JP2013254127A - Colored composition for color filter, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored composition for color filters which has excellent dispersion stability, and can also maintain physical properties such as chemical resistance, and a color filter formed using the coloring composition.SOLUTION: A colored composition for color filters includes a pigment (A), a binder resin (B), a resin type dispersant (C), and a solvent (D). The resin type dispersant (C) has a (meth)acryloyl group, and the double bond amounts of resin components composed of the binder resin (B) and the resin type dispersant (C) are 0.3-5 mmol/g.

Description

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

  In recent years, liquid crystal display devices have been applied to TV monitor applications, personal computer monitor applications, mobile applications, and the like. For color filters used in liquid crystal display devices, the required level of lightness, color purity, etc. has been increasing in order to improve color reproducibility. In addition, since the liquid crystal display device is used for a long time, there is a strong demand for quality regarding color filters, such as heat resistance and light resistance. Furthermore, the required levels of coating uniformity, sensitivity, developability, and pattern shape when forming each color filter segment are also increasing for colored compositions used in the production of color filters. In order to meet these requirements, the concentration of coloring components such as pigments in the colored composition is increased, and the concentration of components of the photocurable resin and the monomer is decreased.

  In order to meet the ever-increasing demand for liquid crystal display devices, the production time of color filters has been shortened by simplifying the process.

  However, increasing the pigment component of the colored composition to reduce the photocuring component, or shortening the UV irradiation time to simplify the color filter manufacturing process, results in poor photocuring of the colored coating film. Specifically, a poorly cured coating film refers to a colored coating film in which a sufficiently cured portion and a portion that is not sufficiently cured are mixed in a portion to be cured. By developing the poorly cured coating film with an alkali, a color difference is produced between a sufficiently cured portion and a portion that is not sufficiently cured. Further, if the colored coating is not sufficiently cured, the resistance to a solvent such as N-methylpyrrolidone is inferior, and thus reliability cannot be maintained.

  Therefore, many studies as described below have been proposed for the above-described problems. For example, a method using a photopolymerization initiator with higher sensitivity (see Patent Document 1) or a thermosetting component such as a melamine resin. Improvements such as a method for improving the resistance of a coating film by addition (see Patent Document 2) or a method using a photo-binder resin (see Patent Document 3) have been proposed. However, the current situation is insufficient to solve problems such as color difference due to poor curing and solvent resistance.

Japanese Patent Laid-Open No. 2005-099488 JP 09-316346 A JP 2001-337450 A

  An object of the present invention is to provide a color composition for a color filter which is excellent in dispersion stability and maintains both physical properties such as chemical resistance, and a color filter formed using the color composition.

  As a result of extensive studies, the present inventors have included a resin-type dispersant (C) having a specific structure, and a resin comprising a binder resin (B) and a resin-type dispersant (C) in a color filter coloring composition. It has been found that the amount of double bonds of the components is 0.3 to 5 mmol / g, so that the coloring composition for color filter can solve the above-described problems, and has been accomplished in the present invention.

  That is, the present invention is a color filter coloring composition comprising a pigment (A), a binder resin (B), a resin-type dispersant (C), and a solvent (D), wherein the resin-type dispersant (C ) Has a (meth) acryloyl group, and the double bond amount of the resin component consisting of the binder resin (B) and the resin-type dispersant (C) is 0.3 to 5 mmol / g, The present invention relates to a color filter coloring composition.

  Further, the present invention is characterized in that the binder resin (B) has an ethylenically unsaturated double bond, and the double bond amount of the binder resin (B) is 0.2 to 2 mmol / g. The present invention relates to a coloring composition for a color filter.

  The present invention also relates to the colored composition for a color filter, wherein the acid value of the resin-type dispersant (C) is 5 to 200 mgKOH / g.

  In addition, the present invention relates to the colored composition for a color filter, wherein the resin type dispersant (C) has a weight average molecular weight of 2,000 to 100,000.

In the present invention, the resin-type dispersant (C) has an acid anhydride group and a molecule in one or more acid anhydrides selected from a tetracarboxylic acid anhydride (a) and a tricarboxylic acid anhydride (b). A polyester part (C1) having a carboxyl group obtained by reacting a hydroxyl group in a compound (g) having two hydroxyl groups and one thiol group, and an ethylenically unsaturated monomer (e) having no hydroxyl group And a vinyl polymer part (C2) formed by radical polymerization of an ethylenically unsaturated monomer (f) having a hydroxyl group, and the vinyl polymer (C2) part has a (meth) acryloyl group. The present invention relates to a coloring composition for a color filter.
About.

  In addition, the present invention relates to the coloring composition for a color filter, wherein the resin type dispersant (C) has a double bond amount of 0.3 to 3.3 mmol / g.

  The present invention also relates to the coloring composition for a color filter, wherein the pigment (A) contains a diketopyrrolopyrrole pigment having an average primary particle diameter of 10 to 40 nm.

  In addition, the present invention relates to the coloring composition for a color filter, wherein the pigment (A) contains a halogenated zinc phthalocyanine pigment having an average primary particle diameter of 10 to 40 nm.

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

  Moreover, this invention comprises the filter segment formed from the said coloring composition for color filters on a base material, The color filter characterized by the above-mentioned.

  The colored composition for a color filter of the present invention can provide a colored composition for a color filter that suppresses aggregation of pigments and has excellent dispersion stability, and a color filter that also has excellent chemical resistance.

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

First, the coloring composition for a color filter of the present invention will be described.
The coloring composition for a color filter of the present invention is a coloring composition for a color filter comprising a pigment (A), a binder resin (B), a resin-type dispersant (C), and a solvent (D), The resin type dispersant (C) has a (meth) acryloyl group, and the double bond amount of the resin component comprising the binder resin (B) and the resin type dispersant (C) is 0.3 to 5 mmol / g. It is characterized by being.

<Pigment (A)>
As the pigment (A), organic or inorganic pigments can be used alone or in admixture of two or more. Among the pigments, pigments having high color developability and high heat resistance, particularly pigments having high heat decomposition resistance are preferred, and organic pigments are usually used.

  Organic pigments include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, halogenated zinc phthalocyanine, and metal-free phthalocyanine, aminoanthraquinone, diaminodi Anthraquinone pigments such as anthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindoline pigment, isoindoline Examples thereof include linone pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.

  Among these, a red pigment is preferably a diketopyrrolopyrrole-based organic pigment, and a green pigment is preferably a halogenated zinc phthalocyanine-based organic pigment because a color filter having excellent brightness and resistance can be obtained.

Examples of the diketopyrrolopyrrole pigment include structures represented by the following general formula, and have excellent light resistance and heat resistance.
In the formula, D ₁ and D ₂ each independently represent —H, a saturated or unsaturated alkyl group that may be substituted, a cyano group, an aryl group that may be substituted, or a halogen group.

  These organic pigments may be used after being refined by a refinement method described later, and the average primary particle diameter is preferably 5 nm or more, more preferably 60 nm, because of good dispersion in the colorant carrier. A particularly preferable range is a range of 10 to 40 nm.

  The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is approximated to a cube having the obtained particle diameter to obtain an average volume, and the length of one side of the cube having this average volume is determined as the average primary The particle size.

  Below, the specific example of the organic pigment which can be used for the coloring composition for color filters of this invention is shown with a color index number.

When forming a red filter segment using the coloring composition of the present invention, for example, C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 166, 168, 176, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 221, 223, 224, 226, 227, 228, 240, Red pigments such as 242, 246, 254, 255, 264, and 272 can be used.
Among these, the pigment is C.I. I. Pigment Red 254 is preferable because it is excellent in lightness and heat resistance, and a high-quality color filter can be obtained.

  The red coloring composition includes C.I. I. Pigment Orange 36, 38, 43, 71, or 73, and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 182,185,187,188,193,194,198,199,213,214,218,219,220, or may be used in combination of a yellow pigment 221, and the like.

When forming a green filter segment using the coloring composition of the present invention, for example, C.I. I. Green pigments such as CI Pigment Green 7, 10, 36, 37, and 58 can be used.
Among these, the pigment is C.I. I. Pigment Green 58 is preferable because it is excellent in lightness and heat resistance, and a high-quality color filter can be obtained.

  The green coloring composition includes C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 1 It can be used in combination with the yellow pigments such as 6,177,179,180,181,182,185,187,188,193,194,199,213,214.

When forming a blue filter segment using the coloring composition of the present invention, for example, C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, and 64 can be used.
The blue coloring composition includes C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination.

Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber And synthetic iron black. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.
The colorant used in the present invention contains the pigment, but in addition, for color matching, a dye may be contained within a range in which the heat resistance is not lowered.

