25 parts of 2- (2- (2-ethylhexyloxy) ethoxy) ethyl-5-bromopentanoate Were further mixed and stirred at 100 ° C. for 2 hours. After allowing to cool, the reaction solution was added to 500 parts of water, and 1000 parts of chloroform was further added to extract the organic layer. Magnesium sulfate was added to the organic layer, dried, filtered and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)), and the specific quinophthalone dye (yellow colorant (YB-13) represented by formula (B-42)) was obtained. )) 27 parts were obtained. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 640 (molecular weight 639.8).

(Production of yellow colorant (YB-14))
20 parts of quinophthalone compound (3) is mixed with 200 parts of N, N-dimethylacetamide, 3 parts of sodium hydroxide, bis (2-ethylhexyl) 7-oxabicyclo [4.1.0] heptane-3,4- 97 parts of diloxylate was further mixed and stirred at 150 ° C. for 10 hours. After allowing to cool, the reaction solution was added to 500 parts of water, and 1000 parts of chloroform was further added to extract the organic layer. Magnesium sulfate was added to the organic layer, dried, filtered and concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (chloroform / ethyl acetate = 10/1 (volume ratio)), and the specific quinophthalone dye represented by formula (B-43) (yellow colorant (YB-14) )) 13 parts were obtained. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 750 (molecular weight 749.9), which confirmed the intended product.

(Production of yellow colorant (YC-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. This kneaded product is put into warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture is dried at 80 ° C. for one day and night, and a yellow colorant ( YC-1) 98 parts were obtained. The average primary particle size was 35.5 nm.

(Production of green colorant (GC-1))
C. I. 100 parts of Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product is poured into 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. for a whole day and night. GC-1) 97 parts were obtained. The average primary particle size was 28.2 nm.

(Production of blue colorant (BC-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 aluminum phthalocyanine (1).

Subsequently, 100 parts of aluminum phthalocyanine (1) and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol in a reaction vessel, heated to 40 ° C., and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of aluminum phthalocyanine (2).

  Furthermore, a salt milling process was performed. 100 parts of aluminum phthalocyanine (2), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product is put into warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture is dried at 80 ° C. for a whole day and night. BC-1) 98 parts were obtained. The average primary particle size was 31.2 nm.

<Method for producing green and blue coloring composition>
(Preparation of green coloring composition (DG-1))
After stirring and mixing a mixture having the following composition to be uniform, using a zirconia bead having a diameter of 0.5 mm, using an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) as a media type wet disperser. After dispersing for 5 hours, it was filtered through a 5 μm filter to produce a green colored composition (DG-1).

Green colorant (GC-1) 10.0 parts Resin type dispersant ("EFKA4300" manufactured by Ciba Japan) 2.0 parts Acrylic resin solution 1 40.0 parts Propylene glycol monomethyl ether acetate 48.0 parts

(Preparation of blue coloring composition (DB-1))
After stirring and mixing a mixture having the following composition to be uniform, using a zirconia bead having a diameter of 0.5 mm, using an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) as a media type wet disperser. After dispersing for 5 hours, the mixture was filtered through a 5 μm filter to prepare a blue colored composition (DB-1).

Blue colorant (BC-1) 10.0 parts Resin type dispersant ("BYK-LPN6919" manufactured by Big Chemie) 5.0 parts Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 50.0 parts

<The manufacturing method of a yellow coloring composition>
[Example 1]
(Preparation of yellow coloring composition (DY-1))
After stirring and mixing a mixture having the following composition to be uniform, using a zirconia bead having a diameter of 0.5 mm, using an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) as a media type wet disperser. After dispersing for 5 hours, the mixture was filtered through a 5 μm filter to produce a yellow colored composition (DY-1).

Yellow colorant (YA-1) 4.8 parts Yellow colorant (YB-1) 4.8 parts Dye derivative (1) 0.4 part Resin-type dispersant ("PB821" manufactured by Ajinomoto Fine Techno Co., Ltd.) 2.0 Acrylic resin solution 1 40.0 parts Cyclohexanone 24.0 parts Propylene glycol monomethyl ether acetate 24.0 parts

[Examples 2 to 42, Comparative Examples 1 to 5]
(Yellow coloring composition (DY-2 to 47))
A yellow colored composition (DY-2 to 47) is obtained in the same manner as the yellow colored composition (DY-1) of Example 1 except that the type and blending amount of the yellow colorant are changed as shown in Table 1. It was. Further, the total content of the yellow colorant is 9.6 parts.

