JP7064090B2 - Pigment compositions for color filters, coloring compositions, and color filters - Google Patents

Description

The present invention relates to a color liquid crystal display device, a solid-state image pickup device represented by a C-MOS (Complementary Metal Oxide Semiconductor), a CCD (Charge Coupled Device), an organic EL display device, and the like. The present invention relates to a coloring composition used for producing a color filter used for electronic paper and the like, and a color filter including a filter segment formed by using the coloring composition.

A transparent electrode for driving a liquid crystal is generally formed on a color filter used in a color liquid crystal display device by vapor deposition or sputtering, and an alignment film for orienting the liquid crystal in a certain direction is formed on the transparent electrode. It is formed. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is generally necessary to carry out the forming step at a high temperature of 230 ° C. or higher, and the color filter is required to have heat resistance.

Contrast ratio and lightness are important quality items required for color filters. If a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light leaks or when light must be transmitted (ON). Since the transmitted light is attenuated in the state), the screen becomes blurry. Therefore, in order to realize a high-quality liquid crystal display device, it is indispensable to increase the contrast ratio. Further, if a color filter having a 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 as light sources. However, from the viewpoint of suppressing power consumption, the trend is to increase the brightness of color filters.

Examples of the colorant used for forming the red filter segment include C.I. I. Pigment Red 254, C.I. I. Pigment Red 291 and C.I. I. Pigment Red 242, and C.I. I. Pigment Red 177 has been widely used in general. C.I., a diketopyrrolopyrrole pigment. I. Pigment Red 254 and C.I. I. Pigment Red 291 is a pigment having particularly excellent brightness, but in recent years, there has been a strong demand for high contrast in color filters, and for that purpose, it is necessary to make the primary particle size of the diketopyrrolopyrrole pigment as fine as possible. However, since the finely divided diketopyrrolopyrrole pigment has the property that crystals easily grow due to the hydrogen bonds between the molecules, crystallization occurs in the heating step when forming the color filter, and foreign matter is generated. The problem is that it ends up.

In Patent Document 1, C.I. I. It has been disclosed that the combined use of Pigment Red 291 and a diketopyrrolopyrrole pigment having a specific structure can suppress crystal precipitation in the heating step, but further improvements in brightness, contrast ratio, heat resistance, solvent resistance, etc. Was sought after.

Japanese Unexamined Patent Publication No. 2012-155232

An object of the present invention is a pigment composition for a color filter, a coloring composition, and a coloring composition using the same, which can form pixels having excellent storage stability, brightness, contrast ratio, heat resistance, solvent resistance, and dye transferability. Is to provide a color filter formed in the above.

As a result of diligent studies, the present inventors have found that the above-mentioned problems can be solved by a pigment composition containing two types of diketopyrrolopyrrole pigments having different structures in a specific mass ratio, and the present invention has been made. I arrived.

[一般式（１）中、Ｘは、ハロゲン原子を表す。]

一般式（２）

[一般式（２）中、ＹおよびＺは、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、炭素数１～２０の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フェニル基である。ただし、YおよびZの少なくとも一つは、炭素数３～１８のアルキル基である。] That is, the present invention is a pigment composition for a color filter containing a diketopyrrolopyrrole pigment represented by the general formula (1) and a diketopyrrolopyrrole pigment represented by the general formula (2). The present invention relates to a pigment composition for a color filter, wherein the mass ratio of the general formula (1) to the general formula (2) is 99.9: 0.1 to 90.0: 10.0.

General formula (1)

[In the general formula (1), X represents a halogen atom. ]

General formula (2)

[In the general formula (2), Y and Z each independently have a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent having 1 to 20 carbon atoms, and a substituent. It is also a good phenyl group. However, at least one of Y and Z is an alkyl group having 3 to 18 carbon atoms. ]

The present invention further relates to the pigment composition for a color filter, which further comprises a dye derivative.

The present invention also relates to a coloring composition for a color filter containing a coloring agent, a resin, and a solvent, wherein the coloring agent contains the pigment composition for a color filter.

The present invention further relates to the coloring composition for a color filter, which further contains a photopolymerizable monomer and / or a photopolymerization initiator.

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

The present invention also relates to a liquid crystal display device including the color filter.

The present invention also relates to a solid-state image pickup device characterized by having the color filter.

According to the present invention, a pigment composition for a color filter, a coloring composition, and a coloring composition thereof capable of forming a pixel having excellent storage stability and good brightness, contrast ratio, heat resistance, solvent resistance, and dye transferability, and using the same. It is possible to provide a color filter formed by the above.

Hereinafter, each component constituting the color filter pigment composition and the color filter coloring composition of the present invention will be described in detail. In addition, "CI" in this application means a color index (CI). In addition, there is no particular explanation when it is described as "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", and "(meth) acryloyloxy". To the extent, they represent "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", and "acryloyloxy and / or methacryloyloxy", respectively. Shall be.

<Pigment composition for color filter>
The pigment composition for a color filter of the present invention contains the diketopyrrolopyrrole pigments of the general formula (1) and the general formula (2) in a mass ratio in the range of 99.9: 0.1 to 90.0: 10.0. By containing it, it has excellent effects on brightness, contrast ratio, heat resistance, solvent resistance, and dye transferability.

(Diketopyrrolopyrrole pigment (A1) of the general formula (1))
The diketopyrrolopyrrole pigment (A1) represented by the general formula (1), which is an essential component of the pigment composition of the present invention, will be described.

[一般式（１）中、Ｘは、ハロゲン原子を表す。] General formula (1)

[In the general formula (1), X represents a halogen atom. ]

Examples of the "halogen atom" in X include fluorine, bromine, chlorine and iodine, and chlorine and bromine are preferable from the viewpoint of brightness and contrast ratio. As a specific example of the diketopyrrolopyrrole pigment of the general formula (1) that can be used in the present invention, C.I. I. Pigment Reds 254 and 291 are, but are not limited to. From the point of view of brightness, C.I. I. Pigment Red 291 is preferred.

(Diketopyrrolopyrrole pigment (A2) of the general formula (2))
The diketopyrrolopyrrole pigment (A2) represented by the general formula (2), which is an essential component of the pigment composition of the present invention, will be described.

[一般式（２）中、ＹおよびＺは、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、炭素数１～２０の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フェニル基である。ただし、ＹおよびＺの少なくとも一つは、炭素数３～１８のアルキル基である。] General formula (2)

[In the general formula (2), Y and Z each independently have a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent having 1 to 20 carbon atoms, and a substituent. It is also a good phenyl group. However, at least one of Y and Z is an alkyl group having 3 to 18 carbon atoms. ]

In Y and Z, examples of the "halogen atom" include fluorine, bromine, chlorine and iodine.

In Y and Z, examples of the "alkyl group which may have a substituent having 1 to 20 carbon atoms" include an unsubstituted or oxyalkylene group having an ether bond, which may be linear or branched, and may be specific. Methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, octadecyl group, icosyl group. , 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-ethoxypropyl group, polyoxyethylene group and the like. It is not limited to these.

In Y and Z, the "phenyl group which may have a substituent" includes an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group and carbon. Examples thereof include a phenyl group having a substituent such as an alkoxyl group having the number 1 to 4. More specifically, phenyl group, p-methylphenyl group, 4-tert-butylphenyl group, p-nitrophenyl group, p-methoxyphenyl group, p-chlorophenyl group, 2,4-dichlorophenyl group, 3-carbamoyl. Examples thereof include, but are not limited to, phenyl groups.

At least one of Y and Z is an "alkyl group having 3 to 18 carbon atoms". Examples of the "alkyl group having 3 to 18 carbon atoms" include a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group and a dodecyl group. Examples thereof include, but are not limited to, an octadecyl group, a 1,5-dimethylhexyl group, a 1,6-dimethylheptyl group, a 2-ethylhexyl group _{, a} cyclohexyl group, and an isobornyl group. The number of carbon atoms of the alkyl group is preferably 4 to 12 from the viewpoint of heat resistance (crystal precipitation in the heating step), contrast ratio, and solvent resistance, and more preferably 4 to 8 carbon atoms. When the length of the alkyl group is long, the steric hindrance effect can suppress the aggregation of the diketopyrrolopyrrole pigment of the general formula (1) due to heat, and the contrast ratio and heat resistance are improved. On the other hand, if the alkyl group is too long, the dispersion stability is deteriorated and the solubility in a solvent is increased, so that the solvent resistance and the dye transfer property tend to be deteriorated.

Specific examples of the diketopyrrolopyrrole pigment of the general formula (2) that can be used in the present invention are given below, but the present invention is not limited thereto.