(Miniaturization of pigment)
When the colorant used in the coloring composition of the present invention is a pigment, it is preferably used after being refined. There are no particular limitations on the method of miniaturization. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As exemplified in the present invention, salt milling treatment by a kneader method, which is one type of wet grinding. Etc. can be made finer. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. When the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult. When the thickness is larger than 90 nm, a sufficient contrast ratio cannot be obtained. For these reasons, a more preferable average primary particle size is in the range of 5 to 60 nm, more preferably 10 to 40 nm.

  Salt milling is a batch or continuous type of mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent, such as a kneader, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. In this process, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a kneader. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

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

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

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

<Dye derivative>
When the pigment is dispersed in the dye carrier, a dye derivative may be appropriately contained. Since the dye derivative has a large effect of preventing re-aggregation of the pigment after dispersion, the coloring composition obtained by dispersing the pigment in the dye carrier using the dye derivative has good brightness and viscosity stability. preferable.

  Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine.

The pigment derivative is a compound represented by the following general formula (1), and has a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent.
General formula (1)
L-D
L: Organic pigment residue D: Basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group

  In the general formula (1), organic pigments constituting the organic pigment residue of C include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, polyazo, copper phthalocyanine, halogenated copper phthalocyanine, and zinc halide. Phthalocyanine pigments such as phthalocyanine and metal-free phthalocyanine, anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigment, dioxazine pigment, perinone pigment Perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.

  In the general formula (1), examples of the basic substituent of D include substituents represented by the following formula (2), formula (3), formula (4), and formula (5). Includes substituents represented by formula (6) and formula (7).

X: represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
n represents an integer of 1 to 10.
R ₁ and R ₂ : each independently an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, an optionally substituted phenyl group, or R ₁ and R ₂ together represent an optionally substituted heterocycle containing an additional nitrogen, oxygen or sulfur atom.
R ₃ represents an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group.
R ₄ , R ₅ , R ₆ , R ₇ : each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or a substituent Represents an optionally substituted phenyl group.
Y: represents —NR ₈ —Z—NR ₉ — or a direct bond.
R ₈ and R ₉ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group. Represents.
Z: represents an optionally substituted alkylene group having 1 to 36 carbon atoms, an optionally substituted alkenylene group having 2 to 36 carbon atoms, or an optionally substituted phenylene group.

R: represents a substituent represented by the general formula (8) or a substituent represented by the general formula (9).
Q: A hydroxyl group, an alkoxyl group, a substituent represented by the general formula (8) or a substituent represented by the general formula (9).

M: represents a hydrogen atom, calcium atom, barium atom, strontium atom, manganese atom or aluminum atom.
i: represents the valence of M.
R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ : each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, substitution Represents an optionally substituted phenyl group or polyoxyalkylene group.

  Examples of the amine component used to form the substituent represented by the general formula (2) to the general formula (5), the general formula (8), and the general formula (9) include dimethylamine, diethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropyl Amine, N, N-sec-butylpropylamine, dibutylamine, disec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) Amine, dioctylamine, N, N-methyloctadecylami , Didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentyla N, N-methyl-laurylaminopropylamine, N, N-ethylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isonicopetic acid, Ethyl isonicopetinate 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N -Ami Nopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine, etc. .

  The amine component used to form the sulfonic acid amine salt of the general formula (7) may be any of primary, secondary, tertiary and quaternary amines. Hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine , Amines such as eocosylamine, or unsaturated amines corresponding to the respective carbon number.

Secondary, tertiary and quaternary amines include dioleylamine, distearylamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylstearylamine, dilaurylmonomethylamine, trioctylamine, dimethyldidodecylammonium chloride, Dimethyl dioleyl ammonium chloride, dimethyl didecyl ammonium chloride, dimethyl dioctyl ammonium chloride, trimethyl stearyl ammonium chloride, dimethyl distearyl ammonium chloride, trimethyl decyl ammonium chloride, trimethyl hexadecyl ammonium chloride, trimethyl octadecyl ammonium chloride, dimethyl dodecyl tetradecyl ammonium chloride , Dimethyl hexadecyl octadec Ammonium chloride, and the like.
Further, any of _{R 10, R 11, R 12} , R 13 in the general formula (7) may represent a polyoxyalkylene group, examples of the polyoxyethylene group, a polyoxypropylene group, and the like.

Specific examples of pigment derivatives are shown below with compound numbers.

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

<Binder resin (B)>
The binder resin (B) contained in the colored composition of the present invention is one that disperses a pigment or is dyed or penetrated, and preferably has a spectral transmittance in the entire wavelength region of 400 to 700 nm in the visible light region. The resin is preferably 80% or more, more preferably 95% or more.

  Examples of the binder resin (B) include conventionally known thermoplastic resins and thermosetting resins. Among these resins, the double bond amount of the resin component composed of the binder resin (B) and the resin-type dispersant (C) is preferably 0.3 to 5 mmol / g. Further, it is preferably a resin having an ethylenically unsaturated double bond, and the double bond amount is preferably 0.2 to 2 mmol / g in order to improve photosensitivity.

  In particular, by using a resin having an ethylenically unsaturated double bond in the side chain, when the coating film is formed by exposure with active energy rays, the colorant is fixed by the three-dimensional crosslinking of the resin, and the heat resistance And color fading (decrease in brightness) due to heat of the colorant can be suppressed. In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development process.

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

  Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer.

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

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

  A thermoplastic resin having an alkali-soluble performance, an ethylenically unsaturated double bond, and an energy ray curing performance is also preferred as the color filter coloring composition.

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

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

  Examples of the resin having an ethylenically unsaturated double bond include resins into which an ethylenically unsaturated double bond has been introduced by the methods (i) and (ii) shown below.

[Method (i)]
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond. There is a method of introducing a carboxyl group having the function of a functional resin and having an alkali-soluble function.

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

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

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

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

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

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

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

(Thermosetting resin)
Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

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

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are TPCgel columns (manufactured by Tosoh Corp.) and GPC (HLC-8120GPC manufactured by Tosoh Corp.) equipped with an RI detector. It is the molecular weight in terms of polystyrene measured using THF.

  The binder resin (B) has a balance of a colorant-adsorbing group and a carboxyl group that functions as an alkali-soluble group during development, an aliphatic group that functions as an affinity group for the colorant carrier and a solvent, and an aromatic group, and the dispersion of the colorant. The resin having an acid value of 20 to 300 mgKOH / g is preferably used. When the acid value is 20 mgKOH / g or more, the solubility in the developer is excellent, and when the acid value is 300 mgKOH / g or less, formation of a fine pattern is good.

  The binder resin (B) is preferably used in an amount of 20 to 500 parts by weight with respect to 100 parts by weight of the pigment (A). When the amount is 20 parts by weight or more, the film formability and various resistances are excellent, and when the amount is 500 parts by weight or less, the concentration of the colorant becomes sufficient and color characteristics can be expressed.

<Resin type dispersant (C)>
The resin-type pigment dispersant (C) in the present invention has a pigment-affinity part having a property of adsorbing to the pigment and a part compatible with the dye carrier, and adsorbs to the pigment to become a pigment dye carrier. It works to stabilize the dispersion.
The double bond amount of the resin type dispersant (C) is such that the double bond amount of the resin component comprising the binder resin (B) and the resin type dispersant (C) is 0.3 to 5 mmol / g. Although it will not restrict | limit if adjusted in this way, it may be 0.3-5 mmol / g only by the resin type dispersing agent (C). Furthermore, the range of 0.3-3.3 mmol / g is preferable from a viewpoint of being excellent in the initial viscosity and solvent tolerance of the coloring composition for color filters.

  The acid value of the resin-type dispersant (C) is not particularly limited as long as it is 500 or less, but is 5 to 200 mgKOH / g from the viewpoint of excellent initial viscosity and solvent resistance of the color filter coloring composition. It is preferable.

  The weight average molecular weight of the resin type dispersant (C) is not particularly limited, but is 2,000 to 100,000 from the viewpoint of excellent initial viscosity and solvent resistance of the color filter coloring composition. Is preferred.

  The resin-type dispersant (C) of the present invention is not limited as long as it has a (meth) acryloyl group, and is polyvinyl, polyurethane, polyester, polyether, formalin condensation, silicone, and these Examples include composite polymers. In addition to the (meth) acryloyl group, the pigment affinity site includes polar groups such as a carboxyl group, a hydroxyl group, a phosphate group, a phosphate ester group, a sulfonate group, a hydroxyl group, an amino group, a quaternary ammonium base, and an amide group. And a group having a hydrophilic polymer chain such as polyethylene oxide, polypropylene oxide, and a composite system thereof, and the like, and the site compatible with the dye carrier includes a long-chain alkyl chain, a polyvinyl chain, and a polyester chain. Etc.

