JP2019113671A - Coloring composition for color filter, color filter and pigment dispersion agent - Google Patents

Abstract

To provide a pigment dispersion agent which exhibits high heat resistance while achieving dispersion performance to wide organic pigments; a coloring composition for color filter which achieves excellent contrast ratio by high dispersibility and brightness even when containing an organic pigment with high concentration, and exhibits high alkali resistance (development property); and a high quality color filter which achieves a high contrast ratio and brightness and exhibits good development property and adhesion.SOLUTION: There are provided a pigment dispersion agent having an organic pigment and a specific isoindoline skeleton represented by general formula (1), and a coloring composition for color filter containing a binder resin and an organic solvent.SELECTED DRAWING: None

Description

  The present invention relates to a coloring composition for color filters used in the manufacture of color filters used in color liquid crystal display devices, solid-state imaging devices and the like, and a color filter formed using the same. Further, the present invention relates to a pigment dispersant which is used for dispersing a pigment and can be widely used for a printing ink, a paint, a resin colorant, a coloring composition such as an inkjet ink, an ink for a color filter, and the like.

In order to achieve high contrast and high lightness of color filters, it is required to disperse them in a minute state (good dispersibility). However, since the finely divided pigment has a large surface area, the cohesion between the pigment particles becomes strong, and if the dispersibility of the pigment is insufficient, the viscosity of the dispersion becomes high, and the contrast of the color filter is increased. Is significantly degraded. It is often difficult to achieve both high level of dispersion and contrast.
Patent Documents 1 and 2 propose a structure having an isoindoline skeleton and introducing an acidic group, but the dispersion effect does not satisfy the currently required contrast and dispersion stability. In addition, since the alkaline developing solution is used when the color filter is formed by the photolithography method, there are problems such as dissolution, increase in development time, and problems such as poor adhesion with a dispersant having an acidic group introduced. . Patent Document 3 proposes a structure in which a basic group is introduced, and the developability and adhesion are improved, but because it is not an isoindoline skeleton, it can meet the currently required brightness, contrast and dispersion stability. Absent. In order to solve these problems, it has been required to propose a pigment dispersant which has a high dispersion stabilizing effect and does not cause a defect during development.

Unexamined-Japanese-Patent No. 2006-146078 JP, 2009-120777, A JP, 2007-156395, A

  An object of the present invention is to provide a pigment dispersant that exhibits high heat resistance while achieving dispersion performance for a wide range of organic pigments. Further, the object of the present invention is to provide a color filter which achieves excellent contrast ratio and lightness by high dispersibility, and exhibits high alkali resistance (developability) even when the organic pigment is contained at a high concentration. It is an object of the present invention to provide a coloring composition. Another object of the present invention is to provide a high quality color filter which realizes high contrast ratio and lightness, and exhibits good developability and adhesion.

The coloring composition for color filters containing a <1> organic pigment, the pigment dispersant represented by following General formula (1), binder resin, and an organic solvent.
General formula (1)

[In general formula (1), X ₁ represents -O- or -NH-, and Y represents an alkylene group which may have a substituent or an arylene group which may have a substituent] And R ₁ represents an alkyl group which may have a substituent. X ₂ represents -O- or -NH-, and R ₂ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. ]

The coloring composition for said color filters whose B in <2> General formula (1) is a structure represented by following formula (2), or a structure represented by following General formula (3).
Formula (2)

General formula (3)
[In general formula (3), X ₂ represents -O- or -NH-, and R ₂ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. ]

The coloring composition for said color filters which is a structure where B in <3> General formula (1) is represented by following formula (2).
Formula (2)

  <4> The organic pigment is C.I. I. Pigment yellow 139 and C.I. I. Pigment composition containing the above pigment yellow 185.

  <5> The colored composition for color filter as described above, further containing at least one selected from the group consisting of a photopolymerizable monomer and a photopolymerization initiator.

  The color filter which comprises the filter segment formed from the coloring composition for said color filters on a <6> board | substrate.

The pigment dispersant represented by <7> following General formula (1).
General formula (1)
[In general formula (1), X ₁ represents —O— or —NH—, and Y represents an alkylene group which may have a substituent or an arylene group which may have a substituent] R ₁ represents a linking group, and R ₁ represents an alkyl group which may have a substituent. X ₂ represents -O- or -NH-, and R ₂ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. ]

  According to the present invention, a pigment dispersant exhibiting high pigment dispersibility can be provided. Further, according to the present invention, it is possible to provide a coloring composition for a color filter capable of forming a coating film excellent in high contrast and suppression of foreign substances by being excellent in dispersibility and further excellent in alkali developability. Further, according to the present invention, it is possible to provide a photosensitive coloring composition for a color filter which can form a coating film exhibiting high lightness, heat resistance, alkali developability and adhesion. Further, according to the present invention, it is possible to provide a high quality color filter which exhibits the above-mentioned effects.

  The pigment dispersant of the present invention is used for gravure ink, various general paints for automobiles, woods, metals, etc., back coat paint of magnetic tape, radiation cure ink, ink for inkjet printer, ink for color filter, etc. It can be used.

  The pigment dispersant of the present invention is characterized by having an isoindoline skeleton represented by the following general formula (1). Further, the coloring composition for a color filter of the present invention is characterized by containing an organic pigment, a pigment dispersant having an isoindoline skeleton represented by the following general formula (1), a binder resin, and an organic solvent.

  Hereinafter, the present invention will be described in detail. In addition, in this specification, when it describes with "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide", Unless otherwise stated, respectively, "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide" It represents ". In addition, “CI” listed in the present specification means a color index (CI).

<Coloring composition for color filter>
<Pigment dispersant>
The pigment dispersant of the present invention has an isoindoline skeleton represented by the following general formula (1).
The compound (pigment dispersant) having an isoindoline skeleton according to the present invention has not only pigment dispersibility such as brightness, contrast, and dispersion stability but also alkali resistance, due to the synergistic effect of the specific skeleton and the specific basic substituent. Demonstrate the effect of improving. It is also excellent in developability and adhesion.

<Isoindoline compound>
General formula (1)

[In general formula (1), X ₁ represents -O- or -NH-, and Y represents an alkylene group which may have a substituent or an arylene group which may have a substituent] And R ₁ represents an alkyl group which may have a substituent. X ₂ represents -O- or -NH-, and R ₂ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. ]
Below, each group in General formula (1) is demonstrated.

As the alkyl group for R ₁ and R ₂ , methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, trifluoromethyl Group, isopropyl group, isobutyl group, isopentyl group, 2-ethylhexyl group, 2-hexyldodecyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, Although a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, 4-decylcyclohexyl group etc. can be mentioned, It is not limited to these. From the viewpoint of heat resistance and dye transfer, methyl and ethyl groups are preferred.

The aryl group in R ₂ is a phenyl group, a biphenylyl group, a terphenylyl group, a quarter phenylyl group, a pentalenyl group, an indenyl group, a naphthyl group, a binaphthalenyl group, a ternaphthalenyl group, a quarternaphthalenyl group, an azulenyl group, a heptalenyl group, a biphenylenyl group Group, indasenyl group, fluoranthenyl group, acephenanthrylenyl group, aceanthrenyl group, phenarenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group Group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexapheny Group, hexacenyl group, rubicenyl group, coronenyl groups, trinaphthylenyl groups, heptacenyl groups, pyranthrenyl groups, there may be mentioned a ovalenyl group, but is not limited thereto.

  As a bivalent linking group containing an alkylene group which may have a substituent or an arylene group which may have a substituent in Y, one hydrogen atom can be selected from the above-mentioned alkyl group and the below-mentioned aryl group It may be a divalent linking group containing an removed alkylene group or arylene group, and the alkylene group or arylene group may be linked to each other, and the alkylene group or arylene group is —O—, —COO—, — It may be linked by a divalent linking group such as CO- or -OCO-. From the viewpoint of heat resistance and migration, an alkylene group having 6 or less carbon atoms or a phenylene group is preferable.

X ₁ represents -O- or -NH-, preferably -NH-.
X ₂ represents -O- or -NH-, preferably -NH-.

  B in the general formula (1) is preferably a structure represented by the following formula (2) or a structure represented by the following general formula (3), more preferably a group represented by the following formula (2) Structure.

Formula (2)

General formula (3)

[In general formula (3), X ₂ represents -O- or -NH-, and R ₂ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. ]

  The substituent in General formula (3) is synonymous with the substituent in the said General formula (1).

Also, in the general formula (1),
Preferably it is -NH- as X _{1 and it} is preferably -NH- as X ₂
R ₁ is preferably an unsubstituted alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group,
Preferably R ₂ is an unsubstituted C 1 -C 6 alkyl or phenyl group,
As Y, Preferably it is an unsubstituted C1-C6 alkylene group or unsubstituted arylene group, More preferably, it is an unsubstituted C2-C4 alkylene group or unsubstituted arylene group.

  Specific examples of the isoindoline compound of the general formula (1) are shown below, but the present invention is not limited thereto.

<Organic pigment>
The coloring composition for color filters of the present invention contains an organic pigment. As the organic pigment, conventionally known various pigments can be arbitrarily selected. Moreover, you may use together 2 or more types. Although the organic pigment which can be used suitably below is described, it is not limited to these.

  Examples of red pigments include 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, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 221, 224, 242, 246, 254, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 2 2,283,284,285,286,287, or include diketopyrrolopyrrole pigments described in JP-T 2011-523433 Patent Publication.

  As an orange pigment, for example, C.I. I. Pigment orange 38, 43, 71 or 73 and the like.

  As a green pigment, for example, C.I. I. Pigment greens 7, 10, 36, 37, 58, 59, 62, 63, JP 2008-19383 A, JP 2007-320986 A, JP 2004 70342 A, etc., and the like. It can be mentioned.

  As a blue pigment, 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, The aluminum phthalocyanine pigment etc. which are described in the patent 4893859 etc. are mentioned.

  Examples of yellow pigments include C.I. I. Pigment yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 181, 181, 181, 181, 82,185,187,188,192,193,194,196,198,199,213,214, may be used yellow pigment quinophthalone pigments described in Japanese Patent No. 4,993,026 discloses. In particular, from the viewpoint of the heat resistance, light resistance and lightness of the filter segment, as a yellow pigment, C.I. I. It is preferable that it is at least 1 sort (s) chosen from the group which consists of pigment yellow 139 and 185.

  The organic pigment is preferably a yellow pigment, more preferably C.I. I. Pigment yellow 139 and at least one selected from the group consisting of 185.