In the present invention, the content of the diketopyrrolopyrrole pigment represented by the general formula (2) is 0.1 mass based on the total mass of the diketopyrrolopyrrole pigments of the general formula (1) and the general formula (2). It is in the range of% to 10% by mass. It is preferably in the range of 0.1% by mass to 5.0% by mass, and more preferably in the range of 0.1% to 3.0%.

When the ratio of the diketopyrrolopyrrole pigment of the general formula (2) exceeds 10% by mass, the effect of improving heat resistance (suppressing crystal precipitation) can be obtained, but the excellent brightness of the diketopyrrolopyrrole pigment of the general formula (1) is obtained. In addition to impairing storage stability and solvent resistance. On the other hand, if the ratio of the diketopyrrolopyrrole pigment represented by the general formula (2) is less than 0.1% by mass, high contrast and heat resistance (suppression of crystal precipitation) are not sufficient. If the effect of suppressing crystal precipitation is not sufficient, light scattering occurs due to the crystalline foreign matter deposited on the surface of the coating film in the heating step, which causes a decrease in brightness and contrast ratio. Therefore, by using a coloring composition containing the diketopyrrolopyrrole pigment of the general formula (2) in the above ratio, high brightness and a high contrast ratio can be achieved, and the diketopyrrolop of the general formula (1) can be achieved even by the heating step. Crystal precipitation of the pyrrolop pigment can be suppressed.

(Manufacturing method of diketopyrrolopyrrole pigment)
The diketopyrrolopyrrole pigment represented by the general formula (1) or the general formula (2) can be produced by a succinic acid diester synthesis method. That is, for 1 mol of the succinic acid diester, 2 mol of the benzonitrile compound according to the following general formula (50) or the general formula (60) is added to an alkali metal or an alkali metal in an inert organic solvent such as tert-amyl alcohol. In the presence of the alkali metal alkoxide, a condensation reaction is carried out at a high temperature of 80 to 110 ° C. to form an alkali metal salt of the diketopyrrolopyrrole compound, and subsequently, with respect to the alkali metal salt of the diketopyrrolopyrrole compound. By protonation with water, an alcohol, an acid or the like, a diketopyrrolopyrrole pigment of the general formula (1) or the general formula (2) can be obtained. At this time, the size of the obtained primary particle size can be controlled by the temperature in protonation, the type, ratio and amount of water, alcohol or acid. The method for producing the diketopyrrolopyrrole pigment represented by the general formula (1) or the general formula (2) is not limited to this method.

[一般式（５０）中、Ｘは、ハロゲン原子を表す。] General formula (50)

[In the general formula (50), X represents a halogen atom. ]

[一般式（６０）中、ＹおよびＺは、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、置換基を有してもよいアルキル基、置換基を有してもよいフェニル基である。ただし、YおよびZの少なくとも一つは、炭素数３～１８の置換基を有してもよいアルキル基である。] General formula (60)

[In the general formula (60), Y and Z are independent hydrogen atoms, halogen atoms, cyano groups, alkyl groups which may have a substituent, and phenyl groups which may have a substituent. .. However, at least one of Y and Z is an alkyl group which may have a substituent having 3 to 18 carbon atoms. ]

(Other colorants)
The pigment composition and coloring composition of the present invention color various conventionally known pigments and dyes in addition to the essential components of the diketopyrrolopyrrole pigments represented by the general formulas (1) and (2). It can be arbitrarily selected as an agent and contained in combination. Hereinafter, typical pigments and dyes that can be used in the present invention are listed.

The red pigment that can be used in the present invention is, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 221, 224, 226, 242, 246, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 295, 296 and the like can be mentioned, but the present invention is not particularly limited thereto. Further, red dyes such as xanthene-based, cyanine-based, azo-based, and anthraquinone-based dyes can also be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene-based acid dyes such as Acid Red 52, 87, 92, 289 and 338.

The orange pigment that can be used in the present invention is, for example, C.I. I. Pigment Orange 38, 43, or 71, but is not particularly limited thereto.

The yellow pigments that can be used in the present invention include, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 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, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221, 231, 233 or the quinophthalone pigment described in Japanese Patent No. 4993026 can be mentioned. , Especially not limited to these. Further, yellow dyes such as quinoline-based, azo-based, methine-based, coumarin-based, and isoindoline-based can also be used.

The green pigments that can be used in the present invention include, for example, C.I. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, JP-A-2008-19383, JP-A-2007-320986, JP-A-2004-70242, International Publication No. 2015/118720 The zinc phthalocyanine pigment described in the above, the aluminum phthalocyanine pigment described in Japanese Patent No. 4893859, and the like can be mentioned, but the present invention is not particularly limited thereto. Further, green dyes such as triarylmethane-based, phthalocyanine-based, and squarylium-based dyes can also be used.

The blue pigment that can be used in the present invention is, for example, 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, JP-A-2004-333817, Examples thereof include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, but the present invention is not particularly limited thereto.

Purple pigments that can be used in the present invention include, for example, C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like can be mentioned, but the present invention is not particularly limited thereto.

The pigment composition of the present invention includes metal oxides such as titanium dioxide, iron oxide, antimony pentoxide, zinc oxide and silica, cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, talc, yellow lead and carbon black. Inorganic pigments such as, etc. can also be used.

When the pigment composition of the present invention is used in combination with other colorants, a red pigment or a yellow pigment is often used in combination in relation to color characteristics. Specific examples of the red pigment to be combined include C.I. I. Pigment Red 177, C.I. I. Pigment Red 242, C.I. I. Pigment Red 269, C.I. I. Pigment Red 296 is preferred from the viewpoint of color characteristics. As the yellow pigment, C.I. I. Pigment Yellow 138 or the quinophthalone pigment described in Japanese Patent No. 4993026, C.I. I. Pigment Yellow 139, 185, C.I. I. Pigment Yellow 150 is preferable from the viewpoint of color characteristics.

<Dye derivative>
The pigment composition or coloring composition of the present invention may contain a pigment derivative for the purpose of suppressing pigment crystal growth and improving pigment dispersibility. As the dye derivative that can be used in the present invention, a known dye derivative having an acidic group, a basic group, a neutral group or the like in the organic dye residue can be used. For example, compounds having an acidic functional group such as a sulfo group, a carboxy group and a phosphoric acid group, amine salts thereof, compounds having a basic functional group such as a sulfonamide group or a tertiary amino group at the terminal, a phenyl group and a phthalimide. Examples thereof include compounds having a neutral functional group such as an alkyl group. Examples of the organic pigment include diketopyrrolopyrrole pigments, copper phthalocyanine, zinc phthalocyanine, aluminum phthalocyanine, halogenated copper phthalocyanine, halogenated zinc phthalocyanine, halogenated aluminum phthalocyanine, metal-free phthalocyanine and other phthalocyanine pigments, aminoanthraquinone and diamino. Anthraquinone pigments such as dianthraquinone, anthrapyrimidine, flavantron, antoanthron, indantron, pyranthron, biolantron, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, Benzimidazolone pigments, indol pigments such as benzoisoindole, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, azo, disazo, polyazo, etc. Examples include azo pigments.
More specifically, Japanese Patent Application Laid-Open No. 61-246261, Japanese Patent Application Laid-Open No. 63-264674, Japanese Patent Application Laid-Open No. 09-272812, Japanese Patent Application Laid-Open No. 10-245501, Japanese Patent Application Laid-Open No. 10-265697, Japanese Patent Application Laid-Open No. 11-19976, 2001-172520, 2001-22520, 2002-201377, 2003-165922, 2003-168208, 20033- 171594, 2004-217842, 2005-213404, 2006-291194, 2007-079094, 2007-226161, 2007-314681. JP-A-2007-314785, JP-A-2008-31281, JP-A-2009-57478, WO2009 / 025325 pamphlet, WO2009 / 081930 pamphlet, JP-A-2011-162662, WO2011 / 052617. Pamphlet, JP2012-1722092, JP2012-208329, JP2012-226110, WO2012 / 102399 Pamphlet, JP2014-5439, WO2016 / 163351, JP2017- Known dye derivatives described in Japanese Patent Publication No. 156397, Japanese Patent No. 5753266, etc. can be mentioned, and these can be used alone or in combination of two or more. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a pigment dispersant, or simply a compound, but the above-mentioned organic dye residue includes an acidic group, a basic group, a neutral group, and the like. A compound having a functional group of is synonymous with a dye derivative.

When a dye derivative is used in the present invention, a dye derivative having a basic substituent is preferable because the effect of suppressing aggregation of pigments is remarkable. Further, as the organic dye residue, those derived from diketopyrrolopyrrole pigments, anthraquinone pigments, thiazineindigo pigments, quinophthalone pigments and azo pigments are preferable from the viewpoint of hue and contrast ratio.