  Specific examples of the resin-type pigment dispersant (C) include a styrene-maleic anhydride cocondensate, an olefin-maleic anhydride copolymer, a poly (meth) acrylate, and a styrene- (having a (meth) acryloyl group). (Meth) acrylic acid copolymer, (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer, (meth) acrylic acid-polyvinyl macromer copolymer, phosphoric ester group-containing acrylic resin, aromatic carboxyl group -Containing acrylic resin, polystyrene sulfonate, acrylamide- (meth) acrylic acid copolymer, carboxymethyl cellulose, polyurethane prepolymer having carboxyl group, formalin condensate of naphthalene sulfonate, and sodium alginate Dispersant; polyvinyl alcohol, polyal Nonionic resin-type pigment dispersants such as lenpolyamine, polyacrylamide, and polymer starch; and cations such as polyethyleneimine, aminoalkyl (meth) acrylate copolymer, polyvinylimidazoline, polyurethane prepolymer having an amino group, and satkinsan Resin-based pigment dispersants, and these can be used alone or in admixture of two or more.

  Among these, preferably, the resin-type dispersant (C) is present in the molecule with an acid anhydride group in one or more acid anhydrides selected from tetracarboxylic acid anhydride (a) and tricarboxylic acid anhydride (b). A polyester part (C1) having a carboxyl group obtained by reacting a hydroxyl group in a compound (g) having two hydroxyl groups and one thiol group, and an ethylenically unsaturated monomer (e) having no hydroxyl group And a vinyl polymer part (C2) formed by radical polymerization of an ethylenically unsaturated monomer (f) having a hydroxyl group, and a resin-type dispersant having a (meth) acryloyl group in the vinyl polymer (C2) part Is

More preferably, the resin-type dispersant (C) has a hydroxyl group in the compound (g) having two hydroxyl groups and one thiol group in the molecule, and an acid anhydride group in the tetracarboxylic anhydride (a). Radical polymerization of an ethylenically unsaturated monomer (e) having no hydroxyl group and an ethylenically unsaturated monomer (f) having a hydroxyl group in the presence of the compound (h1) produced by the reaction of A (meth) acryloyl group obtained by reacting a hydroxyl group in the hydroxyl group-containing compound (k1) thus obtained with an isocyanate group in the compound (i) having one isocyanate group and one or more (meth) acryloyl groups. If you have
Or
Hydroxyl group in compound (g) having two hydroxyl groups and one thiol group in the molecule and hydroxyl group-containing compound (j) having no thiol group, and acid anhydride group in tetracarboxylic acid anhydride (a) Radical polymerization of an ethylenically unsaturated monomer (e) having no hydroxyl group and an ethylenically unsaturated monomer (f) having a hydroxyl group in the presence of the compound (h2) produced by the reaction of A (meth) acryloyl group obtained by reacting a hydroxyl group in the hydroxyl group-containing compound (k2) thus obtained with an isocyanate group in the compound (i) having one isocyanate group and one or more (meth) acryloyl groups. If you have
Or
Of the compound (h3) produced by reacting the hydroxyl group in the compound (g) having two hydroxyl groups and one thiol group in the molecule with the acid anhydride group in the tricarboxylic acid anhydride (b). In the presence, a hydroxyl group in a hydroxyl group-containing compound (k3) obtained by radical polymerization of an ethylenically unsaturated monomer having no hydroxyl group (e) and an ethylenically unsaturated monomer having a hydroxyl group (f); This is a case having a (meth) acryloyl group obtained by reacting one isocyanate group with an isocyanate group in the compound (i) having one or more (meth) acryloyl groups.

The tetracarboxylic anhydride (a) reacts with a hydroxyl group to form an ester bond, and can leave a pendant carboxyl group on the resulting polyester main chain, and remains in the subsequent step. A vinyl copolymer portion can be introduced by radical polymerization of an ethylenically unsaturated monomer using a thiol group as a chain transfer agent.
Compound (g) having two hydroxyl groups and one thiol group:

Then, the reaction formula in the case where the tetracarboxylic anhydride having the core portion X1 is reacted under the condition of excess hydroxyl group and the ethylenically unsaturated monomer is subsequently introduced is shown in the following reaction process formula (1). In the following reaction process formula (1), n is the number of repeating units, and B is a vinyl copolymer portion (C2).

  Similarly, when the tricarboxylic acid anhydride (b) is used, it can react with a hydroxyl group to form an ester bond and leave a carboxyl group. The reaction formula at this time is shown in the following reaction process formula (2). In the following reaction process formula (2), B is a vinyl copolymer (C2) portion.

  In the resin-type dispersant (C) of the present invention, when there are two or more carboxyl groups bonded to the core portions X1 and X2, it is preferable for exhibiting high dispersibility, fluidity, and storage stability. .

  In the resin-type dispersant (C) of the present invention, the core part X1 is a reaction residue after the tetracarboxylic acid anhydride (a) reacts with a hydroxyl group, and the core part X2 is a tricarboxylic acid anhydride (b). Is a reaction residue after reacting with a hydroxyl group, and A is a trivalent residue, for example, linear or branched having 1 to 10 carbon atoms (preferably 1 to 8 carbon atoms). And the two hydroxyl groups bonded to A may be bonded to the same carbon atom or may be bonded to different carbon atoms. B is a vinyl copolymer (C2) portion. A preferred form of the core portion X1 is a reaction residue after the tetracarboxylic acid anhydride (a) represented by the following general formula (2) or general formula (3) has reacted with the polyol compound.

[In General Formula (2), k is 1 or 2. ]

[In General Formula (3), R ⁵¹ represents a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, a formula:

Or a group represented by the formula:

It is group represented by these. ]
A preferable form of the core portion X ₂ is a reaction residue after the tricarboxylic acid anhydride (b) represented by the following general formula (4) has reacted with the polyol compound.

[In General Formula (4), k is 1 or 2. ]

  The resin type dispersant (C) has a compound (g) having two hydroxyl groups and one thiol group, a tetracarboxylic acid anhydride (a) or a tricarboxylic acid anhydride (b), and an optionally added thiol group. A first step of first producing compounds (h1) to (h3) having pendant carboxyl groups by reacting with a hydroxyl group-containing compound (j) not to be added, followed by the above-mentioned compounds (h1) to (h3) Vinyl having a hydroxyl group by radical polymerization of an ethylenically unsaturated monomer (e) having no hydroxyl group and a ethylenically unsaturated monomer (f) having a hydroxyl group using the remaining thiol group as a chain transfer agent A second step of producing the hydroxyl group-containing compounds (k1) to (k3) into which the polymer part B has been introduced; and a compound (i) having one isocyanate group and one or more (meth) acryloyl groups And a third step which is a reaction with A plurality of carboxyl group portions in the dispersant of the present invention function as a pigment adsorbing portion, and a vinyl polymer portion functions as a solvent affinity portion.

“Vinyl polymer part B formed by radical polymerization of ethylenically unsaturated monomer (e) having no hydroxyl group and ethylenically unsaturated monomer (f) having a hydroxyl group” means two hydroxyl groups and 1 Pendant obtained by reacting a compound (g) having two thiol groups with a tetracarboxylic acid anhydride (a) or a tricarboxylic acid anhydride (b) and a hydroxyl group-containing compound (j) having no thiol group to be optionally added It is a continuous part which does not contain the polyester part (C1) having a carboxyl group, and usually one or more vinyl polymer parts (C1) are contained in one molecule constituting the dispersant of the present invention.

The weight average molecular weight of the vinyl polymer portion B formed by radical polymerization of the ethylenically unsaturated monomer (e) having no hydroxyl group and the ethylenically unsaturated monomer (f) having a hydroxyl group is 1,000 to It is preferably 50,000, more preferably 2,000 to 30,000, still more preferably 2,000 to 20,000, and particularly preferably 2,500 to 10,000. This part (C2) becomes an affinity part to the solvent which is a dispersion medium. When the weight average molecular weight of the vinyl polymer part B is less than 1,000, the effect of steric repulsion by the solvent affinity part is reduced, and it is difficult to prevent the aggregation of the pigment, and the dispersion stability may be insufficient. . On the other hand, if it exceeds 50,000, the absolute amount of the solvent-affinity part increases, and the dispersibility effect itself may decrease. Further, the viscosity of the dispersion may increase. The vinyl polymer portion B can be easily adjusted in molecular weight within the above range, and has good affinity for the solvent.
First, compound (g) having two hydroxyl groups and one thiol group in the molecule, tetracarboxylic acid anhydride (a) or tricarboxylic acid anhydride (b), and hydroxyl group containing no thiol group to be optionally added The first step of producing compounds (h1) to (h3) having pendant carboxyl groups by reacting with compound (j) will be described.