  When the yellow pigment is contained, the isoindoline compound represented by the general formula (1) is preferably 1% by mass or more and 60% by mass or less, and 5% by mass or more and 40% by mass with respect to the yellow pigment It is more preferable that Within the above range, the effect of improving the lightness, contrast, alkali resistance, foreign matter suppression, initial viscosity, and storage stability is high, which is preferable.

  From the viewpoint of color characteristics of isoindoline compounds, it is preferable to use a yellow pigment and a phthalocyanine pigment or a diketopyrrolopyrrole pigment in combination as an organic pigment.

  The phthalocyanine pigment used in combination with the above yellow pigment is preferably a halogenated copper phthalocyanine pigment, a halogenated zinc phthalocyanine pigment, an aluminum phthalocyanine pigment, or a halogenated aluminum phthalocyanine pigment, more preferably C.I. I. Pigment green 58, 62 or 63.

  When a yellow pigment and a green pigment are used in combination, the total mass ratio of the isoindoline compound represented by the general formula (1) and the yellow pigment is 10/90 to A range of 80/20 is preferred.

  As the diketopyrrolopyrrole pigment used in combination with the above-mentioned yellow pigment, preferably C.I. I. Pigment red 254.

  When a yellow pigment and a red pigment are used in combination, the mass ratio of the total of the isoindoline compound represented by the red dye / general formula (1) and the yellow pigment is 10/90 or more from the viewpoint of lightness and hue. A range of 80/20 is preferred.

<Other colorants>
Moreover, the coloring agent for color filters of this invention may contain other coloring agents other than an organic pigment. Other colorants include conventionally known dyes and the like, and two or more of them may be used in combination.

  As the red dye, red dyes such as xanthene dyes, azo dyes, disazo dyes and anthraquinone dyes can also be used. Specifically, C.I. I. Salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289, 338 and the like can be mentioned.

  Examples of yellow dyes include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes And naphthoquinone dyes and oxazine dyes.

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

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

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

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

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

(Finening of organic pigment)
In order to obtain high brightness and high contrast, the organic pigment (hereinafter also referred to as a colorant) used in the coloring composition of the present invention may be finely divided into colorant particles by, for example, salt milling, if necessary. And as a coloring agent for color filters. The volume average primary particle size of the colorant is preferably 10 nm or more in order to enhance the dispersibility in the colorant carrier. In addition, in order to obtain a filter segment with high contrast, the thickness is preferably 80 nm or less. The particularly preferred range is in the range of 20 to 60 nm.

  In the salt milling process, a mixture of a colorant, a water-soluble inorganic salt and a water-soluble organic solvent is heated while using a kneader such as a kneader, 2-roll mill, 3-roll mill, ball mill, attritor or sand mill. After mechanical kneading, this is a treatment to remove the water-soluble inorganic salt and the water-soluble organic solvent by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the colorant is broken using salt hardness during salt milling. By optimizing the conditions for salt milling the colorant, it is possible to obtain a colorant having a very fine volume average primary particle diameter and a narrow distribution width and a sharp particle size distribution. .

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

  The water-soluble organic solvent functions to wet the coloring agent 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 used inorganic salt. However, since the temperature rises at the time of salt milling and the solvent is easily evaporated, in view of safety, those having a high boiling point of 120 ° C. or higher are preferable. As such, 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, etc. Is used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by mass, and most preferably 50 to 500% by mass, based on the total mass of the colorant (100% by mass).

When the colorant is subjected to salt milling, a resin may be added as needed. Here, the type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin to be used is solid at room temperature, preferably water-insoluble, and more preferably partially soluble in the water-soluble organic solvent. It is preferable that the usage-amount of resin is the range of 2-200 mass% on the basis of the total mass of a coloring agent (100 mass%).
Moreover, when salt-milling a coloring agent, you may add the iso indoline compound represented by General formula (1) as needed. The isoindoline compound acts as a pigment dispersant and has an effect of promoting miniaturization.

<Binder resin>
The coloring composition for color filters of the present invention is characterized by containing a binder resin. A thermoplastic resin, a thermosetting resin, etc. are mentioned as a specific example of binder resin.

(Thermoplastic resin)
As a thermoplastic resin used for binder resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

(Thermosetting resin)
As a thermosetting resin used for binder resin, an epoxy resin, benzoguanamine resin, rosin modified maleic resin, rosin modified fumaric resin, melamine resin, urea resin, cardo resin, phenol resin etc. are mentioned, for example.

  The thermosetting resin may be, for example, low molecular weight compounds such as epoxy compounds, benzoguanamine compounds, rosin modified maleic acid compounds, rosin modified fumaric acid compounds, melamine compounds, urea compounds, cardo compounds, and phenol compounds, and the present invention It is not limited to this. By including such a thermosetting resin, the resin reacts at the time of firing of the filter segment, the crosslink density of the coating film is increased, the heat resistance is improved, and the effect of suppressing pigment aggregation at the time of firing the filter segment is obtained. Be Among these, epoxy resin, cardo resin or melamine resin is preferable.

  When producing a color filter using the coloring composition for color filters, the binder resin preferably has a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light range. It is preferably a resin. The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, and more preferably in the range of 10,000 to 80,000, in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  The binder resin is preferably used in an amount of 10 parts by mass or more in resin solid content with respect to 100 parts by mass of the total mass of the colorant, because the film forming property and the various resistances are good. The resin solid content is preferably used in an amount of 500 parts by mass or less, since good color characteristics can be exhibited.

  In one embodiment, when the coloring composition is used in the form of an alkali-developable coloring resist material, an alkali-soluble vinyl resin prepared using an acidic group-containing ethylenic unsaturated monomer from the viewpoint of developability It is preferable to use as a binder resin. In another embodiment, a photosensitive coloring composition may be configured for the purpose of improving photosensitivity and improving solvent resistance. In this case, an active energy ray curable resin having an ethylenically unsaturated double bond can be used as the binder resin. Hereinafter, these embodiments will be described more specifically.

  As a vinyl type alkali soluble resin which can be used suitably as a binder, the homopolymer or copolymer prepared using an ethylenically unsaturated monomer which has acidic groups, such as a carboxyl group, a hydroxyl group, and a sulfone group, for example Can be mentioned. As specific examples of the above-mentioned vinyl alkali-soluble resin, acrylic resin having an acidic group, α-olefin / (maleic anhydride) copolymer, styrene / styrene sulfonic acid copolymer, ethylene / (meth) acrylic acid copolymer Or isobutylene / (anhydride) maleic acid copolymer and the like. Among them, at least one resin selected from (meth) acrylic resins having an acidic group and styrene / styrene sulfonic acid copolymers is preferable. In particular, a (meth) acrylic resin having an acidic group is preferably used because of its high heat resistance and transparency.

  As an acidic group in an acidic group containing ethylenically unsaturated monomer used in order to prepare the said resin, what has a carboxylic acid or a hydroxyl group is preferable. Examples of ethylenically unsaturated monomers having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Examples of ethylenically unsaturated monomers having a hydroxyl group include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4 -Hydroxyvinylbenzene, 2-hydroxy 3-phenoxypropyl acrylate, or caprolactone adducts of these monomers (additional mole number is preferably 1 to 5).

  In one embodiment, when forming a photosensitive coloring composition for a color filter, the binder resin comprises a colorant-adsorbing group and an alkali at the time of development from the viewpoints of pigment dispersibility, permeability, developability, and heat resistance. The balance between the carboxyl groups acting as soluble groups and the aliphatic and aromatic groups acting as affinity groups for the colorant carrier and solvent is weight. In one embodiment, it is preferable to use a resin having an acid value of 20 to 300 mg KOH / g as a binder resin from the viewpoint of pigment dispersibility, permeability, developability, and durability. By using a resin having an acid value within the above range, appropriate solubility in a developer can be obtained, and it becomes easy to form a fine pattern.

  From the above viewpoint, the vinyl alkali-soluble resin obtained by polymerizing the above-mentioned acidic group-containing ethylenically unsaturated monomer has an acid value of 20 to 300 mg KOH / g, and a weight average molecular weight (Mw) of 10,000 to 80. Is preferably 1,000. In one embodiment, the resin may be a copolymer of methacrylic acid, 2-hydroxyethyl (meth) acrylate, and other monomers such as n-butyl methacrylate.

  As another embodiment, when forming a photosensitive coloring composition as an alkali-developable coloring resist for color filter, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond as a binder resin, In particular, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain. When the above-mentioned resin having an ethylenically unsaturated double bond in the side chain is used as a binder resin, no coating foreign matter is generated after the resist is applied, and the stability of the colorant in the resist material is improved. Tend. When a linear resin having no ethylenically unsaturated double bond in the side chain is used, the colorant is less likely to be trapped by the resin in the liquid in which the resin and the colorant are mixed, and has a degree of freedom. As a result, the colorant component is easily aggregated and precipitated. On the other hand, in the case of using an active energy ray-curable resin having an ethylenically unsaturated double bond in a side chain, the colorant is easily trapped by the resin in a liquid in which the resin and the colorant are mixed. Therefore, in the solvent resistance test, it is difficult for the dye to be eluted and the colorant component is less likely to be aggregated and precipitated. In addition, when forming a film by exposure to active energy rays, the colorant molecules are fixed by three-dimensional crosslinking of the resin, and even if the solvent is removed in the subsequent development step, the colorant components are aggregated and precipitated. It is estimated that it will be difficult to do.

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

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

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

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

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, which may be used alone or in combination of two or more. I do not mind. It remained by using tricarboxylic acid anhydrides, such as trimellitic acid anhydride, or using tetracarboxylic acid dianhydrides, such as pyromellitic acid dianhydride, as needed, such as increasing the number of carboxyl groups. Anhydride groups can also be hydrolyzed, etc. In addition, unsaturated ethylenic double bonds can be further increased by using, as the polybasic acid anhydride, ethahydrophthalic anhydride having maleic unsaturated double bonds, or maleic anhydride.

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

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

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

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

<Organic solvent>
The coloring composition for color filters of the present invention contains an organic solvent. The organic solvent makes it easy to disperse and infiltrate the colorant into the colorant carrier and apply it on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm to form a colored film. Make it The organic solvent is selected in consideration of the solubility of each component of the photosensitive composition as well as the safety, as well as the coating property of the photosensitive composition is good.

As the organic solvent, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1 2,4-butanediol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5 Trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3 -Methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichloromethane Benzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o -Dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol Monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether Ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate , Diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol Methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene Glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents may be used alone or in combination of two or more at an arbitrary ratio as needed.

  Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, ethylene glycol monomethyl ether, because of good dispersibility of colorant, permeability, and coatability of photosensitive composition. Acetate, ethylene glycol monoethyl ether acetate, 1,3-butylene glycol diacetate, cyclohexanol acetate, 1,4-butanediol diacetate, acetate such as butanediol diacetate, benzyl alcohol, diacetone alcohol, 1-methoxy It is preferable to use alcohols such as -2-propanol and 3-methoxybutanol, ketones such as cyclohexanone, and ethyl 3-ethoxypropionate.

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

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

Examples of monomers and oligomers that cure by ultraviolet light and heat to form a transparent resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate ) Acrylate, trimethylolpropane tri (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, trimethylol Lopan PO modified tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, isocyanuric acid EO modified di (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrolein , Ester acrylates, (meth) acrylic esters of methylolated melamine, epoxy (meth) acrylates, urethane acrylates and other various acrylic esters and methacrylic esters, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, Ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinyl formamide, acrylonitrile and the like can be mentioned, but it is not necessarily limited thereto.
These photopolymerizable compounds can be used alone or in combination of two or more at an arbitrary ratio as needed.

  As these commercial products, KAYARAD R-128H, KAYARAD R526, KAYARAD PEG400DA, KAYARAD MAND, KAYARD NPGDA, KAYARAD R-167, KAYARAD HX-220, KAYARAD R-551, KAYARAD R 712, KAYARAD R 712, KAYARAD R 712, KAYARAD R 712 manufactured by Nippon Kayaku Co., Ltd. -604, KAYARAD R-684, KAYARAD GPO-303, KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPEA-12, KAYARAD DPHA-2C, KAYARAD D-310, KAYARAD D-330, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and Toa Go -Made M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400 , M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, biscoat # 310 HP manufactured by Osaka Organic Co., Ltd. Biscoat # 335 HP, Viscote # 700, Viscote # 295, Viscote # 330, Viscote # 360, Viscote # GPT, Viscote # 400, Viscote # 405, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd. can be suitably used. .

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

(A polymerizable compound having an acid group)
The photopolymerizable monomer in the present invention may contain a photopolymerizable monomer having an acid group. As an acid group, a sulfonic acid group, a carboxyl group, a phosphoric acid group etc. can be mentioned.

  As the photopolymerizable monomer having an acid group, for example, an esterified product of free hydroxyl group-containing poly (meth) acrylates of polyhydric alcohol and (meth) acrylic acid, and dicarboxylic acids; polyhydric carboxylic acid, Examples thereof include esterified products with monohydroxyalkyl (meth) acrylates. As a specific example, monohydroxy oligo acrylates or mono hydroxy oligo methacrylates such as trimethylol propane diacrylate, trimethylol propane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc. And free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4 -Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And free carboxyl group-containing oligoesters with monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. However, the effects of the present invention are not limited to these.

  As these commercial products, Biscoat # 2500P made by Osaka Organic Co., Ltd., and M-5300, M-5400, M-5700, M-510, M-520 etc. made by Toa Synthetic Co., Ltd. can be suitably used.

  These photopolymerizable monomers having an acid group can be used alone or in combination of two or more at an arbitrary ratio as needed.

(Polymerizable compound having a urethane bond)
The photopolymerizable monomer in the present invention may contain a photopolymerizable monomer containing at least one ethylenically unsaturated bond and at least one urethane bond. For example, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional isocyanate obtained by reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth) acrylate having a hydroxyl group Urethane acrylate etc. are mentioned.

  As the (meth) acrylate having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri ( Meta) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide modified penta (meth) acrylate, dipentaerythritol propylene oxide modified penta (meth) acrylate, dipentaerythritol caprolactone modified penta (meth) acrylate, glycerol acrylate Methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloyl propyl methacrylate, epoxy group containing The reaction product of compound and the carboxy (meth) acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

  Moreover, as polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate etc. are mentioned.

  In addition, although the structure of alcohol is not limited, it is preferable to use a polyhydric alcohol because the degree of crosslinking of the cured coating film is increased and the coating film resistance is increased. Examples of polyhydric alcohols include propylene glycol, ethylene glycol, glycerin, trimethylolpropane and pentaerythritol.

  These photopolymerizable monomers having a urethane bond can be used alone or in combination of two or more at an arbitrary ratio as needed.

<Photoinitiator>
A photopolymerization initiator is added to the coloring composition for color filter in order to cure the composition by ultraviolet irradiation and form a filter segment by a photolithography method, and a solvent development type or alkali development type photosensitive coloring composition It can be prepared in the form of

As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, or 3,3'4, 4, Benzophenone compounds such as 4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropyl thioxanthone, or 2,4-diethyl thioxanthone Thioxanthone compounds; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) 4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl)- s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4) -Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- (4 ′ Triazine compounds such as methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)], Oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenyl phosphine oxide or 2,4,6-trimethyl benzoyl diphenyl phosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound etc. are used.
These photopolymerization initiators can be used alone or in combination of two or more at an arbitrary ratio as required.

  As a commercial product, as an acetophenone type compound, "IRGACURE 907" (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one), all manufactured by BASF, "IRGACURE 369" (2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone), “IRGACURE 379” 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -butan-1-one, all as phosphine compounds, “IRGACURE 819” (bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide) manufactured by BASF, "IRGACURE TPO" (2,4,6-trimethyl benzoyl diphenyl phos In'okisaido), and the like.

  As commercially available products of oxime ester compounds, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (IRGACURE OXE-01), ethanone, from BASF. 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02), N-1919 (ADEKA), TRONLY TR-PBG-304, TRONLY TR-PBG-305, and TRONLY TR-PBG-309 (all are manufactured by Changshu Strong New Materials Co., Ltd.) are commercially available. Furthermore, in addition to this, the oximes described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc. It is also possible to use an ester photoinitiator.

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

Among the above-mentioned sensitizers, sensitizers which can be particularly preferably sensitized include thioxanthone derivatives, Michler's ketone derivatives and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 1-chloro-4-propoxy thioxanthone, 4,4'-bis (Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.
These sensitizers can be used alone or in combination of two or more at an arbitrary ratio as needed.

  Commercially available products include "KAYACURE DETX-S" (2,3-diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.), "EAB-F" (4,4'-bis (diethylamino) benzophenone, manufactured by Hodogaya Chemical Industry Co., Ltd.), etc. Be

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

  The content when using the sensitizer is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the radical photopolymerization initiator contained in the coloring composition, and from the viewpoint of photocurability and developability More preferably, it is 5 to 50 parts by mass.

<Antioxidant>
The coloring composition for color filters of this invention can form a color filter with the high transmittance | permeability of a coating film by including the isoindoline compound represented by Chemical formula (1), and antioxidant. The antioxidant is used to prevent the photopolymerization initiator and the thermosetting compound contained in the photosensitive coloring composition for color filter from being oxidized and yellowed due to a thermal process during thermosetting or ITO annealing. The transmittance can be increased. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation in the heating step and to obtain a high transmittance of the coating film.

  In the present invention, the "antioxidant" may be a compound having an ultraviolet absorbing function, a radical trapping function, or a peroxide decomposing function, and specifically, hindered phenol type or hindered amine type as an antioxidant. And compounds of phosphorus, sulfur, benzotriazole, benzophenone, triazine, benzoate, benzimidazole, benzimidazole, hydroxylamine and salicylic acid ester, and known ultraviolet light absorbers, antioxidants, etc. It can be used.

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

  Examples of hindered phenol-based antioxidants include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di) -Tert-Butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-tert-butyl-4-4 Methylphenol, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-t-) (Tyl-5-methylphenol), 2,2'-thio-bis- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'-thiodiethyl bis- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, 1,1,3-tris- (2'-methyl-4'-hydroxy-5'-tert-butylphenyl) -butane, 2 , 2'-methylene-bis- (6- (1-methyl-cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylene bis ( 3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), tetrakis- [methylene-3- (3,5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane and the like It can be mentioned. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.

  Specific examples of hindered phenol-based antioxidants include H-BHT (Honshu Chemical Industry Co., Ltd.), Yoshinox BB, Yoshinox 425 (above, Mitsubishi Chemical Co., Ltd.), Irganox 245, Irganox 259, Irganox 565, Irganox 1010, Irganox 1035, Irganox 1098, Irganox 1135, Irganox 1076, Irganox 1425 WL, Irganox 1330, Irganox 1520 L, Irganox 1726 (above, made by BASF Corporation), Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-330 (above, made by ADEKA , Sumilizer GM, Sumilizer GP, Sumilizer GS, Sumilizer GA-80, Sumilizer BBM-S, Sumilizer MDP-S, Sumilizer WX-R, Sumilizer WX-RC, Sumilizer BP-101, Sumilizer BP-76, Sumilizer BP-101 (all, manufactured by Sumitomo Chemical Co., Ltd.), SYANOX CY- No. 1790, SYANOX CY-2777, D-565 (above, manufactured by Sun Chemical Co., Ltd.) Nocrac 200, Noclac SP, Nocrac NS-5, Nocrac NS-6, Nocrac NS-30, Noclac 300, Noclac PBK, Nocrac NS-K Nocak DAH (manufactured by Ouchi Shinko Chemical Co., Ltd.).

  As the hindered amine antioxidant, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4) -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butane tetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-Tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 1,6,6-Pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine etc. Other oligomeric types having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Specific examples of hindered amine-based antioxidants include CYASORB UV-3346, CYASORB UV-3529, CYASORB UV-3853 (above, manufactured by Sun Chemical Co., Ltd.), Noclack 224, Noclack AW, Noclack B, Noclack PA, Noclack ODA, Noclack AD-F, Nocl CD, Nocl TD, Nocl White, Nocl DP, Nocl 810-NA, Nocl 6 C, Nocl G-1 (above, made by Ouchi Emerging Chemical Industry Co., Ltd.), Adekastab LA-52, Adekastab LA-57, Adekastab LA-63P, Adekastab LA-68, Adekastab LA-72, Adekastab LA-77Y, Adekastab LA-77G, Adekastab LA-81, Adekastab LA-82, Adekastab LA- 7, ADK STAB LA-402AF, ADK STAB LA-502XP (manufactured by ADEKA Corporation), Tinuvin 111FDL, Tinuvin123, Tinuvin144, Tinuvin292, Tinuvin312, Tinuvin700, Tinuvin770, Tinuvin5100, (manufactured by BASF Corporation).