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

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

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

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

In the salt milling treatment, a dye derivative may be used in combination in order to improve the kneading efficiency. It is very effective for the miniaturization and sizing of pigments. In the miniaturization of the diketopyrrolopyrrole pigment composition used in the present invention, it is preferable, but not limited to, the dye derivative is used. The amount of the dye derivative used is preferably in the range of 0.5 to 30% by mass with respect to 100% by mass of the pigment so as not to affect the color tone.

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

<Coloring composition for color filters>
The coloring composition for a color filter of the present invention contains at least a coloring agent, a resin, and a solvent containing the pigment composition for a color filter of the present invention. Further, if necessary, a resin-type dispersant, a photopolymerizable monomer, a photopolymerization initiator, or the like can be used to impart photosensitivity.

<Resin type dispersant>
The coloring composition of the present invention can be used in combination with a resin-type dispersant. The dispersant has a colorant-affinitive moiety having a property of adsorbing to an additive colorant or a dye derivative and a moiety compatible with the colorant carrier, and is adsorbed on the additive colorant to the colorant carrier. It works to stabilize the dispersion. Specific examples of the resin-type dispersant 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 polyaminoamidophosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxy group. Oil-based dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone and the like water-soluble Resins, water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide-added compounds, phosphate ester-based, etc. are used, and these can be used alone or in admixture of two or more. It is not necessarily limited to these.

Of the above resin-type dispersants, a nitrogen atom-containing graft copolymer or a tertiary amino group or a quaternary ammonium base in the side chain, because the viscosity of the dispersion becomes low and a high contrast ratio is exhibited with a small amount of addition. Well-known are nitrogen atom-containing acrylic block copolymers and urethane-based polymer dispersants having a functional group containing a nitrogen-containing heterocycle and the like.

When a resin-type dispersant is used in combination in the present invention, those having an acidic substituent are preferable, and those having an aromatic carboxy group or a phosphoric acid group are particularly effective in preventing the reaggregation of the colorant after dispersion. , Particularly preferred. Examples of the resin-type dispersant having an aromatic carboxy group include WO2008 / 007776, JP-A-2008-029901, JP-A-2009-155406, JP-A-2009-155406, and JP-A-2010-185934. , Japanese Patent Application Laid-Open No. 2011-157416, but the present invention is not limited thereto.

The resin type dispersant is preferably used in an amount of about 5 to 200 parts by mass with respect to the total amount of the colorant, and more preferably about 5 to 100 parts by mass from the viewpoint of film forming property.

<Resin>
The resin which is an essential component of the coloring composition of the present invention is for dispersing, dyeing or permeating a coloring agent, and examples thereof include thermoplastic resins. When used in the form of an alkali-developable colored resist material, it is preferable to use an alkali-soluble vinyl-based resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer. Further, 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-developable colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. By doing so, the colorant is fixed, the heat resistance is improved, and fading (deterioration of spectral characteristics) due to the heat of the colorant can be suppressed. It also has the effect of suppressing aggregation and precipitation of colorant components in the developing process.

The resin preferably has 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.

The weight average molecular weight (Mw) of the resin is preferably in the range of 2,000 to 80,000, more preferably in the range of 3,000 to 40,000 in order to preferably disperse the colorant. The number average molecular weight (Mn) is preferably in the range of 3000 to 40,000, and the value of Mw / Mn is preferably 10 or less.

When the resin is used as a photosensitive coloring composition for a color filter, a carboxy group that acts as a colorant adsorbing group and an alkali-soluble group during development, an aliphatic group that acts as an affinity group for a colorant carrier and a solvent, and an aromatic group. The balance of group groups is important for the dispersibility, permeability, developability, and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. If the acid value is less than 20 mgKOH / g, the solubility in a developing solution is poor and it may be difficult to form a fine pattern. If it exceeds 300 mgKOH / g, fine patterns may not remain.

Since the resin has good film forming properties and various resistances, it is preferable to use the resin in an amount of 20 parts by mass or more with respect to 100 parts by mass of the total mass of the colorant, and the colorant concentration is high and good color characteristics are exhibited. Since it can be used, it is preferable to use it in an amount of 1000 parts by mass or less.

Examples of the thermoplastic resin used for the resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and polyvinyl acetate. Examples thereof include polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin. Above all, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin obtained by copolymerizing the acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxy group and a sulfo group.
Specifically, the alkali-soluble resin includes an acrylic resin having an acidic group, an α-olefin / (maleic) maleic anhydride copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples thereof include isobutylene / (maleic anhydride) maleic anhydride copolymer. Among them, 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.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include a resin in which an unsaturated ethylenically double bond is introduced by the methods (i) and (ii) shown below.

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

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

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

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

As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxy group with one or more other types of monomers. There is a method of adding an unsaturated ethylenic monomer having an epoxy group to a part of the carboxy group to introduce an unsaturated ethylenic double bond and a carboxy group.

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

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

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

<Thermosetting compound>
The coloring composition of the present invention can contain a thermosetting compound. Examples of the thermosetting compound include epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins. Examples include, but are not limited to, urea compounds and / or resins, phenolic compounds and / or resins.
When a thermosetting compound is used in the present invention, an epoxy compound is preferable from the viewpoint of heat resistance, solvent resistance and the like. The epoxy compound is not particularly limited as long as it has an epoxy group, and may be a low molecular weight compound or a high molecular weight compound such as a resin, but a polyfunctional epoxy compound is particularly suitable for coating with a high crosslink density. It is preferable because a film can be obtained.

The preferable weight average molecular weight of the epoxy compound is 200 or more and 100,000 or less. A more preferable molecular weight is 300 or more and 10,000 or less, and further preferably 500 or more and 5000 or less.

As the epoxy compound, any of bisphenol A type epoxy compound, bisphenol F type epoxy compound, cresol novolac type epoxy compound, biphenyl type epoxy compound, alicyclic epoxy compound and the like can be used. A novolak type epoxy compound and an alicyclic epoxy compound are preferable, and an alicyclic epoxy compound is particularly preferable. The number of functional groups is preferably bifunctional or higher, and more preferably trifunctional or higher because of its excellent thermal crosslinkability.

Examples of the bifunctional epoxy compound include EPICLON 830, 840, 850, 860, 1050, 2050, 3050, 4050, 7050, HM-091, 101, Nagase Chemtex Denacol EX-211, 212, 252, 711, and others. 721 and the like can be mentioned.

Examples of the trifunctional or higher functional epoxy compound include a novolak type epoxy compound and EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.), which is a polymer alicyclic main chain epoxy compound. Specific examples of the novolak type epoxy compound include EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-4500, EOCN-4600, XD-1000, XD-1000-L, and XD-1000-. 2L, NC-3000, NC-3000-H (all manufactured by Nippon Kayaku Co., Ltd.), YDPN-638, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN -700-10, YDCN-704, YDCN-704A (all manufactured by Nippon Steel Chemical Co., Ltd.), N-660, N-665, N-670, N-673, N-680, N-690, N-695 , N-665-EXP, N-672-EXP, N-655-EXP-S, N-662-EXP-S (all manufactured by DIC Corporation) and the like. Further, Techmore VG3101 (manufactured by Printec), which is a trifunctional epoxy compound, TETRAD-C, TETRAD-X (all manufactured by Mitsubishi Gas Chemical Company, Inc.), which are tetrafunctional epoxy compounds, and the like can be mentioned. Further, Denacol EX-313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622 and the like manufactured by Nagase Chemtex can be mentioned. Further, JER1031S, 1302H60, 604, 630, 630LSD manufactured by Mitsubishi Chemical Corporation and the like can also be mentioned.

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

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

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

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

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

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

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

<Photopolymerization initiator>
The coloring composition of the present invention may contain a photopolymerization initiator in order to cure the composition by irradiation with ultraviolet rays and form a filter segment by a photolithography method. In addition, it can be prepared in the form of a solvent-developed or alkaline-developed photosensitive coloring composition.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1-. Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 -Acetophenone compounds such as [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one; benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4' -Benzophenone compounds such as methyldiphenyl sulfide or 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 -Thioxanthone compounds such as diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-( p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6- Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4- Triazine compounds such as trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-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-trimethyl) Benzoyl) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone; borate compounds; carbazole Compounds; imidazole compounds; or titanosen compounds are used.
These photopolymerization initiators can be used alone or in admixture of two or more at any ratio as required.