  Examples of the compound (g) having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1 , 2-propanediol (alias: 1-thioglycerol), 2-mercapto-1,3-propanediol, 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methy-1,3-propanediol, 2-mercaptoethyl-2- And ethyl-1,3-propanediol.

  The tetracarboxylic anhydride (a) used in the resin-type dispersant (C) is 1, 2, 3, 4-butanetetracarboxylic anhydride, 1, 2, 3, 4-cyclobutanetetracarboxylic anhydride. 1,3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3,4-cyclopentanetetracarboxylic anhydride, 2,3,5-tricarboxycyclopentylacetic anhydride 3,5,6-tricarboxynorbornane-2-acetic anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic anhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl- 3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo [2,2,2] -oct-7-ene-2, Aliphatic tetracarboxylic anhydrides such as 3,5,6-tetracarboxylic anhydride; pyromellitic anhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol dianhydride tri Mellitic acid ester, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid anhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic acid anhydride, 1,4,5,8-naphthalenetetracarboxylic acid Acid anhydride, 2,3,6,7-naphthalenetetracarboxylic acid anhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic acid anhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane Tetracarboxylic anhydride, 3, 3 ', 4, 4'-tetrafe Rusilanetetracarboxylic anhydride, 1,2,3,4-furantetracarboxylic anhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide anhydride, 4,4'-bis ( 3,4-dicarboxyphenoxy) diphenylsulfone anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane anhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic acid Anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride, bis (phthalic acid) phenylphosphine oxide anhydride, p-phenylene-bis (triphenylphthalic acid) anhydride, m-phenylene-bis (Triphenylphthalic acid) anhydride, bis (triphenylphthalic acid) -4, 4 ' -Diphenyl ether anhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane anhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic anhydride, 9,9-bis [4- ( 3,4-Dicarboxyphenoxy) phenyl] fluorenic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic anhydride, 3,4-dicarboxy-1,2 Aromatic tetracarboxylic anhydrides such as, 3,4-tetrahydro-6-methyl-1-naphthalene succinic anhydride.

  The tetracarboxylic anhydride (a) used in the resin-type dispersant (C) is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydride groups. . These may be used alone or in combination. What is preferably used in the present invention is an aromatic tetracarboxylic dianhydride from the viewpoint of reducing the viscosity of the pigment dispersion or various inks. Further, pyromellitic dianhydride, 3, 3 ′, 4, 4′-benzophenone tetracarboxylic dianhydride, ethylene glycol ditrimellitic anhydride ester, 3, 3 ′, 4, 4′-biphenyl ether tetra Carboxylic dianhydride, 9, 9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 3, 3 ', 4, 4'-biphenylsulfone tetracarboxylic dianhydride, 2, 3, 6 , 7-Naphthalenetetracarboxylic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are preferred. The use of a tricarboxylic acid anhydride (b) is also a preferred form of the dispersant of the present invention. Examples of the tricarboxylic acid anhydride (b) include aliphatic tricarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides.

  Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid. Examples include acid-1,2-anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride, and the like.

  Examples of the aromatic tricarboxylic acid include benzene tricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzenetricarboxylic acid anhydride], etc.), naphthalenetricarboxylic acid, and the like. Acid anhydride (1,2,4-naphthalenetricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 1,2,8-naphthalenetricarboxylic acid anhydride ), 3, 4, 4'-benzophenone tricarboxylic anhydride, 3, 4, 4'-biphenyl ether tricarboxylic anhydride, 3, 4, 4'-biphenyl tricarboxylic anhydride, 2, 3, 2 ' -Biphenyltricarboxylic anhydride, 3, 4, 4'-biphenyl Tan tricarboxylic acid anhydride, 3, 4, 4 '- biphenyl sulfonic tricarboxylic acid anhydrides. When tricarboxylic acid anhydride is used, aromatic tricarboxylic acid anhydride is particularly preferable among the above, and trimellitic acid anhydride is more preferable.

  Moreover, it is possible to use together the compound (g) which has two hydroxyl groups and one thiol group in a molecule | numerator, and the hydroxyl-containing compound (j) which does not have a thiol group in arbitrary ratios. By using the hydroxyl group-containing compound (j) having no thiol group, the ratio of the pigment adsorbing part and the solvent dissolving part can be easily adjusted.

  As a hydroxyl-containing compound (j) which does not have a thiol group, a well-known thing can be used, for example, it does not have a thiol group in 1 molecule, and uses the compound which has 2-4 hydroxyl groups. Can do. Among them, there are those belonging to the following groups (1) to (7) if only typical ones are exemplified.

  (1) Ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1, 4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerin, or Polyhydric alcohols such as hexanetriol;

  (2) Various polyethers such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol Glycols;

  (3) Various polyhydric alcohols or polyether glycols described above and various (cyclic) such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, or allyl glycidyl ether. ) Modified polyether polyols obtained by ring-opening polymerization with an ether bond-containing compound;

  (4) Polyester polyols obtained by co-condensation of at least one of the various polyhydric alcohols or polyether glycols described above with polyhydric carboxylic acids, wherein the polycarboxylic acids are succinic acid, adipine Acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexane Particularly represented by hycarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid Polyester polyols obtained using

  (5) Polycondensation reaction of one or more of the various polyhydric alcohols or polyether glycols described above with various lactones such as ε-caprolactone, δ-valerolactone, or 3-methyl-δ-valerolactone. Or lactone-modified polyester polyols obtained by polycondensation reaction of the above-mentioned various polyhydric alcohols or polyether glycols, polycarboxylic acids and various lactones;

  (6) Various epoxy compounds such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and / or polyhydric alcohols, or glycidyl esters of monobasic acids and / or polybasic acids , Epoxy-modified polyester polyols obtained by combining one or more of these during the synthesis of the polyester polyol;

  (7) Polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated castor oil derivative, hydroxyl group-containing acrylic copolymer, hydroxyl group-containing fluorine-containing compound or hydroxyl group-containing silicon resin Is mentioned.

  Of course, the hydroxyl group-containing compound (j) having no thiol group added arbitrarily shown in (1) to (7) may be used alone or in combination of two or more. As an average molecular weight, 100-10,000 are preferable, More preferably, it is 100-2,000, More preferably, it is 100-1,000.

  A compound having only one hydroxyl group may be used in combination. It is not particularly limited as long as it has only one hydroxyl group. For example, aliphatic alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol, aliphatic aromatic alcohols such as benzyl alcohol and phenethyl alcohol, 2 Examples include alcohols having a photocurable site such as -hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.

  In the resin-type dispersant (C), the “photocurable site” means a functional group that is polymerized by irradiation with active energy rays such as ultraviolet rays and electron beams, and specific examples thereof include a vinyl group and an acryloyl group. And a methacryloyl group.

  A known catalyst can be used as the catalyst used when the acid anhydride group and the hydroxyl group of the resin-type dispersant (C) are reacted. For example, triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene, monobutyltin oxide and the like.

  Compounds (h1) to (h3) having pendant carboxyl groups obtained in the first step are compounds (g) having two hydroxyl groups and one thiol group in the molecule, tetracarboxylic acid anhydride (a), and It can be obtained by reacting optionally added tricarboxylic acid anhydride (b) and a hydroxyl group-containing compound (j) having no thiol group. Compound (g) having an acid anhydride group in tetracarboxylic anhydride (a) and tricarboxylic anhydride (b), two hydroxyl groups and one thiol group in the molecule, and a hydroxyl group not having a thiol group The molar ratio with the hydroxyl group in the contained compound (j) is preferably 0.3 <[(a) + (b)] / [(g) + (j)] <1.0, more preferably 0. .5 <[(a) + (b)] / [(g) + (j)] <1.0, most preferably 0.6 <[(a) + (b)] / [(g) + ( j)] <0.8. If it is 0.3 or less, there may be fewer acid anhydride residues as the pigment adsorbing part, and the acid value of the resin may also be lower. If it is 1.0 or more, unreacted acid anhydride groups May remain, resulting in poor storage stability.

  The reaction temperature is 80 ° C to 180 ° C, preferably 90 ° C to 160 ° C. When the reaction temperature is less than 80 ° C., the reaction rate is slow. When the reaction temperature exceeds 180 ° C. or more, the carboxyl group undergoes an esterification reaction, which may cause a decrease in acid value or gelation. Ideally, the reaction is stopped until the absorption of the acid anhydride is eliminated by infrared absorption, but when the acid value falls within the range of 5 to 200 mgKOH / g, or the hydroxyl value is 20 to 200 mgKOH / g. The reaction may be stopped when entering the range of g.