  As a phosphorus antioxidant, tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 'isopropylidene diphenol alkyl phosphite, tris nonyl phenyl phosphite, tris dinonyl phenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-Di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidene bis (3-methyl-) 6-t-Butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxy phosphonyloxy)-Ben Zen, ethyl phosphite bis (2,4-di-tert-butyl-6-methylphenyl) and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  Specific examples of phosphorus-based antioxidants include Irgafos 168 (BASF), Adekastab PEP-8, Adekastab PEP-36A, Adekastab HP-10, Adekastub 2112, Adekastub 2112RG, Adekastub 1178, Adekastub 1500, Adekastub C, Adekastub 135A. Adeka stub 3010, Adeka stub TPP (above, manufactured by ADEKA Corporation), GSY-P101 (manufactured by Sakai Chemical Industry Co., Ltd.), Noclak TNP (manufactured by Ouchi Emerging Chemical Industry Co., Ltd.).

  As a sulfur-based antioxidant, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like can be mentioned. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  Specific examples of sulfur-based antioxidants include Adekastab AO-503, Adekastab AO-412S (above, made by ADEKA Corporation), Sumilizer TP-D, Sumilizer MB (above, made by Sumitomo Chemical Co., Ltd.), DLTP "Yositomi", DSTP "Yositomi" DMTP "Yositomi" (above, manufactured by Mitsubishi Chemical Corporation), Nocl NBC, Nocl NS-10-N, Nocl TBTU, Nocl 400 (above, Ouchi Emerging Chemical Industry Co., Ltd.).

  As a benzotriazole-based antioxidant, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2-hydroxy-3-t-butyl-5-methylphenyl) -5-chlorobenzotriazole , 2- (2'-hydroxy-5'-t-octphenyl) benzotriazole, 2- [2-hydroxy-3- (4,5,6,7-tetrahydro-1,3-dioxo-1H-isoindole) 2-ylmethyl) -5-methylphenyl] -2H-benzotriazole, 2- (2-hydroxy-3,5-di-t-pentylphenyl) benzotriazole and the like. In addition, oligomer type and polymer type compounds having a benzotriazole structure can also be used.

  Specific examples of benzotriazole-based antioxidants include Tinuvin PS, Tinuvin 99-2, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 384-2, Tinuvin 900, Tinuvin 928, Tinuvin 1130 (above, manufactured by BASF), Adekastab LA-29. , Adekastab LA-31RG, Adekastab LA-31G, Adekastab LA-32, Adekastab LA-36, Adekastab LA-36RG (above, made by ADEKA Corporation), VIOSORB520, VIOSORB550, VIOSORB583, VIOSORB590 (above, made by Joint Pharmaceuticals Co., Ltd.), Sumisorb200 , Sumisorb 250, Sumisorb 300, Sumisorb 340, Su isorb350 (or more, made by Sumika Chemtex Co., Ltd.) and the like.

  Examples of benzophenone antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4. -Octadecyloxy benzophenone, 2,2 'dihydroxy-4-methoxy benzophenone, 2,2' dihydroxy-4,4'-dimethoxy benzophenone, 2,2 ', 4,4'- tetrahydroxy benzophenone, 2-hydroxy-4 -Methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Specific examples of benzophenone-based antioxidants include UV-12, UV-329 (above, manufactured by Sun Chemical Co., Ltd.), Adekastab 1413 (made by Adeka), Viosorb 110, Viosorb 130 (above, manufactured by Kyodoyaku Co., Ltd.), Sumisorb 400 (Sumisorb 400) Chemical Chemtex Co., Ltd.).

  Examples of triazine-based antioxidants include 2,4-bis (dimethylphenyl) -6- (2-hydroxy-4-n-octyloxyphenyl) 1,3,5-triazine and 2,4-bis (allyl)-. 6- (2-hydroxyphenyl) 1,3,5-triazine, 2-ethylhexanoic acid = 2- [3-hydroxy-4- (4,6-diphenyl-1,3,5-triazin-2-yl) And phenoxy] ethyl, 6,6 ′, 6 ′ ′-(1,3,5-triazine-2,4,6-triyl) tris (3-hexyloxy-2-methylphenol) and the like. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.

  Specific examples of triazine-based antioxidants include CYASORB UV-1164 (manufactured by Sun Chemical Co., Ltd.), Adekastab LA-46, Adekastab LA-F70 (all manufactured by ADEKA Co., Ltd.), Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479 (or more). And BASF Corporation).

  As a benzoate series antioxidant, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate Etc. In addition, oligomer type and polymer type compounds having a benzoate structure can also be used.

  Specific examples of benzoate antioxidants include Sumisorb 400 (manufactured by Sumika Chemtex Co., Ltd.) and CYASORB UV-2908 (manufactured by Sun Chemical Co., Ltd.).

  Examples of benzimidazole-based antioxidants include 2-mercaptobenzimidazole and 2-mercaptomethylbenzimidazole. In addition, oligomer type and polymer type compounds having a benzimidazole structure can also be used.

  Specific examples of benzimidazole-based antioxidants include Nocl MB, Nocl MMB, and Nocl MBZ (all manufactured by Ouchi Shinko Chemical Co., Ltd.).

  Examples of hydroxylamine-based antioxidants include dialkylamine oxides and dialkyl-N-methylamine oxides. In addition, oligomer type and polymer type compounds having a hydroxylamine structure can also be used.

  Specific examples of hydroxylamine-based antioxidants include Irgastab FS042 (manufactured by BASF), and GENOX EP (manufactured by Adivant).

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

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

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

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

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

<UV absorber>
The photosensitive composition of the present invention can contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples thereof include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds. .

  The content of the ultraviolet absorber is preferably 5 to 70% by mass in 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. When the content of the ultraviolet absorber is less than the above, the effect of the ultraviolet absorber is small and the resolution can not be ensured, and when the content is more than the above, the sensitivity is low and the pixel peeling and the hole diameter are larger than the design values May cause problems such as

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

  The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass in 100% by mass of the solid content of the photosensitive coloring composition. When the total content of the photopolymerization initiator and the ultraviolet light absorber is less than the above, the adhesion is weakened to cause peeling of the pixel. When the total content is more than the above, the sensitivity may be too high and the resolution may be deteriorated.

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

  2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, octyl-3 [3-tert-butyl as a benzotriazole type organic compound -4-Hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H -Benzotriazol-2-yl) phenyl] propionate mixture, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-t-butyl- 5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2) Hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- (2H- Compounds of benzotriazol-2-yl)-(1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl esters, 2- (2H-benzotriazol-2-yl) -4,6 -Bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3 -Tetramethylbutyl) phenol is mentioned.

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

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

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

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

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

<Polymerization inhibitor>
The color composition for color filters of the present invention may contain a polymerization inhibitor in order to prevent exposure to light by diffracted light of the mask during exposure. By adding a polymerization inhibitor, the effect of preventing curing from progressing to the outside of a desired pattern is obtained by chain polymerization by light exposure.

  As a polymerization inhibitor, catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol , 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert- Alkyl catechol compounds such as butyl catechol, 3,5-di-tert-butyl catechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresor Alkyl resorcinol compounds such as cinol, 2-n-butyl resorcinol, 4-n-butyl resorcinol, 2-tert-butyl resorcinol, 4-tert-butyl resorcinol, methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, tert-butyl hydroquinone, Alkyl hydroquinone compounds such as 2,5-di-tert-butyl hydroquinone, phosphine compounds such as tributyl phosphine, trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, tribenzyl phosphine, trioctyl phosphine oxide, triphenyl phosphine oxide and the like Phosphine oxides such as triphenyl phosphite and tris nonyl phenyl phosphite Compounds, pyrogallol, and the like phloroglucinol. The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass with respect to 100 parts by mass of the colored composition excluding the solvent. In this range, the effect of the polymerization inhibitor is increased, and the linearity of the taper, the wrinkling of the coating film, the pattern resolution and the like become good.

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

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

The leveling agent may be supplemented with an anionic, cationic, nonionic or amphoteric surfactant. The surfactant may be used as a mixture of two or more.
Examples of anionic surfactants to be added to leveling agents include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphoric acid Ester etc. are mentioned.

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

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

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

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butyl pyrocatechol, tetraethyl phosphine, tetraphenyl phosphine and the like. Organic phosphine, phosphite and the like can be mentioned. 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.

  Adhesion improvers include vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinylsilanes such as vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3,3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyl trie Xysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 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.

<Method of Producing Colored Composition for Color Filter>
The coloring composition included in the present invention is a kneader, a 2-roll mill, a 3-roll mill, preferably together with a colorant, a colorant carrier such as a dispersant and a binder resin and / or a solvent, preferably together with a dispersion aid. It can manufacture based on the coloring dispersion manufactured by disperse | distributing finely using various dispersion means, such as a ball mill, a horizontal type sand mill, a vertical type sand mill, an annular type bead mill, or an attritor. At this time, two or more kinds of colorants and the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. When the solubility of the coloring agent such as a dye is high, specifically, the solubility in the solvent to be used is high, and if it is in a state in which no dissolution or foreign matter is observed by stirring, fine dispersion may not be performed. In the present invention, it is preferable to use a resin-type dispersant to disperse the colorant when producing the colored dispersion.

  Moreover, when using as a photosensitive coloring composition for color filters (resist material), it can prepare as a solvent development type or an alkali development type coloring composition. The solvent-developable or alkali-developable coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, another dispersion aid, and an additive. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Dispersion aid>
When the colorant is dispersed in the colorant carrier, dispersion aids such as dye derivatives, resin type dispersants, surfactants and the like can be suitably contained. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the coloring composition formed by dispersing the colorant in the colorant carrier using the dispersion aid has brightness, contrast and storage stability. Sex is good.

  The coloring composition for color filters of the present invention preferably contains a dye derivative. By including the dye derivative, effects such as improvement of the viscosity characteristics of the coloring composition and the physical properties of the coating film are exhibited.

[Dye derivative]
As dye derivatives used in the present invention, known dye derivatives having an acidic group, a basic group, a neutral group and the like in the organic dye residue can be used. For example, a compound having an acidic functional group such as sulfo group, carboxy group or phosphoric acid group, an amine salt thereof, a compound having a basic functional group such as a sulfonamide group or a tertiary amino group at the terminal, a phenyl group or phthalimide The compound which has neutral functional groups, such as an alkyl group, is mentioned. JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP 2003-128669, JP 2004-091497, JP 2007-156395, JP 2008-094873, JP 2008-094986, JP 2008-095007, JP 2008 JP-195916-A, Patent No. 4585781-A, JP-2006-291194-A, JP-A-2007-226161, JP-A-2007-314681, JP-A-2007-314785, JP-A-2012-226110 JP-A-2017-165820 and JP-A-2005- 81383 JP, include known dye derivative according to such. In these documents, a dye derivative may be described as a derivative, a pigment derivative, a pigment dispersant or simply a compound, etc. However, the organic dye residue described above may be an acidic group, a basic group, a neutral group, etc. The compound which has a functional group of is synonymous with a pigment derivative. Moreover, these can be used individually or in mixture of 2 or more types. Among these, from the viewpoint of the spectral stability and viscosity stability, the coloring composition of the present invention is preferably a dye derivative in which the matrix skeleton is an organic pigment residue or a triazine residue, and among them, quinophthalone pigments and azo Organic pigment residues or triazine residues which are based pigments or anthraquinone pigments are preferred.
More preferably, they are azo dye derivatives or anthraquinone dye derivatives. By including an azo dye derivative or an anthraquinone dye derivative, the compatibility with the pigment and the resin type dispersant is improved, and the effect of preventing reaggregation of the isoindoline pigment after dispersion is improved. Further, the improvement of the compatibility improves the effect of suppressing the dry aggregation at the time of coating film preparation when the colored composition or the colored curable composition is applied to glass. Therefore, the physical properties of the coating film are improved.