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

<Sensitizer>
Further, the coloring composition of the present invention may contain a sensitizer.
Examples of the sensitizer include chalcone derivatives, unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, aclysine derivatives, azine derivatives, thiadine derivatives, oxadin derivatives, indolin derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Mihiler ketone derivative, Biimidazole derivative, α -Acyloxyester, acylphosphine oxide, methylphenylglycilate, benzyl, 9,10-phenanthrenquinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalofenone, 3,3', or Examples thereof include 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and 4,4'-diethylaminobenzophenone.
These sensitizers can be used alone or in admixture of two or more at any ratio as required.

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

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

<Thiol compound>
The coloring composition of the present invention can contain a thiol compound that acts as a chain transfer agent.
As the thiol compound, a polyfunctional thiol compound having two or more thiol groups is preferable, and examples thereof include hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, and 1,4-butanediol bisthioglycolate. Ethylene Glycol Bisthioglycolate, Ethylene Glycol Bisthiopropionate, Trimethylol Propanitris Thioglycolate, Trimethylol Propanistrice Propionate, Trimethylol Propantris (3-Mercaptobutyrate), Pentaerythritol Tetrakissthioglycolate , Pentaerythritol tetrakisthiopropionate, tristrimercaptopropionate (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N) -Dibutylamino) -4,6-dimercapto-s-triazine and the like can be mentioned. These polyfunctional thiol compounds can be used alone or in admixture of two or more at any ratio as required.

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

<Antioxidant>
The coloring composition of the present invention can contain an antioxidant. The antioxidant increases the transmittance of the coating film in order to prevent the photopolymerization initiator and the thermosetting compound contained in the coloring composition from being oxidized and yellowed by the thermal process at the time of heat curing or ITO annealing. be able to. Therefore, by containing an antioxidant, it is possible to prevent yellowing due to oxidation during the heating step and obtain a high transmittance of the coating film.

The "antioxidant" in the present invention may be a compound having an ultraviolet absorbing function, a radical trapping function, or a peroxide decomposition function, and specifically, the antioxidant is a hindered phenol-based or a hindered amine-based compound. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, sulfate ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

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

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

The content of the antioxidant is more preferably 0.1 to 5.0% by mass based on the solid content mass (100% by mass) of the coloring composition for a color filter because the brightness and sensitivity are good.

<Amine compounds>
Further, the coloring composition of the present invention may contain an amine compound having a function of reducing dissolved oxygen.
Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

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

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

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

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalline sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include ester.

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

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

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

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

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

<Manufacturing method of coloring composition>
In the coloring composition of the present invention, a colorant is placed in a colorant carrier such as a resin and / or a solvent, preferably with a dispersant aid such as a dye derivative or a resin type dispersant, in a kneader, a two-roll mill, or three. It can be finely dispersed and produced by using various dispersion means such as the present roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, or attritor (colorant dispersion). At this time, two or more kinds of colorants and the like may be dispersed in the colorant carrier at the same time, or separately dispersed in the colorant carrier may be mixed. If the colorant such as a dye is highly soluble, specifically, if it is highly soluble in the solvent used, dissolved by stirring, and no foreign matter is confirmed, it is manufactured by finely dispersing as described above. No need.

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

<Dispersion aid>
When the colorant is dispersed in the colorant carrier, a dispersion aid such as a dye derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing the reaggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has high lightness and viscosity stability. Become good. The dye derivative and the resin type dispersant are as described above.

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

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

<Removal of coarse particles>
The colored composition of the present invention comprises coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more, and coarse particles of 5 μm or more, preferably coarse particles of 0.5 μm or more, by means such as centrifugation, filtration with a sintering filter or a membrane filter. It is preferable to remove the mixed dust. As described above, it is preferable that the coloring composition does not contain particles having a size of 0.5 μm or more. It is more preferably 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment. Further, the color filter may further include a magenta color filter segment, a cyan color filter segment, and a yellow filter segment. In the color filter of the present invention, at least one of the red filter segments is formed from the pigment composition of the present invention.

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

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

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

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

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

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

<Solid image sensor>
The solid-state image sensor of the present invention includes the color filter of the present invention. The configuration of the solid-state image sensor of the present invention is a configuration provided with a color filter for the solid-state image sensor of the present invention, and is not particularly limited as long as it functions as a solid-state image sensor. Configuration can be mentioned.
A transfer electrode made of a plurality of photodiodes, polycarbonate, etc. constituting a light receiving area of a solid-state image sensor (CCD sensor, CMOS sensor, organic CMOS sensor, etc.) is provided on a substrate, and the photodiode and the transfer electrode are on the transfer diode. It has a light-shielding film made of tungsten or the like with only the light-receiving part of the photodiode open, and has a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. It is a configuration having a color filter for a solid-state image sensor of the present invention on a device protective film.
Further, a configuration having a condensing means (for example, a microlens or the like; the same applies hereinafter) on the device protective layer under the color filter (near the substrate), a configuration having a condensing means on the color filter, and the like. May be.
The organic CMOS sensor is composed of a thin-film panchromatic photosensitive organic photoelectric conversion film and a CMOS signal readout substrate as a photoelectric conversion layer, and the organic material plays a role of capturing light and converting it into an electric signal. It is a two-layer hybrid structure in which the inorganic material plays the role of extracting the signal to the outside, and in principle, the aperture ratio can be set to 100% with respect to the incident light. Since the organic photoelectric conversion film is a structure-free continuous film and can be laid on a CMOS signal reading substrate, it does not require an expensive microfabrication process and is suitable for filter segment miniaturization.
The arrangement of the color filter segments is not particularly limited, and a known method can be used.

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

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively. The average primary particle size of the pigment and the weight average molecular weight (Mw) of the resin are as follows.

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

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

Subsequently, a method for producing the resin solution, the resin-type dispersant solution, the dye derivative, and the colorant used in Examples and Comparative Examples will be described.

<Manufacturing of acrylic resin solution>
(Preparation of acrylic resin solution 1)
Put 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable 4-neck flask, and heat to 120 ° C. while injecting nitrogen gas into the vessel. Azobisisobutyro as a catalyst required for the reaction of 16.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 25.0 parts of dicyclopentanyl methacrylate, 16 parts of methyl methacrylate and the precursor at this stage from the dropping tube at temperature. A mixture of 1.0 part of nitrile was added dropwise over 2.5 hours to carry out a polymerization reaction. Next, the inside of the flask was replaced with air, and 17.0 parts of acrylic acid and 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, and the temperature was 120 ° C. The reaction was carried out for 5 hours to obtain a resin solution having a weight average molecular weight of about 12000 (measured by GPC). Since the added acrylic acid ester-bonds to the epoxy group terminal of the glycidyl methacrylate constituent unit, no carboxy group is generated in the resin structure. Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine as a catalyst required for the reaction of the precursor at this stage were added and reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of the two carboxy groups generated by cleavage of the carboxylic acid anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxy group terminal. Propylene glycol monomethyl ether acetate was added so that the non-volatile content was 20% to obtain an acrylic resin solution 1.

(Preparation of acrylic resin solution 2)
100 parts by mass of propylene glycol monomethyl ether acetate was placed in a separable flask equipped with a cooling tube, substituted with nitrogen, and then the temperature was raised to 90 ° C. On the other hand, in the dropping tank 1, 10.0 parts of dimethyl-2,2'-[oxybis (methylenebis)] -2-propionate, 40.1 parts of cyclohexyl methacrylate, 24.2 parts of tetrahydrofurfuryl methacrylate, and 24.7 parts of methacrylic acid. , 2.0 parts of t-butylperoxy-2-ethylhexanoate and 80 parts of propylene glycol monomethyl ether acetate were mixed. Further, 3.1 parts of β-mercaptopropionic acid and 6 parts of propylene glycol monomethyl ether acetate were mixed in the dropping tank 2. While maintaining the reaction temperature at 90 ° C., dropping was carried out from the dropping tanks 1 and 2 into the reaction tank at a constant speed over 2.5 hours. After completion of the dropping, the temperature was maintained at 90 ° C. for 30 minutes, 0.5 part of t-butylperoxy-2-ethylhexanoate was added, and the reaction was continued at 90 ° C. for 30 minutes. Then, the reaction temperature was raised to 115 ° C., and the reaction was continued for 1.5 hours. After cooling to room temperature, 24.7 parts of glycidyl methacrylate, 0.038 parts of 6-t-butyl-2,4-xylenol and 0.38 parts of dimethylbenzylamine were added to adjust the oxygen concentration to 7%. -The temperature was raised to 110 ° C. while bubbling the air mixed gas, and the reaction was carried out for 6 hours. After that, the temperature was raised to 115 ° C. and reacted for 2 hours to complete the reaction, cooled to room temperature, sampled about 2 g of the resin solution, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and the previously synthesized resin was synthesized. Acrylic resin solution 2 was obtained by adding propylene glycol monomethyl ether acetate to the solution so that the non-volatile content was 20% by mass. The weight average molecular weight of the resin was 9000, and the acid value per solid content was 70 mgKOH / g.