  Next, the ethylenically unsaturated monomer (e) having no hydroxyl group and the ethylenically unsaturated monomer having a hydroxyl group using the remaining thiol groups of the compounds (h1) to (h3) as chain transfer agents The second step of producing the hydroxyl group-containing compounds (k1) to (k3) in which the vinyl polymer portion B having a hydroxyl group is introduced by radical polymerization of (f) will be described. By copolymerizing the ethylenically unsaturated monomer (f) having a hydroxyl group in the second step, a hydroxyl group can be introduced into the vinyl polymer portion B of the dispersant, and one isocyanate is obtained in the third step. It can be reacted with a compound (i) having a group and one or more (meth) acryloyl groups.

Examples of the ethylenically unsaturated monomer (e) having no hydroxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl ( (Meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2,2,4-trimethylcyclohexyl (meth) acrylate, stearyl (meth) acrylate Alkyl (meth) acrylates such as lauryl (meth) acrylate and isobornyl (meth) acrylate;
Aromatic (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate;
Heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate;
(N-substituted) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine ( (Meth) acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate;
Nitriles such as (meth) acrylonitrile are exemplified.

  As monomers that can be used in combination with the above acrylic monomers, styrenes such as styrene, α-methylstyrene, and indene, and vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether And fatty acid vinyls such as vinyl acetate and vinyl propionate.

  Moreover, a carboxyl group-containing ethylenically unsaturated monomer can be used in combination. As the carboxyl group-containing ethylenically unsaturated monomer, one or more kinds can be selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like.

  In the resin-type dispersant (C), among the ethylenically unsaturated monomers (e) not having a hydroxyl group exemplified above, a monomer represented by the following general formula (5) is used. It is preferable in terms of dispersibility.

[In General Formula (5), R ⁵² represents a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic alkyl group having 6 to 15 carbon atoms. ]

  As the ethylenically unsaturated monomer (f) having a hydroxyl group, any monomer having a hydroxyl group and having an ethylenically unsaturated double bond may be used. (Meth) acrylate monomers having a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) acrylate And hydroxyalkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate, and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate, or (meth) acrylamide monomers having a hydroxyl group, such as N- (2-hydroxyethyl) (meth) acrylamide, N N- (hydroxyalkyl) (meth) acrylamide such as (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) acrylamide, or vinyl ether monomers having a hydroxyl group, such as 2 -Hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, hydroxyalkyl vinyl ethers such as 2- (or 3- or 4-) hydroxybutyl vinyl ether, or allyl ether monomers having a hydroxyl group, such as 2- Examples include hydroxyalkyl allyl ethers such as hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, and 2- (or 3- or 4-) hydroxybutyl allyl ether.

  Also obtained by adding alkylene oxide and / or lactone to the above hydroxyalkyl (meth) acrylate, alkyl-α-hydroxyalkyl acrylate, N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl vinyl ether or hydroxyalkylallyl ether. The ethylenically unsaturated monomer obtained can also be used as the ethylenically unsaturated monomer (f) having a hydroxyl group in the method of the present invention. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and a combination system of two or more thereof are used. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. As the lactone to be added, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more of these are used. What added both alkylene oxide and lactone may be used.

  In the second step of the resin type dispersant (C), the compounds (h1) to (h3) are mixed with the ethylenically unsaturated monomer (e) and the molecular weight of the target vinyl polymer part B. Hydroxyl-containing compounds (k1) to (k3) in which a vinyl polymer part B having a hydroxyl group is introduced by mixing and heating an ethylenically unsaturated monomer (f) having a hydroxyl group and a polymerization initiator. Can be manufactured. Preferably, 10 to 300 parts by weight of the compounds (h1) to (h3) are added to 100 parts by weight of the ethylenically unsaturated monomer (e) and the ethylenically unsaturated monomer (f) having a hydroxyl group. Used for bulk polymerization or solution polymerization. The reaction temperature is 40 to 150 ° C., preferably 50 to 110 ° C., and the reaction time is 3 to 30 hours, preferably 5 to 20 hours.

  During polymerization, 0.001 to 5 parts by weight of a polymerization initiator is arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer (e) and the ethylenically unsaturated monomer (f) having a hydroxyl group. can do. As the polymerization initiator, azo compounds and organic peroxides can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.

  In the case of solution polymerization, as a polymerization solvent, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, etc. are used, but are not particularly limited thereto. It is not a thing. These polymerization solvents may be used as a mixture of two or more.

  Next, the reaction between the hydroxyl group-containing compounds (k1) to (k3) and the compound (i) having one isocyanate group and one or more (meth) acryloyl groups in the third step will be described. The dispersant of the present invention reacts the hydroxyl group in the hydroxyl group-containing compounds (k1) to (k3) with the isocyanate group in the compound (i) having one isocyanate group and one or more (meth) acryloyl groups. Is obtained. Thereby, a (meth) acryloyl group can be arbitrarily introduced mainly into the vinyl polymer part B in the dispersant, and a curable dispersant having curability at the solvent affinity site can be obtained.

The compound (i) having one isocyanate group and one or more (meth) acryloyl groups used in the third step is a compound having one isocyanate group and one or two (meth) acryloyl groups. Specifically, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate are preferable.
The compound (i) having one isocyanate group and one or more (meth) acryloyl groups used in the present invention is not limited to the compounds exemplified above, and may have an isocyanate group and one or more (meth) acryloyl groups. Any structure is acceptable. These may be used alone or in combination.

The molar ratio of the hydroxyl group in the hydroxyl group-containing compounds (k1) to (k3) to the isocyanate group in the compound (i) having one isocyanate group and one or more (meth) acryloyl groups is determined by the hydroxyl group-containing compound (k1). ) To (k3) with respect to 1 mol of hydroxyl group, the isocyanate group in compound (i) having one isocyanate group and one or more (meth) acryloyl groups is 0.2 to 1.0 mol. Is more preferably 0.3 to 1.0 mol, and most preferably 0.5 to 1.0 mol. If the amount is less than 0.2 mol, the amount of (meth) acryloyl groups may be reduced, so that the curability may be insufficient. If the amount exceeds 1.0 mol, unreacted isocyanate groups are present in the resin. It may remain and storage stability may deteriorate.
The reaction temperature is 50 ° C to 150 ° C, preferably 70 ° C to 120 ° C. When the reaction temperature is less than 50 ° C., the reaction rate is slow, and when it exceeds 150 ° C., the urethane group produced by the reaction is decomposed.

The resin-type dispersant (C) can be produced using only the raw materials listed so far, but it is preferable to use a solvent in order to avoid problems such as high viscosity and non-uniform reaction. As the solvent to be used, known solvents can be used. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile and the like can be mentioned. The solvent used for the reaction can be removed by an operation such as distillation after the completion of the reaction, or can be used as a part of the product as it is.
The weight average molecular weight of the obtained dispersant is preferably 2,000 to 100,000. If the weight average molecular weight is less than 2,000, the stability of the pigment composition may decrease, and if it exceeds 100,000, the interaction between the resins may become strong and the viscosity of the pigment composition may increase. . Further, the acid value of the obtained dispersant is preferably 5 to 200 mgKOH / g. More preferably, it is 5-150 mgKOH / g, Most preferably, it is 5-100 mgKOH / g. When the acid value is less than 5 mgKOH / g, the pigment adsorbing ability may be lowered and there may be a problem in pigment dispersibility. When the acid value exceeds 200 mgKOH / g, the interaction between resins becomes strong and the viscosity of the pigment dispersion composition increases. There is a case.

<Surfactant>
The coloring composition of the present invention may contain a surfactant.
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When the surfactant is added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the pigment. When the blending amount of the surfactant is within this range, the dispersibility and stability can be improved.

<Solvent (D)>
In the colored composition of the present invention, a pigment is sufficiently dispersed and permeated in a pigment carrier, and applied to a substrate such as a glass substrate so that a dry film thickness is 0.2 to 5 μm to form a filter segment. In order to make it easy to do, a solvent (D) is contained. The solvent (D) is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the solvent (D) include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4 -Dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m- Xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N -Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene , Tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether , Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Chill isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

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

  Moreover, since the solvent (D) can adjust the coloring composition to an appropriate viscosity and can form a filter segment having a desired uniform film thickness, it is 500 to 4000 parts by weight with respect to 100 parts by weight of the pigment (A). It is preferable to use it in an amount.

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

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the pigment (A), and 10 to 300 parts by weight from the viewpoint of photocurability and developability. More preferred.

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

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

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

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

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

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

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

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

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

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

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

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di ( , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy)- Benzene, phosphorous acid ethyl 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.

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

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

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

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

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

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

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the colored composition because the brightness and sensitivity are good.