Yellow colorant (YC-2); I. Disperse Yellow 54
Yellow colorant (YC-3); I. Disperse Yellow 64

<Evaluation of yellow coloring composition>
Evaluation of spectral transmittance, contrast ratio, coloring power, heat resistance, and light resistance of the yellow coating film produced using the obtained yellow coloring composition (DY-1 to 47) was performed by the following methods. Table 2 shows the evaluation results.

(Spectral transmittance evaluation)
The yellow coloring composition (DY-1 to 47) is applied on a glass substrate having a thickness 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, and then at 220 ° C. for 20 minutes. A coated substrate was prepared by heating and cooling for a minute. The prepared coated substrate is subjected to heat treatment at 220 ° C. so that the transmittance at 450 nm is 5%, and a spectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) is used to perform spectroscopic analysis at 500 nm and 550 nm. The transmittance was measured. The higher the transmittance at 500 nm and 550 nm, the better the brightness. The spectral transmittances at 500 nm and 550 nm were determined according to the following criteria.
○: 99% or more Δ: 97 or more, less than 99% ×: less than 97%

(Contrast ratio evaluation)
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 coating film substrate used for the contrast ratio evaluation was applied with a yellow colored composition (DY-1 to 47) on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and then 70 It was prepared by drying at 20 ° C. for 20 minutes, then heating at 220 ° C. for 20 minutes and allowing to cool. The prepared coated substrate was adjusted to a chromaticity of x = 0.440 with a C light source after heat treatment at 220 ° C. The contrast ratio was determined according to the following criteria.
○: 3000 or more Δ: 2000 or more and less than 3000 ×: less than 2000

(Coloring power evaluation)
Using the same coating film as that used for the contrast ratio evaluation, the film thickness when x (C) = 0.440 chromaticity was measured was measured and judged according to the following criteria. It can be said that the smaller the film thickness that gives the chromaticity of x (C) = 0.440, the greater the coloring power, and the better.
○: Less than 2.0 [μm]
Δ: 2.0 or more and less than 3.0 [μm]
×: 3.0 or more [μm]

(Heat resistance evaluation)
The yellow coloring composition (DY-1 to 47) is applied on a glass substrate having a thickness 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, and then at 220 ° C. for 20 minutes. A coated substrate was prepared by heating and cooling for a minute. The prepared coated substrate was adjusted to a chromaticity of x = 0.440 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 three stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
○: ΔEab * is less than 5.0 Δ: ΔEab * is 5.0 or more and less than 10.0 ×: ΔEab * is 10.0 or more

(Light resistance evaluation)
A coated substrate is prepared in the same manner as in the heat resistance evaluation, and the chromaticity ([L * (1), a * (1), b * (1)]) with a C light source is measured with a microspectrophotometer ( Measurement was performed using “OSP-SP100” manufactured by Olympus Optical Co., Ltd. Subsequently, an ultraviolet cut filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya Co., Ltd.) is attached on the substrate, and irradiated with ultraviolet rays using a 470 W / m ² xenon lamp for 100 hours, and then the chromaticity ([ L * (2), a * (2), b * (2)]) were measured, and the color difference ΔEab * was determined by the above formula and evaluated according to the same criteria as for heat resistance.

  As shown in Table 2, the yellow coloring composition of the Example containing the quinophthalone pigment [A] and the quinophthalone dye [B] as the colorant that is a feature of the present invention has a spectral transmittance, a contrast ratio, and The coloring power was excellent, and the heat resistance and light resistance of the coating film were satisfactory.

  On the other hand, the yellow coloring composition (DY-43-45) of Comparative Examples 1-3 was a result with low brightness. Specific quinophthalone dye used alone, and C.I. The yellow colored compositions (DY-46, 47) of Comparative Examples 4 and 5 used in combination with I. Pigment Yellow 138 had good brightness but a low contrast ratio. In addition, the existing pigment C.I. The yellow coloring composition (DY-43) of Comparative Example 1 using I. Pigment Yellow 138 alone had a problem that the coloring power was low in addition to low brightness. C. not quinophthalone dye [B] I. Disperse Yellow 54, and C.I. I. The yellow coloring compositions (DY-44, 45) of Comparative Examples 2 and 3 using Disperse Yellow 64 had poor contrast ratio, heat resistance, and light resistance.