<Manufacturing of resin type dispersant solution>
(Preparation of resin type dispersant solution 1)
A flask equipped with a cooling tube and a stirrer was charged with 1.0 part by mass of AIBN (2,2'-azobisisobutyronitrile) and 186 parts by mass of propylene glycol monomethyl ether acetate, followed by 27 parts by mass of methyl methacrylate and butyl methacrylate. 27 parts by mass, 21 parts by mass of 2-ethylhexyl methacrylate, 18 parts by mass of benzyl methacrylate and 3.6 parts by mass of cumyldithiobenzoate were charged and replaced with nitrogen for 30 minutes. After that, the temperature of the reaction solution was raised to 60 ° C. by gentle stirring, and this temperature was maintained for 24 hours for living radical polymerization. Next, to this reaction solution, a solution prepared by dissolving 1.0 part by mass of AIBN and 35 parts by mass of dimethylaminoethyl methacrylate in 70 parts by mass of propylene glycol monomethyl ether acetate and substituting with nitrogen for 30 minutes was added, and living radical polymerization was carried out at 60 ° C. for 24 hours. A solution of the block copolymer was obtained. To the obtained block copolymer solution, 25 parts by mass of benzyl chloride and 50 parts by mass of propylene glycol monomethyl ether were added, and the reaction was carried out at 80 ° C. for 2 hours to adjust the solid content concentration to 40%, thereby forming a resin mold. Dispersant solution 1 was obtained. The resin type dispersant 1 has an A block having a repeating unit derived from methacryloyloxyethyl benzyldimethylammonium chloride and dimethylaminoethyl methacrylate and a B block having a repeating unit derived from methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and benzyl methacrylate. It is a block copolymer composed of. As a result of proton NMR measurement, the copolymerization ratio of each repeating unit was methacryloxyethyl benzyldimethylammonium chloride / dimethylaminoethyl methacrylate / methyl methacrylate / butyl methacrylate / 2-ethylhexyl methacrylate / benzyl methacrylate = 34/4/18/18 /. It was 14/12 (mass ratio).

(Preparation of resin type dispersant solution 2)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 6.5 parts of 3-mercapto-1,2-propanediol, 4.0 parts of pyromellitic acid anhydride, 0.01 part of dimethylbenzylamine, 41.8 parts of methoxypropyl acetate was charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., 67 parts of methyl methacrylate, 5.0 parts of methacrylic acid, and t-butyl. 16.0 parts of acrylate, 10.0 parts of (3-ethyloxetane-3-yl) methyl methacrylate, 2.0 parts of ethyl acrylate were charged, and 2,2'-azobisisobutyronitrile 0.10 part and methoxypropyl. 60.0 parts of acetate was added and reacted for 10 hours. It was confirmed by solid content measurement that the polymerization proceeded by 95%, and the reaction was terminated to obtain a polyester dispersant having an acid value of 47 mgKOH / g and a number average molecular weight of 15,000. Methoxypropyl acetate was added thereto so that the solid content was 40% by solid content measurement to obtain a resin-type dispersant solution 2 having an aromatic carboxy group.

(Preparation of resin type dispersant solution 3)
A commercially available “Disperbyk-110 (solid content 52%)” manufactured by Big Chemie was used as the resin-type dispersant solution 3.

<Manufacturing of dye derivatives>

(Manufacturing of dye derivative 1)
A dye derivative 1 represented by the following structure was produced with reference to Synthesis Example 3 of Japanese Patent No. 5748665.

Dye derivative 1

(Manufacturing of dye derivative 2)
The organic dye derivative (D4) of JP-A-2010-163500 was designated as the dye derivative 2.

Dye derivative 2

(Manufacturing of dye derivative 3)
The dye derivative 3 was obtained according to the synthesis method described in JP-A-2004-067715.

Dye derivative 3

(Manufacturing of dye derivative 4)
With reference to Production Example 6 of Japanese Patent No. 4983061, the dye derivative 4 represented by the following structure was produced.

Dye derivative 4

<Manufacturing method of colorant>
<Manufacturing of Diketopyrrolopyrrole Pigment of General Formula (2)>
(Manufacturing of Diketopyrrolopyrrole Pigment (A2-1))
To a stainless steel reaction vessel equipped with a reflux tube, 200 parts of molecularly dehydrated tert-amyl alcohol and 140 parts of sodium-tert-amyl alkoxide were added under a nitrogen atmosphere, and the mixture was heated to 100 ° C. with stirring to prepare an alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate and 122.5 parts of 4-propylbenzonitrile were added to a glass flask and heated to 90 ° C. with stirring to dissolve them to prepare a solution of a mixture thereof. The heated solution of this mixture was slowly added dropwise to the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring. After completion of the dropping, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to the reaction vessel with a glass jacket, and the mixture was cooled to −10 ° C. The cooled mixture was cooled to 75 ° C. using a high-speed stirring disperser while rotating a share disk having a diameter of 8 cm at 4000 rpm, and the alkali metal salt of the previously obtained diketopyrrolopyrrole compound was cooled therein. The solution was added in small portions. At this time, the rate of adding the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid, and water is always maintained at -5 ° C. or lower. Was added in small portions over approximately 120 minutes. After the addition of the alkali metal salt, red crystals were precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C. and then filtered off to obtain a red paste. This paste was redistributed in 3500 parts of methanol cooled to 0 ° C. to prepare a suspension having a methanol concentration of about 90%, and the mixture was stirred at 5 ° C. for 3 hours to perform particle sizing and washing with crystal transition. Subsequently, the water paste of the obtained diketopyrrolopyrrole compound was filtered off with an extraneous filter, dried at 80 ° C. for 24 hours, and pulverized to obtain the diketopyrrolop of the following formula (A2-1). 129.6 parts of the pyrrolop pigment was obtained.

Equation (A2-1)

(Manufacturing of Diketopyrrolopyrrole Pigment (A2-2))
The procedure was the same as for the production of the diketopyrrolopyrrole pigment (A2-1) except that 122.5 parts of 4-propylbenzonitrile was changed to 134.4 parts of 4-tert-butylbenzonitrile, and the following formula (A2-2) was used. ) Was obtained in 135.4 parts of the diketopyrrolopyrrole pigment.

） Equation (A2-2

)

(Manufacturing of Diketopyrrolopyrrole Pigment (A2-3))
The procedure was the same as for the production of the diketopyrrolopyrrole pigment (A2-1) except that 122.5 parts of 4-propylbenzonitrile was changed to 134.4 parts of 3-tert-butylbenzonitrile, and the following formula (A2-3) was used. ) Was obtained in 133.4 parts of the diketopyrrolopyrrole pigment.

Equation (A2-3)

(Manufacturing of Diketopyrrolopyrrole Pigment (A2-4))
The procedure was the same as for the production of the diketopyrrolopyrrole pigment (A2-1) except that 122.5 parts of 4-propylbenzonitrile was changed to 181.7 parts of 4- (2-ethylhexyl) benzonitrile, and the following formula (A2) was used. 173.3 parts of the diketopyrrolopyrrole pigment represented by -4) was obtained.

Equation (A2-4)

(Manufacturing of Diketopyrrolopyrrole Pigment (A2-5))
The procedure was the same as for the production of the diketopyrrolopyrrole pigment (A2-1) except that 122.5 parts of 4-propylbenzonitrile was changed to 229.1 parts of 4-dodecylbenzonitrile, and the following formula (A2-5) was used. 206.2 parts of the represented diketopyrrolopyrrole pigment was obtained.

Equation (A2-5)

(Manufacturing of Diketopyrrolopyrrole Pigment (A2-6))
The procedure was the same as for the production of the diketopyrrolopyrrole pigment (A2-1) except that 122.5 parts of 4-propylbenzonitrile was changed to 300.1 parts of 4-octadecylbenzonitrile, and the following formula (A2-6) was used. 238.8 parts of the represented diketopyrrolopyrrole pigment was obtained.

Equation (A2-6)

<Manufacturing of other diketopyrrolopyrrole pigments>
(Manufacturing of Diketopyrrolopyrrole Pigment (A3-1))
While 220 parts of tert-amyl alcohol was placed in the reaction vessel 1 and cooled in a water bath, 32 parts of 60% NaH was added, and the mixture was heated and stirred at 90 ° C. Next, 100 parts of tert-amyl alcohol, 99.2 parts of the compound of the following formula (700) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and the benzonitrile compound of the formula (N-1) were placed in the reaction vessel 2. 71.8 parts were heated and dissolved, and this was added dropwise to the reaction vessel 1 over 2 hours. After reacting at 120 ° C. for 10 hours, the mixture was cooled to 60 ° C., 400 parts of methanol and 50 parts of acetic acid were added, and then filtration and washing with methanol were performed. 79.1 parts of the pyrrolop pigment was obtained.