  The content of the dye derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more, with respect to 100 parts by mass of the colorant, from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less.

  The pigment derivative is adsorbed on the pigment surface by adding the pigment derivative to the pigment and performing dispersion processing such as wet dispersion using two rolls, three rolls, and beads, and the pigment surface has polarity and adsorption of the resin type dispersant Is promoted, and compatibility with pigments, pigment derivatives, resin type dispersants, solvents, and other additives is improved, and dispersion stability and viscosity stability over time when formed into a colored composition or a colored curable composition are improved. Do. In addition, since the compatibility is improved, the coating film is excellent in the temporal stability of the coating when the colored curable composition is applied to glass, and the waiting time from the application of the colored curable composition to the exposure (PCD: Post Coating Delay) And the stability / characteristic dependency of the pattern shape and the like with respect to the waiting time (PED: Post Exposure Delay) from exposure to heat treatment, and line width sensitivity stability. Furthermore, development time variations and development residues are also suppressed.

[Resin type dispersant]
The coloring composition of the present invention may contain a conventionally known resin-type dispersant.
The resin type dispersant has a colorant affinity site having a property of adsorbing to the additive colorant, and a site compatible with the colorant carrier, and is adsorbed to the additive colorant and dispersed in the colorant carrier Work to stabilize the Specific examples of the resin type dispersant include polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt , Polysiloxane, long chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkyleneimine) with polyester having free carboxyl group, and salts thereof Etc., (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Water-soluble resin, water-soluble polymer compound, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, used phosphoric acid ester and the like, they may be used alone or in combination, is not necessarily limited thereto.

(Basic resin type dispersant)
The dispersant used in the present invention is preferably a basic resin type dispersant having a basic functional group, and a nitrogen atom-containing graft copolymer, a tertiary amino group in the side chain, a quaternary ammonium base, a nitrogen-containing complex A nitrogen atom-containing acrylic block copolymer and a urethane polymer dispersant having a functional group containing a ring and the like are preferable. The resin-type dispersant is preferably used at about 5 to 200% by mass with respect to the total amount of the colorant, and more preferably about 10 to 100% by mass from the viewpoint of film formability.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, manufactured by BIC Chem. Japan. 167, 168, 170, 171, 174, 180, 181, 182, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2070, 2095, 2150, 2155, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P 104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen et al., SOLSPERSE-3000, 9000, 1300, manufactured by Nippon Lebrizole. , 13240, 13650, 13940, 16000, 17000, 18000, 20000, 20000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32500, 32500, 34750, 35100, 36600, 38500, 41000, 41090, 53095 , 55000, 56000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 453, 454, 4540, 4550, 4560, 4800, 010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of Ajisupa -PA111, PB711, PB821, PB822, PB824, and the like are preferable.

(Acid resin type dispersant)
Moreover, as a resin type dispersing agent used by this invention, an acidic resin type dispersing agent can also be used suitably. As a resin type dispersing agent used by this invention, it is also preferable to contain following (S1) or (S2) as a resin type dispersing agent which has a carboxyl group.
(S1) A resin type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride.
(S2) a weight obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride Resin type dispersant which is united.

«Resin type dispersant (S1)»
The resin type dispersant (S1) can be produced by a known method such as WO 2008/007776, JP 2008-029901, JP 2009-155406 and the like. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at an end, and for example, the ethylenically unsaturated monomer (r) is polymerized in the presence of the compound (q) having a hydroxyl group It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Among them, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used because the terminal hydroxyl group is preferably plural.

  That is, a polymer having two hydroxyl groups at one end, which is a more preferable example, has a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer (p1) obtained by polymerizing the ethylenically unsaturated monomer (r) contained. The hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride to form an ester bond, while the anhydride ring is opened to form a carboxylic acid. Produces

«Resin type dispersant (S2)»
The resin type dispersant (S2) can be produced by a known method such as JP2009-155406A, JP2010-185934A, JP2011-157416A, etc. For example, a compound having a hydroxyl group By polymerizing the ethylenically unsaturated monomer (r) in the presence of the reaction product of the hydroxyl group of (q) and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride can get. Among them, in the presence of a reaction product of a hydroxyl group of a compound (q1) having two hydroxyl groups and one thiol group in the molecule and an acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride Preferably, it is a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing a monomer (r1).

(S1) and (S2) are differences in whether the introduction of the polymer portion obtained by polymerizing the ethylenically unsaturated monomer (r) is performed first or later. Although molecular weight etc. may differ somewhat depending on various conditions, if the raw material and the reaction conditions are the same, theoretically the same one can be obtained.

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

  When a surfactant is added, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant. When the content of the surfactant is less than 0.1 parts by mass, the added effect is difficult to be obtained, and when the content is more than 55 parts by mass, the dispersing agent may affect the dispersion due to an excess of the dispersing agent. .

<Removal of coarse particles>
The coloring composition for color filters is preferably subjected to bead dispersion with zirconium oxide or inorganic glass in the production process, and in that case, beads having different diameters may be used. After dispersion of the beads, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0. It is preferable to remove coarse particles of 5 μm or more and mixed dust.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention comprises a filter segment formed using a green coloring composition containing the isoindoline pigment of the present invention. Color filters include those comprising red and blue filter segments.

  The coloring composition for color filters of the present invention is mainly used to form a green filter segment, and the filter segments of the other colors are formed using a red coloring composition and a blue coloring composition which are conventionally used. it can. The coloring composition of each color other than the coloring composition of the present invention can be formed using each coloring composition containing each color pigment, the binder resin, the photopolymerizable composition and the like.

<Solid-state imaging device>
The formation of the color filter segment according to the present invention can be formed using a known method without particular limitation, but since the filter segment of the imaging device is as fine as submicron to about several tens of microns, photolithography is used Is preferred.
An embodiment of the present invention is a method for producing a color filter characterized by having a color filter segment formed by curing the above-mentioned coloring composition. It contains a color filter segment obtained by curing the coloring composition according to the embodiment of the present invention described above.
The color filter according to the present embodiment includes the green filter segment, the red filter segment, and the blue filter segment described above. Other than the colored filter segment according to the present invention, it may be formed using a known colored composition containing a color pigment, containing a color dye, or containing both a color pigment and a color dye. Although the method of forming the colored filter segment is not particularly limited, it is general to use a photosensitive coloring composition which is a negative resist.
When the color filter segment is formed on a predetermined corresponding photoelectric conversion element, a negative-type color resist layer is formed of a negative-type green film formed of a negative-type photosensitive green composition, and in this case, the negative type The thickness of the color resist layer is set in the range of 0.1 μm to 3.0 μm.
The surface of the negative type color resist layer formed of the negative type colored film is subjected to pattern exposure of a plurality of portions corresponding to a plurality of photoelectric conversion elements to be formed using a photomask.
The photomask has dimensions of 4 to 5 times the dimensions of the pattern to be actually formed, and is reduced to 1/4 to 1/5 during pattern exposure to perform pattern exposure.
This photomask is a 4 to 5 times reticle, and has a pattern with a size of 4 to 5 times the size of the pattern exposed on the surface of the negative color resist layer. Then, using a stepper exposure apparatus (not shown), the pattern of the photomask is reduced to 1/4 to 1/5 and the surface of the negative color resist layer is exposed.
Subsequent to the exposure step, an alkali development treatment (developing step) is carried out to elute the uncured part after exposure to the developer and leave the photocured part. By this development step, a pattern-like film composed of color filter segments can be formed.
The development method may be any of a dip method, a shower method, a spray method, a paddle method, etc. These may be combined with a swing method, a spin method, an ultrasonic method or the like.
Before the developer is touched, the surface to be developed may be moistened with water or the like in advance to prevent uneven development. As a developing solution, an organic alkali developing solution which does not cause damage to a circuit of a base or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.
Examples of the alkaline agent contained in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4, 0] organic alkaline compounds such as -undecene, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate and the like.
As a developing solution, an alkaline aqueous solution diluted with pure water is preferably used so that the concentration of these alkaline agents is 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass. . When a developer composed of such an alkaline aqueous solution is used, generally, after development, the developer is washed (rinsed) with pure water to wash away excess developer and then dried.
Finally, the filter segments thus formed are hardened.
In the manufacturing method of the present invention, after performing the colored layer forming step, the exposing step and the developing step described above, the curing step is carried out by curing the formed colored pattern by post heating (post baking) or post exposure if necessary. May be included. Post-baking is a heat treatment after development to complete curing, and is usually heat-cured at 100 ° C. to 270 ° C. When light is used, it can be performed by g-ray, h-ray, i-ray, excimer laser such as KrF or ArF, electron beam, X-ray, etc., but at a low temperature of about 20 to 50 ° C with an existing high pressure mercury lamp. The irradiation time is preferably 10 seconds to 180 seconds, and more preferably 30 seconds to 60 seconds. In the case of combined use of post-exposure and post-heating, it is preferable to carry out post-exposure first.
By repeating the colored layer formation step, the exposure step, and the development step (further, if necessary, a curing step) as described above for the desired number of hues, a color filter having a desired hue is produced.

<Image sensor>
The solid-state imaging device of the present invention comprises the color filter of the present invention. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter for the solid-state imaging device of the present invention, and is not particularly limited as long as it functions as a solid-state imaging device. Configuration is mentioned.
A transfer electrode comprising a plurality of photodiodes and polysilicon forming a light receiving area of a solid-state imaging device (CCD sensor, CMOS sensor, organic CMOS sensor, etc.) is provided on a substrate, and the photodiode and the transfer electrode are formed on the substrate. It has a light shielding film made of tungsten or the like in which only the light receiving portion of the photodiode is opened, 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 light shielding film and the photodiode light receiving portion. It is a structure which has a color filter for solid-state image sensors of this invention on a device protective film.
Furthermore, a configuration having a condensing means (for example, a micro lens etc. hereinafter the same) on the device protective layer and under the color filter (closer to the substrate), a configuration having a condensing means on the color filter, etc. It may be
The organic CMOS sensor includes a thin film panchromatic photosensitive organic photoelectric conversion film and a CMOS signal readout substrate as a photoelectric conversion layer, and an organic material plays a role of capturing light and converting it into an electric signal. This 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 100% with respect to incident light. The organic photoelectric conversion film is a structure-free continuous film and can be laid on a CMOS signal reading substrate, so 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 known methods can be used.