<Method for producing green photosensitive coloring composition>
[Example 43]
(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) 23.5 parts Yellow coloring composition (DY-1) 21.5 parts Acrylic resin solution 2 2.0 parts Photopolymerizable monomer ("Aronix M402" manufactured by Toagosei Co., Ltd.) 4.4 parts Photopolymerization initiator ("Irgacure OXE02" manufactured by Ciba Japan) 1.2 parts Cyclohexanone 20.0 parts Propylene glycol monomethyl ether acetate 27.4 parts

[Examples 44 to 97, Comparative Examples 6 to 15]
(Production of green photosensitive coloring composition (RG-2 to 65))
Using the yellow coloring composition shown in Table 3, and the green coloring composition or the blue coloring composition, and at the time of coating film evaluation, the chromaticity of x = 0.290 and y = 0.600 with a C light source The photosensitive coloring composition (RG-) except that the ratio of the yellow coloring composition and the green coloring composition or the blue coloring composition is changed so as to match (the ratio is changed so that the total amount of the coloring composition is 45 parts). A photosensitive coloring composition (RG-2 to 65) was prepared in the same manner as 1).

<Evaluation of green photosensitive coloring composition>
The following methods evaluated the brightness, contrast ratio, coloring power, heat resistance, light resistance, and sensitivity of the green coating film produced using the obtained green photosensitive coloring composition (RG-1 to 65). Table 4 shows the evaluation results.

(Brightness evaluation)
The green photosensitive coloring composition (RG-1 to 65) was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and then dried at 70 ° C. for 20 minutes to obtain ultrahigh pressure mercury. 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 and cooling at 220 ° C. for 20 minutes, the brightness Y (C) of the obtained coating film substrate was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The prepared coated substrate was adjusted to a chromaticity of x = 0.290 and y = 0.600 with a C light source after heat treatment at 220 ° C. As an alkali developer, sodium carbonate 1.5% by weight, sodium hydrogen carbonate 0.5% by weight, an anionic surface active agent (“Perex NBL” manufactured by Kao Corporation) 8.0% by weight and water 90% by weight Was used. Furthermore, the brightness value was determined according to the following criteria.
○: 60.5 or more Δ: 58.5 or more, less than 60.5 ×: less than 58.5

(Contrast ratio evaluation)
About the measuring method of the contrast ratio of a coating film, it measured by the method similar to the contrast ratio measurement of a yellow coloring composition. The contrast ratio was calculated using the same coating film that was evaluated for brightness, and judged according to the following criteria.
○: 3500 or more Δ: 3000 or more and less than 3500 ×: less than 3000

(Coloring power evaluation)
Using the same coating film as the one subjected to lightness evaluation, the film thickness when the chromaticity of x (C) = 0.290 and y (C) = 0.600 was measured was measured and judged according to the following criteria. The smaller the film thickness that gives the chromaticity of x (C) = 0.290 and y (C) = 0.600, the greater the coloring power, and the better.
○: Less than 2.5 [μm]
Δ: 2.5 or more and less than 3.0 [μm]
×: 3.0 or more [μm]

(Heat resistance evaluation)
The green photosensitive coloring composition (RG-1 to 65) was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and then dried at 70 ° C. for 20 minutes to obtain ultrahigh pressure mercury. 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 20 minutes and allowed to cool to obtain a coated substrate. The prepared coated substrate was adjusted to a chromaticity of x = 0.290 and 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 three stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
○: ΔEab * is less than 5.0 Δ: ΔEab * is 5.0 or more and less than 10.0 ×: ΔEab * is 10.0 or more

(Light resistance evaluation)
A coated substrate is prepared in the same manner as in the heat resistance evaluation, and the chromaticity ([L * (1), a * (1), b * (1)]) with a C light source is measured with a microspectrophotometer ( Measurement was performed using “OSP-SP100” manufactured by Olympus Optical Co., Ltd. Subsequently, an ultraviolet cut filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya Co., Ltd.) is attached on the substrate, and irradiated with ultraviolet rays using a 470 W / m ² xenon lamp for 100 hours, and then the chromaticity ([ L * (2), a * (2), b * (2)]) were measured, and the color difference ΔEab * was determined by the above formula and evaluated according to the same criteria as for heat resistance.