Equation (700)

Equation (N-1)

Equation (A3-1)

<Manufacturing of Diketopyrrolopyrrole Pigment Composition>
[Example 1]
(Production of Diketopyrrolopyrrole Pigment Composition (P-1))
C. I. Pigment Red 254 (CINIC "Cinilex DPP Red ST") 97.0 parts, formula (A2-1) 3.0 parts, sodium chloride 1000 parts, and diethylene glycol 120 parts, 1 gallon kneader made of stainless steel (manufactured by Inoue Seisakusho) It was charged inside and kneaded at 60 ° C. for 12 hours. Next, the kneaded mixture was put into warm water, stirred for 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water to remove salt and diethylene glycol, dried at 80 ° C. overnight, and pulverized. To obtain 98.3 parts of the diketopyrrolopyrrole pigment composition (P-1). The average primary particle size was 28.5 nm.

[Examples 2 to 14]
(Production of Diketopyrrolopyrrole Pigment Composition (P-2-14))
"CI Pigment Red 254 (CINIC" Cinilex DPP Red ST ") 97.0 parts, formula (A2-1) 3.0 parts" is classified into the diketopyrrolopyrrole pigments and dye derivatives shown in Table 1. Diketopyrrolopyrrole pigment compositions (P-2 to 14) were obtained by the same method as in Example 1 except that the amount was changed. The average primary particle size of each pigment composition is as shown in Table 1.

[Comparative Examples 1 to 6]
(Production of Diketopyrrolopyrrole Pigment Compositions (P-S1 to S6))
"CI Pigment Red 254 (CINIC" Cinilex DPP Red ST ") 97.0 parts, formula (A2-1) 3.0 parts" is classified into the diketopyrrolopyrrole pigments and dye derivatives shown in Table 1. Diketopyrrolopyrrole pigment compositions (P-S1 to S6) were obtained by the same method as in Example 1 except that the amount was changed. The average primary particle size of each pigment composition is as shown in Table 1.

ＰＲ２５４ ： ＣＩＮＩＣ社「Ｃｉｎｉｌｅｘ ＤＰＰ Ｒｅｄ ＳＴ」
ＰＲ２９１ ： ＣＩＮＩＣ社「Ｃｉｎｉｌｅｘ ＤＰＰ Ｒｅｄ ＭＴ－ＣＦ」
ＰＲ２７２： ＢＡＳＦ社「Ｉｒｇａｚｉｎ ＲＥＤ Ｋ３８００」

PR254: CINIC "Cinilex DPP Red ST"
PR291: CINIC "Cinilex DPP Red MT-CF"
PR272: BASF "Irgazin RED K3800"

<Manufacturing of Diketopyrrolopyrrole Coloring Composition>
[Example 101]
(Production of Diketopyrrolopyrrole Coloring Composition (DR-1))
The mixture having the following composition is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, and then the pore diameter. The mixture was filtered through a 5.0 μm filter to prepare a colored composition (DR-1).
Diketopyrrolopyrrole pigment composition (P-1) 10.7 parts Dye derivative 1 1.0 part Dye derivative 4 0.3 part Resin type dispersant solution 1 6.0 parts Resin type dispersant solution 2 6.0 parts Resin type dispersant solution 3 1.0 part Acrylic resin solution 1 13.4 parts Propropylene glycol monomethyl ether acetate 56.6 parts Propropylene glycol monomethyl ether 5.0 parts

[Examples 102 to 114, Comparative Examples 101 to 106]
(Production of Diketopyrrolopyrrole Coloring Compositions (DR-2 to 14, DR-S1 to S6))
The coloring compositions (DR-2-14, DR-) are the same as the coloring composition (DR-1) except that the diketopyrrolopyrrole pigment composition (P-1) is changed to the pigment composition shown in Table 2. S1 to S6) were manufactured.

<Manufacturing of other coloring compositions>
(Manufacturing of PR177 coloring composition (DR-177A) for toning)
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm for 5 hours, and then the pore diameter is 5. The mixture was filtered through a 0 μm filter to prepare a PR177 colored composition (DR-177A).
Anthraquinone pigment (CINIC "Cinilex RED SR3C") 11.6 parts Dye derivative 3 0.4 parts Resin type dispersant solution 1 6.0 parts Resin type dispersant solution 2 6.0 parts Acrylic resin solution 2 16.0 parts 55.0 parts of propylene glycol monomethyl ether acetate 5.0 parts of propylene glycol monomethyl ether

<Evaluation of coloring composition>
The obtained coloring compositions (DR-1 to 14, DR-S1 to S6) were evaluated by the following methods. The results are shown in Table 2.

(Evaluation of contrast ratio)
The coloring composition (DR-1 to 14, DR-S1 to S6) was applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, and heated in a clean oven at 80 ° C. for 15 minutes. The solvent was removed, and the mixture was heated in a clean oven at 230 ° C. for 60 minutes and allowed to cool to obtain a red coated film substrate. After the heat treatment at 230 ° C., the red coating film substrate was adjusted to the chromaticity of x = 0.660 with a C light source. Next, a method for measuring the contrast ratio will be described. The light emitted from the backlight unit for a liquid crystal display passes through the polarizing plate, is polarized, passes through the dry coating film of the coloring composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing plate and the polarizing plane of the polarizing plate are parallel, the light passes through the polarizing plate, but if the polarizing plane is orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dry coating film of the coloring composition, scattering due to the pigment particles or the like occurs and a part of the polarizing surface is displaced, when the polarizing plates are parallel. The amount of light transmitted through the polarizing plate is reduced, and when the polarizing plate is orthogonal, part of the light is transmitted through the polarizing plate. This transmitted light was measured as the brightness on the polarizing plate, and the ratio (contrast ratio) between the brightness when the polarizing plates were parallel and the brightness when the polarizing plate was orthogonal was calculated. 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. At the time of measurement, a black mask having a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.
(Contrast ratio) = (Brightness when parallel) / (Brightness when orthogonal)
The contrast ratio was evaluated in the following four stages.
⊚: 5000 or more (extremely good)
◯: 4000 or more and less than 5000 (good: practicality possible)
Δ: 3000 or more and less than 4000 (defective)
×: Less than 3000 (extremely defective)

(Evaluation of storage stability)
The initial viscosities of the coloring compositions (DR-1 to 14, DR-S1 to S6) were measured at 25 ° C. using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Subsequently, after storing in a constant temperature machine at 40 ° C. for 2 weeks and accelerating with time, the viscosity after aging is measured by the same method as the viscosity measurement, and the rate of change in viscosity before and after storage at 40 ° C. for 2 weeks is calculated. However, it was evaluated on a three-point scale according to the following criteria.
⊚: When the absolute value of the viscosity change rate is less than 10% (good)
◯: When the absolute value of the viscosity change rate is 10% to 20% (normal)
×: When the absolute value of the viscosity change rate exceeds 20% (defective)

As shown in Table 2, the coloring composition using the diketopyrrolopyrrole pigment composition of the present invention had good results in both contrast ratio and storage stability.

<Manufacturing method of photosensitive coloring composition>
[Example 201]
(Manufacturing of Photosensitive Coloring Composition (RR-1))
The mixture having the following composition was uniformly stirred and mixed, and then filtered through a filter having a pore size of 1.0 μm to obtain a red photosensitive coloring composition (RR-1).
PR177 Coloring Composition (DR-177A) 16.28 parts Diketopyrrolopyrrole Coloring Composition (DR-1) 33.72 parts Acrylic resin solution 1 3.60 parts Epoxy compound (“EHPE-3150” manufactured by Dycel) 0. 16 parts photopolymerizable monomer ("Aronix M402" manufactured by Toa Synthetic Co., Ltd.) 1. 10 parts photopolymerizable monomer ("Aronix M350" manufactured by Toa Synthetic Co., Ltd.) 1.45 parts Polymerization initiator (BASF Co., Ltd. "" Irga Cure OXE02 ”) 0.15 part Photopolymerization Initiator (BASF“ Irga Cure 369 ”) 0.30 Part Sensitizer (“KAYACURE DETX-S” manufactured by Nippon Kayaku Co., Ltd.) 0.05 part thiol compound ( Pentaerythritol tetrakisthiopropionate) 0.20 part Leveling agent ("BYK-330" manufactured by Big Chemie) 0.05 part Antioxidant ("IRGANOX1010" manufactured by BASF) 0.10 part propylene glycol monomethyl ether acetate 32.84 parts Ethyl 3-ethoxypropionate 10.00 parts

[Examples 202 to 214, Comparative Examples 201 to 206]
(Manufacturing of photosensitive coloring compositions (RR-2 to 14, RR-S1 to S6))
The total content of the coloring composition in the photosensitive coloring composition is fixed at 50.00 parts, and the photosensitive coloring composition is the same as in Example 201 except that the type and blending ratio of the dyeing composition are changed. Objects (RR-2 to 14, RR-S1 to S6) were obtained. The types of the coloring composition were as shown in Table 3, and the blending ratio of the coloring composition was such that the chromaticity after the substrate was prepared was (x = 0.660, y = 0.324) with the C light source.