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

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

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

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

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

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

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

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

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

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

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

<Method for producing colored composition>
In the coloring composition of the present invention, the pigment (A) is preferably incorporated into a dye carrier such as the binder resin (B) and / or the solvent (D), preferably a resin-type dispersant (C), a dye derivative, or a surfactant. Etc., and finely dispersed using various dispersing means such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor ( Pigment dispersion). At this time, two or more kinds of pigments may be simultaneously dispersed in the dye carrier, or those separately dispersed in the dye carrier may be mixed.
The resin-type dispersant (D) may be added in its entirety at the stage of dispersing the pigment, and is added to the prepared colored composition later to form the binder resin (B) and the resin-type dispersant (C). You may adjust so that the amount of double bonds of a resin component may be 0.3-5 mmol / g.

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

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. Coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention is provided with a filter segment formed on the base material from the coloring composition for a color filter of the present invention, and a general color filter has at least one red filter segment, at least one. One green filter segment and at least one blue filter segment. The color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

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

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

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

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

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

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

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

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

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

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

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

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

  First, the binder resin solution, the resin-type dispersant solution, and the method for producing the fine pigment used in Examples and Comparative Examples will be described.

<Method for producing binder resin solution>
(Binder resin solution (B1))
560 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 22.0 parts of methacrylic acid, 22.0 parts of n-butyl methacrylate, 2-hydroxyethyl methacrylate 104. A polymerization reaction was carried out by dropping a mixture of 0 part and 4.0 part of 2,2′-azobisisobutyronitrile over 1 hour. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained.
Next, a mixture of 33.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate and 130.0 parts of cyclohexanone was added to 338 parts of the obtained transparent resin solution at 70 ° C. over 3 hours. The solution was dropped to obtain a photosensitive transparent resin solution. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Thus, cyclohexanone was added to obtain a binder resin solution (B1). The weight average molecular weight Mw of the obtained resin was 20000, and the double bond equivalent was 470.

(Binder resin solution (B2))
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone are put into 9.3 parts of acrylic acid (100% of glycidyl group) and the container is placed at 120 ° C. The reaction was continued for 6 hours, and when the acid value of the solid content reached 0.5, the reaction was terminated to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a photosensitive transparent resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. A binder resin solution (B2) was obtained. The weight average molecular weight (Mw) of the obtained resin was 19000, and the double bond equivalent was 402.

(Binder resin solution (B3))
480 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 32.0 parts of methacrylic acid, 24.0 parts of methyl methacrylate, 16.0 parts of n-butyl methacrylate, 29.0 parts of benzyl methacrylate, 19.0 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 15.0 parts of glycerol monomethacrylate, 2,2′-azobisisobutyronitrile 4 0.0 part of the mixture was added dropwise over 1 hour to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 80 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained.
Next, with respect to 445 parts of the obtained transparent resin solution, a mixture of 14.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate and 55.0 parts of cyclohexanone was added at 70 ° C. over 3 hours. The solution was dropped to obtain a photosensitive transparent resin solution. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The previously synthesized photosensitive transparent resin solution has a non-volatile content of 20% by weight. Thus, cyclohexanone was added to obtain a binder resin solution (B3). The weight average molecular weight Mw of the obtained resin was 21000, and the double bond equivalent was 1000.

(Binder resin solution (B4))
70 parts of cyclohexanone is put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 14.4 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 3. A mixture of 2 parts, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) and 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. The polymerization reaction was carried out. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A photosensitive transparent resin solution was obtained.
After cooling to room temperature, about 2 g of the non-photosensitive transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The non-photosensitive transparent resin solution synthesized earlier had a non-volatile content of 20% by weight. Cyclohexanone was added so that a binder resin solution (B4) was obtained. The weight average molecular weight Mw of the obtained resin was 25000.

<Method for Producing Resin Type Dispersant Solution>
(Resin Dispersant Solution (C1))
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 87 parts of 1-thioglycerol, 24 parts of 1,6-hexanediol, 235 parts of 3,3 ′, 4,4′-biphenyltricarboxylic acid anhydride, After 650 parts of PGMAC and 0.2 part of monobutyltin oxide as a catalyst were substituted with nitrogen gas, the reaction was carried out at 120 ° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 523 parts in terms of solid content, 100 parts of 2-hydroxypropyl methacrylate, 50 parts of ethyl acrylate, 300 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, 200 parts of benzyl methacrylate, 50 parts of acid and 663 parts of PGMAC were charged, the inside of the reaction vessel was heated to 80 ° C., 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and reacted for 12 hours (second) Process). It was confirmed that 95% had reacted by solid content measurement. Finally, 500 parts of a 50% PGMAC solution of the compound obtained in the second step, 31.0 parts of 2-acryloyloxyethyl isocyanate (AOI) and 0.1 part of hydroquinone were charged, and 2270 cm based on isocyanate groups by IR. The reaction was continued until the disappearance of the -1 peak was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the solid content was adjusted with PGMAC to obtain a resin-type dispersant solution (C1) having a solid content of 50%. The obtained dispersant had an acid value of 118 mgKOH / g, a double bond equivalent of 1274, and a weight average molecular weight of 7,000.

(Resin Dispersant Solution (C2))
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 108 parts of 1-thioglycerol, 174 parts of pyromellitic acid anhydride, 650 parts of PGMAC, and 0.2 part of monobutyltin oxide as a catalyst. After the substitution, the reaction was carried out at 120 ° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate Part, 50 parts of methacrylic acid and 663 parts of PGMAC, the inside of the reaction vessel was heated to 80 ° C., 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and reacted for 12 hours. (Second step). It was confirmed that 95% had reacted by solid content measurement. Finally, 500 parts of a 50% PGMAC solution of the compound obtained in the second step, 54.0 parts of 2-methacryloyloxyethyl isocyanate (MOI) and 0.1 part of hydroquinone were charged, and 2270 cm based on isocyanate groups by IR. The reaction was continued until the disappearance of the -1 peak was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the solid content was adjusted with PGMAC to obtain a resin-type dispersant solution (C2) having a solid content of 50%. The obtained dispersant had an acid value of 62 mgKOH / g, a double bond equivalent of 874, and a weight average molecular weight of 13,000.

(Resin Dispersant Solution (C3))
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 287 parts of 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 650 parts of PGMAC, and catalyst After charging 0.2 parts of monobutyltin oxide and replacing with nitrogen gas, the mixture was reacted at 120 ° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 246 parts in terms of solid content of the compound obtained in the first step, 100 parts of 2-hydroxybutyl methacrylate, 50 parts of hydroxybutyl vinyl ether, 200 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, methyl methacrylate 200 parts, 200 parts of n-butyl methacrylate, 50 parts of methacrylic acid and 663 parts of PGMAC are charged, the inside of the reaction vessel is heated to 80 ° C., and 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) And reacted for 12 hours (second step). It was confirmed that 95% had reacted by solid content measurement. Finally, 500 parts of a 50% PGMAC solution of the compound obtained in the second step, 16.0 parts of 1,1-bis (acryloyloxymethyl) ethyl isocyanate (BEI), and 0.1 part of hydroquinone were charged to IR. The reaction was continued until the disappearance of the peak at 2270 cm −1 based on the isocyanate group was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the solid content was adjusted with PGMAC to obtain a resin-type dispersant solution (C3) having a solid content of 50%. The obtained dispersant had an acid value of 82 mgKOH / g, a double bond equivalent of 573, and a weight average molecular weight of 13,000.

(Resin Dispersant Solution (C4)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 87 parts of 1-thioglycerol, 24 parts of 1,6-hexanediol, 235 parts of 3,3 ′, 4,4′-biphenyltricarboxylic acid anhydride, After 650 parts of PGMAC and 0.2 part of monobutyltin oxide as a catalyst were substituted with nitrogen gas, the reaction was carried out at 120 ° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 15 parts of the compound obtained in the first step in terms of solid content, 100 parts of 2-hydroxypropyl methacrylate, 50 parts of ethyl acrylate, 300 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, 250 parts of benzyl methacrylate, PGMAC663 Then, the inside of the reaction vessel was heated to 80 ° C., and 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted for 12 hours (second step). It was confirmed that 95% had reacted by solid content measurement. Finally, 500 parts of a 50% PGMAC solution of the compound obtained in the second step, 24.0 parts of 2-acryloyloxyethyl isocyanate (AOI) and 0.1 part of hydroquinone were charged, and 2270 cm based on isocyanate groups by IR. The reaction was continued until the disappearance of the -1 peak was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the solid content was adjusted with PGMAC to obtain a resin-type dispersant solution (C4) having a solid content of 50%. The obtained dispersant had an acid value of 4 mgKOH / g, a double bond equivalent of 1609, and a weight average molecular weight of 86000.