(Sensitivity evaluation)
After coating the green photosensitive coloring composition (RG-1 to 65) on a 10 cm × 10 cm glass substrate by a spin coating method, the solvent was removed by heating in a clean oven at 70 ° C. for 15 minutes, and about 2 μm A coating film 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 220 ° C. for 20 minutes in a clean oven. The pattern film thickness in the 100 μm photomask portion of the filter segment formed by the above method was measured, and the minimum exposure amount that was 90% or more with respect to the film thickness after coating was determined according to the following criteria. It can be said that the smaller the minimum exposure, the higher the sensitivity and the better the photosensitive coloring composition.
○: Less than 50 mJ / cm ² Δ: 50 mJ / cm ² or more, less than 100 mJ / cm ² ×: 100 mJ / cm ² or more

  As shown in Table 4, the green photosensitive coloring composition of the example containing the quinophthalone pigment [A] and the quinophthalone dye [B] as the colorant that is a feature of the present invention has brightness, contrast ratio, and The coloring power was excellent, and the heat resistance and light resistance of the coating film were satisfactory. Furthermore, despite the fact that it contains a dye, the sensitivity was also good.

  On the other hand, C.I. which is an existing pigment as a yellow colorant. The green photosensitive coloring compositions (RG-56 and 61) of Comparative Examples 6 and 11 using I. Pigment Yellow 138 alone had a low coloring power. A specific quinophthalone dye alone as a yellow colorant, and C.I. The green photosensitive coloring compositions (RG-59, 60, 64, and 65) of Comparative Examples 9, 10, 14, and 15 used in combination with I. Pigment Yellow 138 have good brightness but a low contrast ratio. The result was poor sensitivity. As a yellow colorant, C.I. which is not a quinophthalone dye [B]. I. Disperse Yellow 54, and C.I. I. The green photosensitive coloring compositions (RG-57, 58, 62, 63) of Comparative Examples 7, 8, 12, and 13 using Disperse Yellow 64 had bad results in all characteristics.

<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 Acrylic resin Solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

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 Acrylic resin solution 2 13.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907") 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 39.6 parts

(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 Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 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 the blue photosensitive coloring composition (RB-1).

Blue coloring composition (DB-1) 34.0 parts Acrylic resin solution 2 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907") 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 45.1 parts ethylene glycol monomethyl ether acetate

(Production of color filter)
A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (RR-1) was applied on the substrate with a spin coater to form a colored coating. 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. Here, the red filter segment was adjusted to a chromaticity of x = 0.640 and y = 0.330 in a C light source (hereinafter also used for green and blue) after heat treatment at 220 ° C. In the same manner, the green filter segment is matched with the chromaticity of x = 0.290 and y = 0.600 using the green photosensitive coloring composition (RG-22) of the present invention, and the blue filter The segments were matched to the chromaticity of x = 0.150 and y = 0.060 using the blue photosensitive coloring composition (RB-1), and each filter segment was formed to obtain a color filter.

  By using the green photosensitive coloring composition (RG-22) of the present invention, the brightness and color contrast of the color filter can be increased, and other physical properties can be suitably used without any problem.

Claims (5)

A color filter coloring composition containing a colorant, a binder resin, and an organic solvent, wherein the colorant is selected from the following general formula (1), general formula (2), and general formula (3): A coloring composition for a color filter, comprising at least one kind of quinophthalone pigment [A] and a quinophthalone dye [B] represented by the following general formula (4).

[In General Formulas (1) to (3), R ^{14 to} R ²⁸ , R ^{29 to} R ⁴³ , and R ^{44 to} R ⁶⁰ may each independently have a hydrogen atom, a halogen atom, or a substituent. A good alkyl group, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, —SO ₃ H; —COOH; and monovalent to trivalent metal salts of these acidic groups; It represents a salt, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent. ]

[In General Formula (4), R ^{4 to} R ⁹ each independently have a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. An aryl group which may be substituted, or —OR ¹⁰ ;
R ¹⁰ is an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent.
However, R ^{4 to} R ⁹ are not all hydrogen atoms. ] The R ^{14 to} R ²⁸ , R ^{29 to} R ⁴³ , and R ^{44 to} R ^{60 in the} general formulas (1) to (3) are each independently a hydrogen atom or a halogen atom. Coloring compositions for color filters. The colored composition for a color filter according to claim 1, wherein at least one of R ^{4 to} R ⁹ in the general formula (4) is —OR ¹⁰ .   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.