[Example 215]
(Manufacturing of Photosensitive Coloring Composition (RR-15))
The mixture having the following composition was uniformly stirred and mixed, and then filtered through a filter having a pore size of 1.0 μm to obtain a red photosensitive coloring composition (RR-15).
PR177 Coloring Composition (DR-177A) 15.09 Parts Diketopyrrolopyrrole Coloring Composition (DR-14) 34.91 Parts Acrylic Resin Solution 1 3.85 Parts Epoxy Compound (“TEPIC-S” manufactured by Nissan Chemical Industries, Ltd.) 0.16 parts photopolymerizable monomer ("KAYARAD DPCA-30" manufactured by Nippon Kayaku Co., Ltd.) 1.85 parts photopolymerizable monomer ("UA-510H" manufactured by Kyoeisha Chemical Co., Ltd.) 0.50 parts photopolymerization Initiator (BASF "Irgacure OXE01") 0.55 part photopolymerization initiator (BASF "Irgacure 907") 0.20 part sensitizer ("EAB-F" manufactured by Hodoya Chemical Industry Co., Ltd.) 0.05 part silane coupling agent (Shinetsu Silicone Co., Ltd. "KBM-403") 0.03 part Polymerization inhibitor (methylhydroquinone) 0.02 part UV absorber (BASF company "TINUVIN P") 0.05 part Leveling Agent ("Megafuck F-551" manufactured by DIC Co., Ltd.) 0.05 part propylene glycol monomethyl ether acetate 32.69 parts 1,3-butylene glycol diacetate 5.00 parts 3-methoxybutanol 5.00 parts

<Evaluation of photosensitive coloring composition>
The obtained photosensitive coloring composition was evaluated by the following method. The results are shown in Table 3.
(Evaluation of brightness)
The photosensitive coloring composition (RR-1 to 15, RR-S1 to S6) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, and in a clean oven at 80 ° C. for 15 minutes. The solvent was removed by heating to obtain a coating film. Subsequently, ultraviolet exposure was performed with an integrated light amount of 100 mJ / cm ² using an ultra-high pressure mercury lamp, and development was performed with an alkaline developer at 23 ° C. to obtain a coating film substrate. Then, after heating in a clean oven at 230 ° C. for 30 minutes and allowing to cool, the brightness Y (C) of the obtained coating film substrate was measured using a microspectroscopy meter (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). After the heat treatment at 230 ° C., the red coating film substrate was adjusted to the chromaticity of (x = 0.660, y = 0.324) with a C light source. The alkaline developer consists of 1.5% by mass of sodium carbonate, 0.5% by mass of sodium hydrogencarbonate, 8.0% by mass of anionic surfactant ("Perirex NBL" manufactured by Kao Co., Ltd.) and 90% by mass of water. Was used. The brightness was evaluated in the following four stages.
⊚: 18.5 or more (extremely good)
◯: 18.3 or more and less than 18.5 (good)
Δ: 18.1 or more and less than 18.3 (defective)
×: Less than 18.1 (extremely defective)

(Evaluation of contrast ratio)
Contrast ratio measurements were performed using the substrate used in the brightness evaluation. The contrast ratio was evaluated in the following four stages.
⊚: 5000 or more (extremely good)
◯: 4000 or more and less than 5000 (good)
Δ: 3000 or more and less than 4000 (defective)
×: Less than 3000 (extremely defective)

(Evaluation of storage stability)
The initial viscosity of the obtained photosensitive coloring composition was measured at 25 ° C. using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Subsequently, after storing in a constant temperature machine at 40 ° C. for 2 weeks and accelerating with time, the viscosity after aging is measured by the same method as the viscosity measurement, and the rate of change in viscosity before and after storage at 40 ° C. for 2 weeks is calculated. However, it was evaluated on a three-point scale according to the following criteria.
⊚: When the absolute value of the viscosity change rate is less than 5% (good)
◯: When the absolute value of the viscosity change rate is 5% to 10% (normal)
×: When the absolute value of the viscosity change rate exceeds 10% (defective)

(Evaluation of heat resistance)
The photosensitive coloring composition (RR-1 to 15, RR-S1 to S6) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, and in a clean oven at 70 ° C. for 15 minutes. The solvent was removed by heating to obtain a dry coating film. At this time, the dry coating film was applied so as to have a thickness of 2.5 μm. Subsequently, using an ultra-high pressure mercury lamp, ultraviolet exposure was performed through a photomask having a 100 μm width (pitch 200 μm) stripe pattern with an integrated light intensity of 100 mJ / cm ² , and development was performed with an alkaline developer at 23 ° C. to form a stripe. A coated substrate was obtained. Subsequently, the heat treatment was performed at 230 ° C. for 60 minutes, and then the heat treatment was further performed at 240 ° C. for 60 minutes and at 280 ° C. for 60 minutes. The surface of the coating film on the substrate after the heat treatment was observed with an optical microscope, and the presence or absence of crystal precipitation was determined according to the following four-step criteria.
◎ ・ ・ ・ No crystal precipitation even after heat treatment at 230 ° C. for 60 minutes, further heat treatment at 240 ° C. for 60 minutes, and further heat treatment at 280 ° C. for 60 minutes ○ ・ ・ ・ After heat treatment at 230 ° C. for 60 minutes, and further 240 ° C. 60 Crystal precipitation does not occur even after a minute heat treatment, but crystal precipitation occurs after a further heat treatment at 280 ° C. for 60 minutes.・ ・ Crystal precipitation occurs after heat treatment at 230 ° C for 60 minutes

(Evaluation of solvent resistance)
The photosensitive coloring composition (RR-1 to 15, RR-S1 to S6) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, and in a clean oven at 70 ° C. for 15 minutes. The solvent was removed by heating to obtain a dry coating film. At this time, the dry coating film was applied so as to have a thickness of 2.5 μm. Subsequently, using an ultra-high pressure mercury lamp, ultraviolet exposure was performed through a photomask having a 100 μm width (pitch 200 μm) stripe pattern with an integrated light intensity of 100 mJ / cm ² , and development was performed with an alkaline developer at 23 ° C. to form a stripe. A coated substrate was obtained. Then, the heat treatment was performed at 230 ° C. for 60 minutes in a clean oven. Here, after measuring the chromaticity (L ^* (1), a ^* (1), b ^* (1)) with a C light source, the mixture is immersed in NMP (N-methylpyrrolidone) at 40 ° C. for 30 minutes, and further. The chromaticity (L ^* (2), a ^* (2), b ^* (2)) at the C light source was measured. The color difference ΔE * ab was calculated by the following formula using the chromaticity values before and after NMP immersion, and the solvent resistance of the coating film was evaluated in the following three stages.
Calculation formula: ΔE * ab = [[L * (2) －L * (1)] ² + [a * (2) －a * (1)] ² + [b * (2) －b * (1) ] ² ] ^1/2
⊚: ΔE ^* ab is less than 1.0 (extremely good)
〇: ΔE ^* ab is 1.0 or more and less than 3.0 (good)
Δ: ΔE ^* ab is 3.0 or more and less than 5.0 (defective)
×: ΔE ^* ab is 5.0 or more (extremely defective)

(Evaluation of dye transferability)
The photosensitive coloring composition was applied onto a glass substrate using a slit die coater, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 2.4 μm. Next, after cooling the substrate on which the coating film was formed to room temperature, radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was applied to the coating film at 1,000 J / m via a striped photomask using a high-pressure mercury lamp. It was exposed with an exposure amount of ² . After alkaline development, the cells were washed with ultrapure water and post-baked at 230 ° C. for 20 minutes to form red striped pixels on the substrate. Subsequently, the transmittance at 520 nm on a glass substrate 8 μm away from the red striped pixels was measured (T1). Further, the acrylic resin solution 2 was applied onto this substrate using a slit die coater, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 2.5 μm. Further, post-baking was performed at 230 ° C. for 20 minutes. Subsequently, the transmittance at 520 nm on a glass substrate 8 μm away from the red striped pixels was measured (T2). The difference between T1 and T2 was evaluated as ΔT (%) in the following four stages. It can be said that the smaller the ΔT value, the less the decrease in luminance due to color transfer to the adjacent other color filter segments, and the less the dye transferability is suppressed.
⊚: ΔT is less than 1.0% (extremely good)
◯: ΔT is 1.0% or more and less than 2.0% (good)
Δ: ΔT is 2.0% or more and less than 3.0% (defective)
×: ΔT is 3.0% or more (extremely defective)