(Resin Dispersant Solution (C5)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 87 parts of 1-thioglycerol, 24 parts of 1,6-hexanediol, 235 parts of 3,3 ′, 4,4′-biphenyltricarboxylic acid anhydride, After 650 parts of PGMAC and 0.2 part of monobutyltin oxide as a catalyst were substituted with nitrogen gas, the reaction was carried out at 120 ° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 523 parts in terms of solid content, 100 parts of 2-hydroxypropyl methacrylate, 50 parts of ethyl acrylate, 250 parts of methyl methacrylate, 200 parts of benzyl methacrylate, 400 parts of methacrylic acid, 663 parts of PGMAC Was heated to 80 ° C., and 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted for 12 hours (second step). It was confirmed that 95% had reacted by solid content measurement. Finally, 500 parts of a 50% PGMAC solution of the compound obtained in the second step, 31.0 parts of 2-acryloyloxyethyl isocyanate (AOI) and 0.1 part of hydroquinone were charged, and 2270 cm based on isocyanate groups by IR. The reaction was continued until the disappearance of the -1 peak was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the solid content was adjusted with PGMAC to obtain a resin-type dispersant solution (C5) having a solid content of 50%. The obtained dispersant had an acid value of 232 mg KOH / g, a double bond equivalent of 1274, and a weight average molecular weight of 7,000.

(Resin Dispersant Solution (C6)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 87 parts of 1-thioglycerol, 24 parts of 1,6-hexanediol, 235 parts of 3,3 ′, 4,4′-biphenyltricarboxylic acid anhydride, After 650 parts of PGMAC and 0.2 part of monobutyltin oxide as a catalyst were substituted with nitrogen gas, the reaction was carried out at 120 ° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 12 parts of the compound obtained in the first step, 100 parts of 2-hydroxypropyl methacrylate, 50 parts of ethyl acrylate, 300 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, 200 parts of benzyl methacrylate, methacrylic methacrylate, 50 parts of acid and 663 parts of PGMAC were charged, the inside of the reaction vessel was heated to 80 ° C., 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and reacted for 12 hours (second) Process). It was confirmed that 95% had reacted by solid content measurement. Finally, 500 parts of a 50% PGMAC solution of the compound obtained in the second step, 24.0 parts of 2-acryloyloxyethyl isocyanate (AOI) and 0.1 part of hydroquinone were charged, and 2270 cm based on isocyanate groups by IR. The reaction was continued until the disappearance of the -1 peak was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the solid content was adjusted with PGMAC to obtain a resin-type dispersant solution (C6) having a solid content of 50%. The obtained dispersant had an acid value of 32 mgKOH / g, a double bond equivalent of 1609, and a weight average molecular weight of 108,000.

(Resin Dispersant Solution (C7)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 87 parts of 1-thioglycerol, 24 parts of 1,6-hexanediol, 147 parts of 3,3 ′, 4,4′-biphenyltricarboxylic acid anhydride, After 650 parts of PGMAC and 0.2 part of monobutyltin oxide as a catalyst were substituted with nitrogen gas, the reaction was carried out at 120 ° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 523 parts in terms of solid content, 100 parts of 2-hydroxypropyl methacrylate, 50 parts of ethyl acrylate, 300 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, 200 parts of benzyl methacrylate, 50 parts of acid and 663 parts of PGMAC were charged, the inside of the reaction vessel was heated to 80 ° C., 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and reacted for 12 hours (second) Process). It was confirmed that 95% had reacted by solid content measurement. Finally, 500 parts of a 50% PGMAC solution of the compound obtained in the second step, 60.0 parts of 2-acryloyloxyethyl isocyanate (AOI) and 0.1 part of hydroquinone were charged, and 2270 cm based on isocyanate groups by IR. The reaction was continued until the disappearance of the -1 peak was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the solid content was adjusted with PGMAC to obtain a resin-type dispersant solution (C7) having a solid content of 50%. The obtained dispersant had an acid value of 78 mgKOH / g, a double bond equivalent of 729, and a weight average molecular weight of 1800.

(Resin Dispersant Solution (C8)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 87 parts of 1-thioglycerol, 24 parts of 1,6-hexanediol, 235 parts of 3,3 ′, 4,4′-biphenyltricarboxylic acid anhydride, After 650 parts of PGMAC and 0.2 part of monobutyltin oxide as a catalyst were substituted with nitrogen gas, the reaction was carried out at 120 ° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 15 parts of the compound obtained in the first step in terms of solid content, 100 parts of 2-hydroxypropyl methacrylate, 50 parts of ethyl acrylate, 300 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, 250 parts of benzyl methacrylate, methacrylic acid 8 parts of acid and 663 parts of PGMAC were charged, the inside of the reaction vessel was heated to 80 ° C., 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and reacted for 12 hours (second) Process). It was confirmed that 95% had reacted by solid content measurement. Finally, 500 parts of a 50% PGMAC solution of the compound obtained in the second step, 24.0 parts of 2-acryloyloxyethyl isocyanate (AOI) and 0.1 part of hydroquinone were charged, and 2270 cm based on isocyanate groups by IR. The reaction was continued until the disappearance of the -1 peak was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the solid content was adjusted with PGMAC to obtain a resin-type dispersant solution (C8) having a solid content of 50%. The obtained dispersant had an acid value of 8 mgKOH / g, a double bond equivalent of 1609, and a weight average molecular weight of 86000.

(Resin Dispersant Solution (C9)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 87 parts of 1-thioglycerol, 24 parts of 1,6-hexanediol, 235 parts of 3,3 ′, 4,4′-biphenyltricarboxylic acid anhydride, After 650 parts of PGMAC and 0.2 part of monobutyltin oxide as a catalyst were substituted with nitrogen gas, the reaction was carried out at 120 ° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 15 parts of the compound obtained in the first step in terms of solid content, 100 parts of 2-hydroxypropyl methacrylate, 50 parts of ethyl acrylate, 300 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, 250 parts of benzyl methacrylate, methacrylic acid 300 parts of acid and 663 parts of PGMAC were charged, the inside of the reaction vessel was heated to 80 ° C., 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and reacted for 12 hours (second) Process). It was confirmed that 95% had reacted by solid content measurement. Finally, 500 parts of a 50% PGMAC solution of the compound obtained in the second step, 24.0 parts of 2-acryloyloxyethyl isocyanate (AOI) and 0.1 part of hydroquinone were charged, and 2270 cm based on isocyanate groups by IR. The reaction was continued until the disappearance of the -1 peak was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the solid content was adjusted with PGMAC to obtain a resin-type dispersant solution (C9) having a solid content of 50%. The obtained dispersant had an acid value of 179 mgKOH / g, a double bond equivalent of 1609, and a weight average molecular weight of 86000.

(Resin Dispersant Solution (C10))
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 108 parts of 1-thioglycerol, 174 parts of pyromellitic acid anhydride, 650 parts of PGMAC, and 0.2 part of monobutyltin oxide as a catalyst. After the substitution, the reaction was carried out at 120 ° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate Part, 50 parts of methacrylic acid and 663 parts of PGMAC, the inside of the reaction vessel was heated to 80 ° C., 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and reacted for 12 hours. (Second step). It was confirmed that 95% had reacted by solid content measurement. A resin type dispersant solution (C10) having a solid content of 50% was obtained by adjusting the solid content with PGMAC. The obtained dispersant had an acid value of 75 mgKOH / g and a weight average molecular weight of 12,000.

The acid value (mgKOH / g), double bond equivalent, and weight average molecular weight of the resin-type dispersant are summarized in Table 1.

<Production method of fine pigment>
(Red refined pigment (R-1))
Diketopyrrolopyrrole red pigment C.I. I. 120 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by Ciba Japan Co., Ltd.), 1000 parts of crushed salt and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. The mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 115 parts of red A refined pigment (R-1) was obtained. The average primary particle size was 24.8 nm.

(Green refined pigment (G-1))
Halogenated zinc phthalocyanine pigment C.I. I. 120 parts of Pigment Green 58 (“FASTGEN Green A110” manufactured by DIC), 1000 parts of crushed salt and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. Add to 2000 parts of warm water, stir for 1 hour while heating to 80 ° C. to form a slurry, filter and wash repeatedly to remove salt and solvent, then dry at 80 ° C. overnight, 115 parts of green refined pigment (G-1) was obtained, and the average primary particle size was 30.0 nm.

[Example 1]
(Coloring composition for red color filter (DR-1))
After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A red pigment dispersion 1 was prepared.

-Red fine pigment (R-1) 11.0 parts diketopyrrolopyrrole pigment (CI Pigment Red 254)
Pigment derivative: Compound 3 1.0 part
Binder resin solution (B1) (nonvolatile content 20%) 16.0 parts Resin-type dispersant solution (C1) (nonvolatile content 50%) 9.6 parts Solvent 62.4 parts Propylene glycol monomethyl ether acetate (PGMAC)

Next, the mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a colored composition for red color filter (DR-1).