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

(Polymerization average molecular weight (Mw) of resin)
The polymerization average molecular weight (Mw) of the resin was measured using a TSK gel column (manufactured by Tosoh Corporation) and a GPC equipped with a RI detector (HLC-8120GPC manufactured by Tosoh Corporation), using polystyrene as the developing solvent and polystyrene conversion It is a weight average molecular weight (Mw).

(Acid number of resin)
80 ml of acetone and 10 ml of water are added to 0.5 to 1.0 parts of the resin solution, and the mixture is stirred and uniformly dissolved, and a 0.1 mol / L KOH aqueous solution is used as a titration solution to make an automatic titrator ("COM-555") The acid value of the resin solution was measured by titration using Hiranuma Sangyo Co., Ltd.). And the acid value per solid content of resin was computed from the acid value of resin solution, and solid content concentration of resin solution.

(Method of identifying a compound having an isoindoline skeleton)
Identification of the isoindoline compound of the present invention is carried out using a mass spectrum obtained from Waters ACQUITY UPLS H-Class (using column: ACQUITY UPLC BEH C18 Column 130 Å, 1.7 μm, 2.1 mm × 50 mm) / Ms TAP XEVO TQD Identification of the obtained compound was performed with agreement of the molecular ion peak and the mass number obtained by calculation. The respective theoretical values and the measured values are summarized in Table 1.

<Production of a Compound Having an Isoindoline Skeleton>
[Example 1] (Isoindoline Compound A-1)
To 35.17 parts of 3-diethylaminopropylamine was added 29.70 parts of ethyl cyanoacetate, and the mixture was heated at 50 ° C. for 2 hours. 1815 parts of water, 73 parts of 28% ammonia water and 36.3 parts of 1,3-diiminoisoindoline were added thereto, and the mixture was stirred at 50 ° C. until the raw material 1,3-diiminoisoindoline disappeared. Disappearance of the raw material was confirmed by UPLC. Next, 363 parts of 80% acetic acid and 33.63 parts of barbituric acid were added, and the mixture was stirred at 85 ° C. until int-1 disappeared. After cooling to room temperature, 28% ammonia water is added so that the pH is 7.0 to 8.0, and after the solid content is separated by filtration, washing is performed with 1000 parts of methanol and 2000 parts of water, To give 75.58 parts (yield 72%) of isoindoline compound A-1.

[Example 2] (Isoindoline Compound A-2)
A reaction procedure is carried out in the same manner as isoindoline compound A-1 except that 35.17 parts of 3-diethylaminopropylamine is changed to 36.78 parts of 4-dimethylaminoaniline and int-2 is synthesized, and isoindoline compound A-2 85.19 parts (yield 77%) were obtained.

[Example 3] (Isoindoline Compound A-3)
The reaction is carried out in the same manner as isoindoline compound A-1 except that 35.17 parts of 3-diethylaminopropylamine is changed to 45.99 parts of 1-amino-4- (diethylamino) cyclohexane and int-3 is synthesized. 51.24 parts (yield 43%) of the indoline compound A-3 were obtained.

[Example 4] (Isoindoline Compound A-4)
To 56.21 parts of 3- (dimethylamino) propylamine was added 59.40 parts of ethyl cyanoacetate, and the mixture was heated at 50 ° C. for 2 hours. Thereto, 1815 parts of water, 363 parts of 80% acetic acid and 36.3 parts of 1,3-diiminoisoindoline were added, and the mixture was stirred at 85 ° C. until the raw materials and intermediates disappeared. After cooling to room temperature, 28% ammonia water is added so that the pH is 7.0 to 8.0, and after the solid content is separated by filtration, washing is performed with 1000 parts of methanol and 2000 parts of water, To give 39.35 parts (yield 35%) of isoindoline compound A-4.

[Example 5] (Isoindoline Compound A-5)
The reaction was carried out in the same manner as in Example 2 to obtain int-2, and then 363 parts of 80% acetic acid and 25.76 parts of cyano-N-methylacetamide were added, and the mixture was stirred at 85 ° C until int-2 disappeared. After cooling to room temperature, 28% ammonia water is added so that the pH is 7.0 to 8.0, and after the solid content is separated by filtration, washing is performed with 1000 parts of methanol and 2000 parts of water, To give 52.60 parts (yield 51%) of isoindoline compound A-5.

[Example 6] (Isoindoline Compound A-6)
After changing 35.17 parts of 3-diethylaminopropylamine to 32.73 parts of 2,4-dimethylaniline to synthesize int-4, 33.63 parts of barbituric acid was synthesized in Example 4 3- (dimethylamino) The reaction is carried out in the same manner as the isoindoline compound A-1 except that the reaction product of propylamine and ethyl cyanoacetate is changed to 44.43 parts, 64.44 parts (yield 55%) of the isoindoline compound A-6 Obtained.

[Example 7] (Isoindoline Compound A-7)
After 35.17 parts of 3-diethylaminopropylamine was changed to 23.81 parts of 2-dimethylaminoethylamine to synthesize int-5, then 33.63 parts of barbituric acid was changed to 29.70 parts of ethyl cyanoacetate The reaction procedure was carried out in the same manner as for the isoindoline compound A-1 to obtain 64.44 parts (yield 55%) of the isoindoline compound A-7.

[Example 8] (Isoindoline Compound A-8)
38.94 parts of 1-naphthol, 22.33 parts of cyanoacetic acid, 6.10 parts of p-toluenesulfonic acid were added, and the mixture was heated and stirred at 120 ° C. for 5 hours. After cooling to 50 ° C, add 1815 parts of water, 73 parts of 28% ammonia water, and 36.30 parts of 1,3-diiminoisoindoline, and at 50 ° C until the disappearance of the raw material 1,3-diiminoisoindoline It stirred. Disappearance of the raw material was confirmed by UPLC. Next, 363 parts of 80% acetic acid and 44.43 parts of the reaction product of 3- (dimethylamino) propylamine and ethyl cyanoacetate synthesized in Example 6 were added, and the mixture was stirred at 85 ° C. until int-6 disappeared. After cooling to room temperature, 28% ammonia water is added so that the pH is 7.0 to 8.0, and after the solid content is separated by filtration, washing is performed with 1000 parts of methanol and 2000 parts of water, To give 64.04 parts (yield 58%) of isoindoline compound A-8.

[Example 9] (Isoindoline Compound A-9)
31.65 parts of 2-diethylaminoethanol, 22.33 parts of cyanoacetic acid, 6.10 parts of p-toluenesulfonic acid were added, and the mixture was heated and stirred at 120 ° C. for 5 hours. After cooling to 50 ° C, add 1815 parts of water, 73 parts of 28% ammonia water, and 36.30 parts of 1,3-diiminoisoindoline, and at 50 ° C until the disappearance of the raw material 1,3-diiminoisoindoline It stirred. Disappearance of the raw material was confirmed by UPLC. Next, 363 parts of 80% acetic acid and 33.63 parts of barbituric acid were added, and the mixture was stirred at 85 ° C. until int-7 disappeared. After cooling to room temperature, 28% ammonia water is added so that the pH is 7.0 to 8.0, and after the solid content is separated by filtration, washing is performed with 1000 parts of methanol and 2000 parts of water, To give 78.35 parts (yield 74%) of isoindoline compound A-9.

[Example 10] (Isoindoline Compound A-10)
An isoindoline compound A-9 except that 31.65 parts of 2-diethylaminoethanol was changed to 44.62 parts of p-diethylaminophenol and 6.10 parts of p-toluenesulfonic acid to 6.70 parts to synthesize int-8. The reaction procedure was similarly carried out to obtain 95.50 parts (yield 81%) of isoindoline compound A-10.

[Example 11] (Isoindoline Compound A-11)
Except that 31.65 parts of 2-diethylaminoethanol was changed to 35.97 parts of 2- [2- (dimethylamino) ethoxy] ethanol and 6.10 parts of p-toluenesulfonic acid to 5.80 parts to synthesize int-9 The reaction procedure of isoindoline compound A-9 was carried out in the same manner as above to obtain 57.14 parts (yield 52%) of isoindoline compound A-11.

[Example 12] (Isoindoline Compound A-12)
To 64.47 parts of 2-diethylaminoethanol, 44.67 parts of cyanoacetic acid and 10.90 parts of p-toluenesulfonic acid were added and heated at 120 ° C. for 5 hours. After cooling to 50 ° C., 1815 parts of water, 363 parts of 80% acetic acid and 36.30 parts of 1,3-diiminoisoindoline were added, and the mixture was stirred at 85 ° C. until the raw materials and intermediates disappeared. After cooling to room temperature, 28% ammonia water is added so that the pH is 7.0 to 8.0, and after the solid content is separated by filtration, washing is performed with 1000 parts of methanol and 2000 parts of water, To give 37.18 parts (yield 31%) of isoindoline compound A-12.

[Example 13] (Isoindoline Compound A-13)
31.65 parts of 4-dimethylamino-1-butanol, 22.33 parts of cyanoacetic acid, 5.40 parts of p-toluenesulfonic acid were added, and the mixture was heated and stirred at 120 ° C. for 5 hours. After cooling to 50 ° C, add 1815 parts of water, 73 parts of 28% ammonia water, 36.3 parts of 1,3-diiminoisoindoline, and at 50 ° C until the disappearance of the raw material 1,3-diiminoisoindoline It stirred. Disappearance of the raw material was confirmed by UPLC. Next, 363 parts of 80% acetic acid, water 1815, and 49.42 parts of a reaction product of 2,4-dimethylaniline and ethyl cyanoacetate synthesized in Example 6 were added, and the mixture was stirred at 85 ° C. until int-10 disappeared. After cooling to room temperature, 28% ammonia water is added so that the pH is 7.0 to 8.0, and after the solid content is separated by filtration, washing is performed with 1000 parts of methanol and 2000 parts of water, To give 41.11 parts (yield 34%) of isoindoline compound A-13.