As shown in Table 3, the diketopyrrolopyrrole pigments of the general formula (1) and the general formula (2), which are the features of the present invention, have a mass ratio of 99.9: 0.1 to 90.0: 10.0. The photosensitive coloring compositions of Examples 201 to 215 contained in the range were very good in all of the items of brightness, contrast ratio, storage stability, heat resistance, solvent resistance, and dye transferability without any problem in practicality. It was a good result. On the other hand, Comparative Examples 201 and 203 to 205, which do not contain the diketopyrrolopyrrole pigment of the general formula (2), are inferior in crystal precipitation in the heating step as compared with Examples, and the brightness and contrast ratio are also affected by the crystal precipitation. The result was worse than the example. Further, Comparative Examples 202 and 206 containing more than 10% by mass of the diketopyrrolopyrrole pigment of the general formula (2) had poorer stability, solvent resistance, and dye transferability than the examples. It is considered that this is because the diketopyrrolopyrrole pigment of the general formula (2) itself has poor dispersion stability, solvent resistance, and dye transferability as compared with the diketopyrrolopyrrole pigment of the general formula (1).

<Making color filters>
First, a green and blue photosensitive coloring composition used for producing a color filter was produced.

(Preparation of Green Photosensitive Coloring Composition (RG-100))
The mixture having the following composition is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, and then the pore diameter. The mixture was filtered through a 5.0 μm filter to prepare a green coloring composition (DG-100).
Green pigment (CI Pigment Green 58) 8.6 parts Yellow pigment (CI Pigment Yellow 138) 3.4 parts Resin type dispersant (BASF "EFKA4300") 3.0 parts Acrylic resin solution 1 25.0 parts propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1.0 μm to prepare a green photosensitive coloring composition (RG-100).
Green coloring composition (DG-100) 42.0 parts Acrylic resin solution 1 13.2 parts Photopolymerizable monomer ("Aronix M402" manufactured by Toa Synthetic Co., Ltd.) 2.8 parts Photopolymerization initiator (BASF Co., Ltd. "" Irgacure 907 ") 2.0 parts Sensitizer ("EAB-F "manufactured by Hodoya Chemical Industry Co., Ltd.) 0.4 parts propylene glycol monomethyl ether acetate 39.6 parts

(Preparation of Blue Photosensitive Coloring Composition (RB-100))
The mixture having the following composition is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, and then the pore diameter. The mixture was filtered through a 5.0 μm filter to prepare a blue coloring composition (DB-100).
Blue pigment (CI Pigment Blue 15: 6) 7.2 parts Purple pigment (CI Pigment Violet 23) 4.8 parts Resin type dispersant (BASF "EFKA4300") 1.0 part Acrylic resin Solution 1 35.0 parts propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1.0 μm to prepare a blue photosensitive coloring composition (RB-100).
Blue coloring composition (DB-100) 34.0 parts Acrylic resin solution 2 15.2 parts Photopolymerizable monomer ("Aronix M402" manufactured by Toa Synthetic Co., Ltd.) 3.3 parts Photopolymerization initiator (BASF Co., Ltd. "" Irgacure 907 ") 2.0 parts Sensitizer ("EAB-F "manufactured by Hodoya Chemical Industry Co., Ltd.) 0.4 parts propylene glycol monomethyl ether acetate 45.1 parts

(Manufacturing of color filters for liquid crystal displays)
A black matrix was patterned on a glass substrate, and the red photosensitive coloring composition (RR-14) of the present invention was applied onto the substrate with a spin coater to form a colored film. The film was irradiated with ultraviolet rays of 200 mJ / cm ² using an ultrahigh pressure mercury lamp via a photomask. Then, after spray-developing with an alkaline developer consisting of 0.2% by mass of sodium carbonate aqueous solution to remove the unexposed portion, the substrate was washed with ion-exchanged water, and the substrate was heated at 230 ° C. for 30 minutes to obtain a red filter segment. Formed. Here, the red filter segment was adjusted to match the chromaticity of x = 0.660 in the C light source after the heat treatment at 230 ° C. Further, by the same method, the green filter segment is adjusted to match the chromaticity of y = 0.570 by using the green photosensitive coloring composition (RG-100), and the blue filter segment is the blue photosensitive coloring composition. (RB-100) was used to match the chromaticity of y = 0.045, and each filter segment was formed to obtain a color filter.

By using the photosensitive coloring composition (RR-14) of the present invention for forming the red filter segment, it is possible to increase the brightness and contrast of the color filter, and it is suitably used without any problem in other physical characteristics. I was able to. Further, the color filter of the present invention is bonded to the facing substrate using a sealing agent, the liquid crystal is injected from the injection port provided in the sealing portion, the injection port is sealed, and the polarizing film and the retardation film are placed on the outside of the substrate. By laminating, a liquid crystal display device having excellent brightness and contrast ratio was obtained.

(Manufacturing of color filters for solid-state image sensors)
A resist solution for a flattening film (HL-18s: manufactured by Nippon Steel Chemical Co., Ltd.) was applied onto a 6-inch silicon wafer by a spin coating method, and heat-treated on a hot plate at 100 ° C. for 6 minutes as a prebake. Further, it was treated in an oven at 230 ° C. for 1 hour to cure the coating film to form a 1.0 μm flattening film, and a wafer with a flattening film was obtained.

The green photosensitive coloring composition (RG-100) was applied on a silicon wafer with a flattening film with a spin coater, and heat-treated on a hot plate at 100 ° C. for 1 minute as a prebake. The film thickness after prebaking was adjusted to 0.9 μm.

Then, using an i-line stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.), a pattern was applied at an exposure amount of 150 mJ / cm ² through a photomask for forming 1.0 μm square red pixels at a wavelength of 365 nm. The exposure was performed.

The coated film after exposure was paddle-developed with an organic alkaline developer for 1 minute. After paddle development, the product was rinsed with pure water in a spin shower for 20 seconds, and then washed with pure water for 20 seconds. Then, the water droplets remaining on the wafer were blown off with high-pressure air, the substrate was naturally dried, and further heat-treated on a hot plate having a surface temperature of 230 ° C. for 5 minutes to form a square pixel pattern. The film thickness of the green pattern after the heat treatment was 0.80 μm.

Next, a red photosensitive coloring composition (RR-12) is used to form a red coloring pixel layer in the same manner as the green coloring pixel layer, and further, a blue photosensitive coloring composition (RB-100) is used. A blue colored pixel layer was formed, and a color filter for a solid-state image sensor was obtained. The color filter for a solid-state image sensor manufactured in this manner has very good red spectral characteristics and excellent heat resistance. Therefore, a solid-state image sensor using the color filter for a solid-state image sensor is available. In particular, it was excellent in the reproducibility of skin color.

Claims (7)

A pigment composition for a color filter containing a diketopyrrolopyrrole pigment (A1) represented by the general formula (1) and a diketopyrrolopyrrole pigment (A2) represented by the general formula (2). A pigment composition for a color filter, wherein the mass ratio of the diketopyrrolopyrrole pigment (A1) to the diketopyrrolopyrrole pigment (A2) is 99.9: 0.1 to 90.0: 10.0. ..

General formula (1)

[In the general formula (1), X represents a halogen atom. ]

General formula (2)

[In the general formula (2), Y and Z each independently have a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent having 1 to 20 carbon atoms, or a substituent. Represents a optionally phenyl group. However, at least one of Y and Z is an alkyl group having 3 to 18 carbon atoms. ] The pigment composition for a color filter according to claim 1, further comprising a dye derivative. A coloring composition for a color filter containing a colorant, a resin, and a solvent, wherein the colorant contains the pigment composition for a color filter according to claim 1 or 2. thing. The coloring composition for a color filter according to claim 3, further comprising a photopolymerizable monomer and / or a photopolymerization initiator. A color filter comprising a filter segment formed from the coloring composition for a color filter according to claim 3 or 4. A liquid crystal display device comprising the color filter according to claim 5. A solid-state image pickup device comprising the color filter according to claim 5.