・ Red pigment dispersion 1 52.0 parts ・ Photopolymerizable monomer 4.0 parts (“NK ESTER ATMPT” trimethylolpropane triacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.)
-Photopolymerization initiator 3.4 parts ("Irgacure 907" 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one manufactured by Ciba Geigy)
・ Sensitizer 0.4 part (“EAB-F” 4,4′-bis (diethylamino) benzophenone manufactured by Hodogaya Chemical Co., Ltd.)
・ Solvent 40.2 parts Propylene glycol monomethyl ether acetate (PGMAC)

[Examples 2 to 13, Comparative Examples 1 to 4]
(Coloring composition for red color filter (DR-2 to 13, DR-C1 to C4))
In the same manner as in Example 1 (red pigment dispersion (CR-1)), the pigment, pigment derivative, binder resin solution, resin-type dispersant, and solvent shown in Table 2 are shown in Table 2 in parts (parts by weight). Blended and dispersed to produce red pigment dispersions CR-2 to 13 and comparative red pigment dispersions CR-C1 to C4, and the same as Example 1 (coloring composition for red color filter (DR-1)) The coloring composition for red color filters (DR-2 to 13) and the coloring composition for comparative red color filter (DR-C1 to C4) were obtained.

[Example 14]
(Coloring composition for green color filter (DG-1))
After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A green pigment dispersion 1 was prepared.

Green refined pigment (G-1) 12.0 parts Zinc halide phthalocyanine pigment (CI Pigment Green 58)
Binder resin solution (B1) (nonvolatile content 20%) 16.0 parts Resin-type dispersant solution (C2) (nonvolatile content 50%) 9.6 parts Solvent 62.4 parts Propylene glycol monomethyl ether acetate (PGMAC)

Next, the mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a colored composition for green color filter (DG-1).

-52.0 parts of green pigment dispersion 1-4.8 parts of photopolymerizable monomer ("NK ester ATMPT" trimethylolpropane triacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator 2.8 parts (“Irgacure 907” 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one manufactured by Ciba Geigy)
・ Sensitizer 0.2 part (“EAB-F” 4,4′-bis (diethylamino) benzophenone manufactured by Hodogaya Chemical Co., Ltd.)
・ Solvent 40.2 parts Propylene glycol monomethyl ether acetate (PGMAC)

[Examples 11 and 12]
(Coloring composition for green color filter (DG-2, 3, DG-C1 to C3))
In the same manner as in Example 7 (green pigment dispersion (CG-1)), the pigment, binder resin, resin dispersant, and solvent shown in Table 2 were blended and dispersed in the proportions (parts by weight) shown in Table 2. Thus, green pigment dispersions 2 and 3 were prepared, and a green color filter coloring composition (DG-2, 3) was obtained in the same manner as in Example 14 (green color filter coloring composition (DG-1)). It was.

<Evaluation of coloring composition>
Evaluation of the viscosity, stability over time, and solvent resistance of the coating film produced using the obtained colored composition was performed by the following methods. Table 3 shows the evaluation results.

(1) Viscosity measurement About the coloring composition for color filters obtained in Examples and Comparative Examples, using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd. under the condition of a rotation speed of 20 rpm at 25 ° C. Measured with

(2) Evaluation of stability over time After the color composition for color filter obtained was stored in a thermostat at 40 ° C. for 1 week and accelerated over time, the viscosity of the color composition for color filter after time elapsed was (1) It was measured by the same method as “viscosity measurement” and the rate of change in viscosity before and after storage at 40 ° C. for 1 week was calculated and evaluated in three stages according to the following criteria.

[Viscosity change rate] = (viscosity with time−initial viscosity) / initial viscosity × 100 (%)

○: When the viscosity change rate is within ± 10% and no sediment is formed.
Δ: When precipitates are formed even when the rate of change in viscosity is within 10%.
×: When the viscosity change rate exceeds ± 10%.

(3) Evaluation of solvent resistance Rotational speed at which the colored composition for color filter obtained in Examples and Comparative Examples is dried on a 100 mm × 100 mm, 0.7 mm thick glass substrate to 2.0 μm. The substrate coated with a spin coater at 100 ° C. was dried at 100 ° C. for 100 minutes, and then exposed to ultraviolet light using an ultrahigh pressure mercury lamp at a light amount of 40 mJ, and unexposed with a 0.2 wt% potassium hydroxide aqueous solution at 23 ° C. The filter segment was washed away and baked in a hot air oven at 230 ° C. for 20 minutes to form a filter segment. The obtained filter segment was cut into 1 cm × 5 cm, immersed in 16 g of NMP (N-methylpyrrolidone) at 80 ° C. for 40 minutes, and then pigmented using a spectrophotometer (Hitachi Instrument Service Co., Ltd. “U-3300 type”). The absorbance of the NMP solution eluted with was measured and evaluated in three stages.
In addition, about the red coloring composition, it determined in accordance with the following reference | standard by the absorbance value of the peak value in wavelength 450nm, and the green coloring composition by the absorbance value of peak value in wavelength 550nm.

○: Less than 1.5, good solvent resistance Δ: 1.5 or less, less than 3.0, slightly inferior in solvent resistance ×: 3.0 or more, poor solvent resistance

  The colored compositions for color filters obtained in Examples 1 to 16 are superior in stability over time as compared with those obtained in Comparative Examples 1 to 4 and also have excellent solvent resistance. Had. Among these, the colored filter coloring compositions obtained in Examples 1 to 6, 8 to 9, and 14 to 16 had a low initial viscosity and particularly good solvent resistance.

  In addition, the colored composition of Comparative Example 4 had an initial viscosity that was too high to evaluate the solvent resistance.

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

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

Red pigment (CI Pigment Red 254) 9.6 parts Red Pigment (CI Pigment Red 177) 2.4 parts Resin-type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Binder resin Solution (B4) 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

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

Red coloring composition 1 42.0 parts Binder resin solution (B1) 13.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (manufactured by Ciba Japan “ Irgacure 907 ") 2.0 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 39.6 parts

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

Blue pigment (CI Pigment Blue 15: 6) 7.2 parts Purple Pigment (CI Pigment Violet 23) 4.8 parts Resin Type Dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Binder resin solution (B4) 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

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

Blue coloring composition 1 34.0 parts Binder resin solution (B1) 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (manufactured by Ciba Japan Co., Ltd.) Irgacure 907 ") 2.0 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 45.1 parts

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

By using the coloring composition for a color filter of the present invention, the brightness of the color filter can be increased, and other physical properties can be suitably used without any problem.

Claims (10)

  A coloring composition for a color filter comprising a pigment (A), a binder resin (B), a resin type dispersant (C), and a solvent (D), wherein the resin type dispersant (C) is (meth) Coloring for color filters characterized by having a double bond amount of a resin component having an acryloyl group and comprising a binder resin (B) and a resin-type dispersant (C) of 0.3 to 5 mmol / g Composition.   The binder resin (B) has an ethylenically unsaturated double bond, and the double bond amount of the binder resin (B) is 0.2 to 2 mmol / g. Coloring compositions for color filters.   The coloring composition for a color filter according to claim 1 or 2, wherein the acid value of the resin-type dispersant (C) is 5 to 200 mgKOH / g.   The colored composition for a color filter according to any one of claims 1 to 3, wherein the resin type dispersant (C) has a weight average molecular weight of 2,000 to 100,000.   The resin-type dispersant (C) comprises an acid anhydride group in one or more acid anhydrides selected from tetracarboxylic acid anhydride (a) and tricarboxylic acid anhydride (b), two hydroxyl groups in the molecule and one Polyester part (C1) having a carboxyl group obtained by reacting a hydroxyl group in the compound (g) having a thiol group, an ethylenically unsaturated monomer (e) having no hydroxyl group, and an ethylenic group having a hydroxyl group A vinyl polymer part (C2) obtained by radical polymerization of an unsaturated monomer (f), and the vinyl polymer (C2) part has a (meth) acryloyl group. The coloring composition for color filters of any one.   The coloring composition for a color filter according to any one of claims 1 and 3, wherein the double bond amount of the resin-type dispersant (C) is 0.3 to 3.3 mmol / g.   The coloring composition for a color filter according to any one of claims 1 to 6, wherein the pigment (A) contains a diketopyrrolopyrrole pigment having an average primary particle diameter of 10 to 40 nm.   The coloring composition for a color filter according to any one of claims 1 to 6, wherein the pigment (A) contains a zinc halide phthalocyanine pigment having an average primary particle diameter of 10 to 40 nm.   Furthermore, the coloring composition for color filters of any one of Claim 1 thru | or 8 containing a photopolymerizable monomer and / or a photoinitiator.   A color filter comprising a filter segment formed from the colored composition for color filter according to any one of claims 1 to 9 on a substrate.