[Example 14] (Isoindoline Compound A-14)
23.0 parts of cyclopentylamine and 29.70 parts of ethyl cyanoacetate were added and heated at 50 ° C. for 2 hours. 1815 parts of water, 73 parts of 28% ammonia water and 36.3 parts of 1,3-diiminoisoindoline were added thereto, and the mixture was stirred at 50 ° C. until the raw material 1,3-diiminoisoindoline disappeared. Disappearance of the raw material was confirmed by UPLC. Next, 363 parts of 80% acetic acid and 48.37 parts of a reaction product of 2-diethylaminoethanol and cyanoacetic acid synthesized in Example 9 were added, and the mixture was stirred at 85 ° C. until int-11 disappeared. After cooling to room temperature, 28% ammonia water is added so that the pH is 7.0 to 8.0, and after the solid content is separated by filtration, washing is performed with 1000 parts of methanol and 2000 parts of water, To give 35.81 parts (yield 32%) of isoindoline compound A-14.

[Example 15] (Isoindoline Compound A-15)
27.86 parts of 3- (dimethylamino) -1-propanol, 22.33 parts of cyanoacetic acid, and 5.01 parts of p-toluenesulfonic acid were added, and the mixture was heated and stirred at 120 ° C. for 5 hours. After cooling to 50 ° C, add 1815 parts of water, 73 parts of 28% ammonia water, 36.3 parts of 1,3-diiminoisoindoline, and at 50 ° C until the disappearance of the raw material 1,3-diiminoisoindoline It stirred. Disappearance of the raw material was confirmed by UPLC. Next, 363 parts of 80% acetic acid, water 1815, and 42.32 parts of phenyl cyanoacetate were added, and the mixture was stirred at 85 ° C. until int-12 disappeared. After cooling to room temperature, 28% ammonia water is added so that the pH is 7.0 to 8.0, and after the solid content is separated by filtration, washing is performed with 1000 parts of methanol and 2000 parts of water, To give 48.69 parts (yield 44%) of isoindoline compound A-15.

  Table 1 shows the results of mass spectrometry of the isoindoline compounds (A-1 to A-15). Further, the theoretical value is -1 from the mass number of the calculated value because H of the compound is eliminated due to the nature of the measurement.

Comparative Example 1 (Basic Derivative A-16)
According to the synthesis method described in Japanese Patent No. 4871634, a basic derivative A-16 having a quinophthalone skeleton was obtained.

Comparative Example 2 (Acidic derivative A-17)
According to the synthesis method described in JP-A-2006-146078, an acid derivative A-17 of isoindoline skeleton was obtained.

<Manufacture of binder resin>
(Preparation of Acrylic Resin Solution 1)
800 parts of cyclohexanone is put in a reaction vessel, and heated to 100 ° C. while injecting nitrogen gas into the vessel, and 60.0 parts of methacrylic acid, 65.0 parts of methyl methacrylate, 65.0 parts of butyl methacrylate from the dropping tube at the same temperature. A mixture of 60.0 parts of 2-hydroxyethyl methacrylate and 10.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After dropping, the mixture is further reacted at 80 ° C. for 3 hours, then, a solution of 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone is added, and the reaction is further continued at 80 ° C. for 1 hour to obtain weight average molecular weight Obtained a solution of about 40,000 acrylic resin.
After cooling to room temperature, about 2 g of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and cyclohexanone is added to the previously synthesized resin solution so that the non-volatile content is 20%. An acrylic resin solution 1 was prepared.

(Preparation of Acrylic Resin Solution 2)
Add 100 parts of propylene glycol monomethyl ether acetate to a reaction vessel equipped with a separable 4-neck flask, a thermometer, a condenser, a nitrogen gas inlet pipe, and a stirrer, and heat it at 120 ° C while injecting nitrogen gas into the vessel. A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 parts of azobisisobutyronitrile is added dropwise over 2.5 hours from the dropping tube at a temperature for 2.5 hours. The reaction was done.
Next, the inside of the flask is replaced with air, and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone are added to 17.0 parts of acrylic acid, and the reaction is continued at 120 ° C. for 5 hours. The reaction was terminated when it reached .8, and a resin solution having a weight average molecular weight of about 12,000 was obtained.
Furthermore, 30.4 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours, and propylene glycol monomethyl ether acetate was added to make the non-volatile content 20% to prepare an acrylic resin solution 2

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

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

(Red processed pigment R-1)
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of CI Pigment Red 254 ("B-CF" manufactured by BASF Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80C for 6 hours. Next, this kneaded material is added to 8000 parts of hot water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. , 190 parts of a finely divided red pigment (R-1) were obtained.

<Production of Colored Composition for Color Filter>
[Example 16]
(Production of Colored Composition (YP-1))
A mixture consisting of the following components 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) using zirconia beads of 0.5 mm in diameter, It filtered with a 5 micrometer filter, and produced coloring composition 1 (YP-1).
Refined yellow pigment (Y-1): 9.5 parts Isoindoline compound (A-1): 0.5 parts Resin type dispersant ("PB 821" manufactured by Ajinomoto Fine Techno Co., Ltd.): 1.0 part Acrylic resin solution 1 45.0 parts Propylene glycol monomethyl ether acetate: 44.0 parts

[Examples 17 to 36, Comparative Examples 1 to 6]
Coloring is carried out in the same manner as the coloring composition (YP-1) except that the finely divided yellow pigment (Y-1) and the isoindoline compound (A-1) are changed to the finely divided pigment described in Table 2 and the isoindoline compound. Compositions (YP-2 to RP-5) were produced.

<Evaluation of color composition for color filter>
About the obtained coloring composition, a coating film was produced and contrast ratio, dispersion stability, and a foreign material were evaluated as follows. The results are shown in Table 3.

(Contrast ratio (CR) evaluation of coating film)
The resulting colored composition is coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, dried at 70 ° C. for 20 minutes, then heated at 230 ° C. for 60 minutes, and released The coated substrate was produced by cooling. The contrast ratio (CR) of the obtained coated substrate was measured. The prepared coated substrate was adjusted to have a film thickness of 1.5 μm after heat treatment at 230 ° C. The contrast ratio was determined according to the following criteria.
A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as a luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as a polarizing plate. In the measurement, it measured through the black mask which opened the 1-cm square hole in the measurement part.

(YP-1) to (YP-22) containing the finely divided yellow pigment were judged on the basis of the following criteria.
A: Contrast ratio (CR) is 3000 or more: extremely good O: contrast ratio (CR) is 2000 or more and less than 3000: good C: contrast ratio (CR) is 1500 or more and less than 2000: practicable x: contrast ratio (CR) is Less than 1500: Defective

(RP-1) to (RP-5) containing the finely divided red pigment were judged on the basis of the following criteria.
:: Contrast ratio (CR) is 8000 or more: extremely good :: contrast ratio (CR) is 7,000 to less than 8000: good Δ: contrast ratio (CR) is 6,000 to less than 7,000: practicable x: contrast ratio (CR) is Less than 6000: Defective

(Viscosity characteristics (dispersion stability))
The viscosity of the obtained coloring composition measured the initial viscosity in 25 degreeC using E-type viscosity meter (the Toki Sangyo Co., Ltd. "ELD-type viscosity meter"). Separately, 25 g of the coloring composition was allowed to stand at 40 ° C. for 24 hours in a sealed state in a glass container, and then the viscosity was measured by the same method as described above to obtain the viscosity over time.
Viscosity change rate = (initial viscosity-viscosity over time) / initial viscosity x 100 (%) was calculated, and the dispersion stability was evaluated based on the following criteria. Furthermore, ○ is a practically good level, Δ is a practicable level, and x is a level not suitable for practical use.
◎: When the viscosity change rate was within ± 10% and no sediment was generated.
○: When the viscosity change rate exceeds ± 10% and within 15%, and no sediment occurs.
Δ: When the viscosity change rate exceeds ± 15% and within 20%, and the sediment is not generated.
X: When the rate of viscosity change exceeds ± 20%, or when the rate of change in viscosity is within ± 20%, precipitation occurs.

(Foreign body evaluation)
The evaluation of the generation of foreign matter was carried out by applying the coloring composition on a transparent substrate so that the dried film would be about 1.5 μm, heating in an oven at 250 ° C. for 60 minutes, and allowed to cool down. The number of foreign objects in it was counted. The surface was observed using a metallurgical microscope "BX60" manufactured by Olympus Systems Corporation. The magnification was set to 500 times, and the number of foreign substances observable in any five fields of view was measured in transmission.
:: The number of foreign matter is less than 3: extremely good ○: the number of foreign matter is 3 or more and less than 20: practicable ×: the number of foreign matter is 21 or more and less than 100: poor

(Alkali resistance evaluation)
The evaluation of the alkali resistance is performed by applying the coloring composition on a transparent substrate so that the dry coating film is about 1.5 μm, drying by heating in an oven at 60 ° C. for 20 minutes, and leaving it to cool. It was immersed in 0.5% aqueous sodium hydroxide solution and 0.5% aqueous sodium carbonate solution at 20 ° C. for 30 minutes. It was observed whether each alkaline aqueous solution colored.
:: no coloring of alkaline aqueous solution ×: coloring of alkaline aqueous solution

From Table 3, the colored compositions of Examples 16 to 36 containing the isoindoline compound represented by the general formula (1) are excellent in contrast ratio, dispersion stability, less foreign matter on the substrate, and excellent in alkali resistance. It became clear that Among them, when B in the general formula (1) is a structure represented by the formula (2), excellent effects are exhibited in contrast, dispersion stability, and foreign matter evaluation.
On the other hand, although the alkali resistance is good in Comparative Examples 1, 3 and 5 using a quinophthalone-based basic derivative A-16 which is basic but whose dye skeleton is not isoindoline, the coloring composition has a contrast ratio, The coloring compositions of Comparative Examples 2, 4 and 6 using A-17, which has poor dispersion stability, many foreign substances on the substrate, and the dye skeleton is isoindoline but is acidic, have a contrast ratio and dispersion stability It became clear that it is inferior, there are many foreign substances on a substrate, and alkali resistance is also inferior.

<Preparation of Green, Red and Blue Colored Compositions>
(Preparation of Colored Composition (GP-1))
Phthalocyanine-based green pigment C.I. I. Pigment Green 58 ("FASTOGEN GREEN A110" manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material was introduced into 8000 parts of hot water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered, and after repeated washing with water to remove sodium chloride and diethylene glycol, the slurry was dried overnight at 85 ° C. to obtain a finely divided green pigment (G-1).

The mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads of 0.5 mm in diameter. Thereafter, the obtained mixture was filtered with a filter having a pore diameter of 5.0 μm to prepare a colored composition (GP-1) having a nonvolatile component of 20% by mass.
Fine green pigment (G-1) 10.0 parts Resin type dispersant ("EFKA 4300" manufactured by BASF Corp.) 1.0 part Acrylic resin solution 1 45.0 parts Propylene glycol monomethyl ether acetate 44.0 parts

(Preparation of a coloring composition (BP-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Color Co., Ltd., specific surface area 60 m ² / g) 200 parts And kneading at 80 ° C. for 6 hours. Next, this kneaded material was introduced into 8000 parts of hot water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered, and after repeated washing with water to remove sodium chloride and diethylene glycol, the slurry was dried overnight at 85 ° C. to obtain a finely divided blue pigment (B-1).

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

The mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads of 0.5 mm in diameter. Thereafter, the obtained mixture was filtered with a filter having a pore diameter of 5.0 μm to prepare a colored composition (BP-1) having a nonvolatile component of 20% by mass.
Refined blue pigment (B-1) 7.2 parts Refined violet pigment (V-1) 4.8 parts Resin type dispersant ("EFKA 4300" manufactured by BASF Corp.) 1.0 part Acrylic resin solution 1 35.0 parts 52.0 parts of propylene glycol monomethyl ether acetate

<Production of Photosensitive Colored Composition for Color Filter>
[Example 37]
(Photosensitive coloring composition (GR-1))
The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a filter with a pore size of 1 μm to produce a green photosensitive colored composition (GR-1).
Colored composition (GP-1): 20.9 parts Colored composition (YP-1): 29.1 parts Acrylic resin solution 2: 7.5 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd. "ALONIX M-" 402 "): 2.0 parts Photopolymerization initiator (" IRGACURE OXE-02 "manufactured by BASF Corporation): 1.2 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Industry Co., Ltd.): 0.3 parts Cyclohexanone: 39.0 parts

[Examples 38 to 44, Comparative Examples 7 to 8]
(Photosensitive coloring composition (GR-2) to (GR-10))
Green photosensitive coloring compositions as in Example 37 except that the coloring compositions (GP-1) and (YP-1) in Example 37 were changed to the components and parts by mass shown in Table 4 (GR-2) to (GR-10) were obtained.

[Example 45]
(Photosensitive coloring composition (RR-1))
The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a filter with a pore size of 1 μm to prepare a red photosensitive coloring composition (RR-1).
Coloring composition (RP-1) 33.6 parts Coloring composition (YP-1) 8.4 parts Acrylic resin solution 2 13.2 parts Photopolymerizable monomer ("ALONIX M400" manufactured by Toagosei Co., Ltd.) 8 parts Photopolymerization initiator ("IRGACURE OXE-02" manufactured by BASF Corp.) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.4 parts ethylene glycol monomethyl ether acetate 39.6 Department

[Examples 46 to 47, Comparative Example 9]
(Photosensitive coloring composition (RR-2) to (RR-4))
Red photosensitive coloring composition as in Example 42 except that the coloring compositions (RP-1) and (YP-1) in Example 42 were changed to the components and parts by mass shown in Table 4 (RR-2) to (RR-4) were obtained.

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

(Evaluation of lightness)
The obtained photosensitive coloring composition is uniformly coated on a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater to form a coating film, and the formed coating film is 50 mJ / cm. After exposing to ultraviolet light with an exposure dose of ² , spray development was performed for 30 seconds in a 0.2% aqueous solution of sodium carbonate at 23 ° C., and the chromaticity of the substrate obtained by baking at 230 ° C. in an oven was C light source The coated substrate which becomes the following chromaticity in each was obtained, respectively. The lightness (Y) of the obtained substrate was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.), and evaluated according to the following criteria.

(GR-1)-(GR-10) measured the lightness in x = 0.297 and y = 0.570, and judged it on the following reference | standard.
:: 66.5 or more: good ○: 65.9 or more and less than 66.5: practicable ×: less than 65.3: defective

(RR-1)-(RR-4) measured the lightness in x = 0.640 and y = 0.328, and judged it on the following reference | standard.
:: 20.0 or more: good :: 19.5 or more and less than 20.0: practicable ×: less than 19.5: defective

(Evaluation of heat resistance)
The obtained photosensitive coloring composition was applied to a glass substrate on which a black matrix is formed in advance by a spin coating method, and then dried in a clean oven at 70 ° C. for 20 minutes. Then, the substrate was cooled to room temperature and then exposed to ultraviolet light through a photomask using an extra-high pressure mercury lamp. Thereafter, the substrate was spray developed for 30 seconds in a 0.2% by mass aqueous solution of sodium carbonate at 23 ° C., washed with ion exchanged water, and dried. Further, heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a stripe-like colored pixel layer on the substrate. The prepared colored pixel layer was adjusted to have a film thickness of 2.0 μm after heat treatment at 230 ° C. [L ^* (1), a ^* (1), b ^* (1)] was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.) of the obtained coating film. Further, the chromaticity [L ^* (2), a ^* (2), b ^* (2)] after heat treatment at 250 ° C. for 60 minutes was measured, and the color difference ΔE ^* ab was determined by the following equation. The heat resistance was determined according to the following criteria.
ΔE ^* ab = [[L ^* (2) -L ^* (1)] ² + [a ^* (2) -a ^* (1)] ² + [b ^* (2) -b ^* (1)] ² ] ^1/2
:: ΔE ^* ab = 1 less than: good Δ: ΔE ^* ab = 1 or more, less than 3: practicable ×: ΔE ^* ab = 5 or more: defective

(Evaluation of developability)
Using the photosensitive coloring composition thus obtained, a spin coater is used to apply a film thickness of 2.0 μm on a 100 mm × 100 mm, 1.1 mm thick glass substrate, and the film thickness is made to be 2.0 μm. It dried and produced the coating film board | substrate. The substrate was spray-developed with a 0.2% by mass aqueous solution of sodium carbonate at 23 ° C., and the time (development time) in which development was performed until the coating film was completely eliminated was calculated, and the developability was evaluated. The judgment criteria are shown below.
:: Development time less than 20 seconds: Extremely good ○: Development time 20 seconds or more and less than 30 seconds: Good Δ: Development time 30 seconds or more and less than 40 seconds: Practicality possible ×: Development time 40 seconds or more: Impossible level

(Evaluation of adhesion)
The substrate coated with the photosensitive coloring composition on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater at a rotational speed of 2 μm after drying is dried at 70 ° C. for 20 minutes An ultraviolet light of 150 mJ / cm ² was irradiated using a super high pressure mercury lamp through a photomask having 100 openings of 10 μm × 10 μm. Subsequently, after spray development was carried out with an alkaline developing solution consisting of a 0.2% by mass aqueous solution of sodium carbonate to remove an unexposed part, the resultant was washed with ion exchanged water. At this time, the adhesion was evaluated based on how many 10 μm × 10 μm patterns remain. Further, the evaluation of developability was judged according to the following criteria. X is a difficult level to use.
:: 90 or more patterns remaining ○: 70 or more to less than 90 patterns remaining Δ: 60 or more to less than 70 patterns remaining ×: 0 to 60 or less Those with a remaining pattern

  It was shown that the photosensitive resin coloring composition containing the isoindoline compound of the present invention is excellent in lightness, heat resistance, developability and adhesion.

<Preparation of color filter>
Color filters were made using the red and green photosensitive coloring compositions of the present invention. In addition, the blue photosensitive coloring composition was prepared as follows.

(Preparation of blue photosensitive coloring composition (BR-1))
The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a blue photosensitive colored composition (BR-1).
Blue colored composition (BP-1) 34.0 parts Acrylic resin solution 15.2 parts Photopolymerizable monomer ("Alonix M400" manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (manufactured by BASF Corporation) Irgacure OXE-02 ") 2.0 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.4 parts ethylene glycol monomethyl ether acetate 45.1 parts

[Example 48]
(Color filter (CF-1))
The red photosensitive coloring composition (RR-1) of the present invention was applied to a glass substrate on which a black matrix had been previously formed by spin coating, and then dried at 70 ° C. for 20 minutes in a clean oven . The substrate was then cooled to room temperature, and then exposed to ultraviolet light through a photomask using an extra-high pressure mercury lamp.
Thereafter, the substrate was spray developed for 30 seconds in a 0.2% by mass aqueous solution of sodium carbonate at 23 ° C., washed with ion exchanged water, and dried. Further, heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a stripe-like colored pixel layer on the substrate.
Next, using the green photosensitive coloring composition (GR-1) of the present invention, a green colored pixel layer was formed in the same manner as the red colored pixel layer. Furthermore, the blue photosensitive pixel composition was similarly formed using blue photosensitive coloring composition (BR-1), and the color filter (CF-1) was obtained. The formed film thickness of each colored pixel layer was 2.0 μm.

Comparative Example 10
(Color filter (CF-2))
(CF-1) except that in the preparation of the color filter (CF-1), the red photosensitive coloring composition used was changed to (RR-4) and the green photosensitive coloring composition was changed to (GR-9) A regular color filter (CF-2) was produced in the same manner as in the above. The formed film thickness of each colored pixel layer was 2.0 μm.

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

Claims (7)

The coloring composition for color filters containing an organic pigment, the pigment dispersant represented by following General formula (1), binder resin, and an organic solvent.
General formula (1)

[In general formula (1), X ₁ represents -O- or -NH-, and Y represents an alkylene group which may have a substituent or an arylene group which may have a substituent] And R ₁ represents an alkyl group which may have a substituent. X ₂ represents -O- or -NH-, and R ₂ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. ] The coloring composition for color filters according to claim 1, wherein B in the general formula (1) is a structure represented by the following formula (2) or a structure represented by the following general formula (3).
Formula (2)

General formula (3)

[In general formula (3), X ₂ represents -O- or -NH-, and R ₂ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. ] The coloring composition for color filters according to claim 1 or 2, wherein B in the general formula (1) is a structure represented by the following formula (2).
Formula (2)
  Organic pigments such as C.I. I. Pigment yellow 139 and C.I. I. Pigment yellow 185, The coloring composition for color filters of any one of Claims 1-3.   Furthermore, the coloring composition for color filters of any one of Claims 1-4 containing at least 1 sort (s) chosen from the group which consists of a photopolymerizable monomer and a photoinitiator.   A color filter comprising a filter segment formed from the coloring composition for color filter according to any one of claims 1 to 5 on a substrate. The pigment dispersant represented by following General formula (1).
General formula (1)
[In general formula (1), X ₁ represents —O— or —NH—, and Y represents an alkylene group which may have a substituent or an arylene group which may have a substituent] R ₁ represents a linking group, and R ₁ represents an alkyl group which may have a substituent. X ₂ represents -O- or -NH-, and R ₂ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. ]