JP2011057909A - Coloring composition, photosensitive coloring composition for color filter, and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring composition excellent in heat resistance and light resistance, satisfying color density, color purity, and transparency, containing no halogen atom or, if contained, traces thereof dealing with issues of safety and health, and environmental pollution; to provide a photosensitive coloring composition for color filters using the coloring composition, and a color filter. <P>SOLUTION: This coloring composition includes at least a thermoplastic resin (A) and a colorant (B) containing aluminum phthalocyanine pigment, where the glass transition temperature (Tg) of the thermoplastic resin (A) is 70-170°C. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a coloring composition, a photosensitive coloring composition for a color filter, and a color filter. The coloring composition of the present invention can be used as ink and paint, gravure ink, various general paints for automobile, wood, metal, etc., back coat paint for magnetic tape, radiation cure ink, ink for ink jet printer It can be used for applications such as color filter inks. Moreover, the photosensitive coloring composition for color filters of this invention can be used especially for the filter segment of the color filter for liquid crystal display devices, and for the filter segment of the color filter for solid-state image sensors.
Furthermore, the coloring composition of the present invention and the photosensitive coloring composition for a color filter do not contain a halogen atom or are contained in a very small amount. Useful for.

  In recent years, the development of environmentally friendly products with low environmental impact has been actively promoted, and more stringent standards have been set accordingly. Halogen atoms are one of the chemical substances that are desired to be removed as environmentally friendly products. Currently used green colorants such as prints and colorants are generally mixed colors of colorants centered on halogenated phthalocyanine represented by high chlorinated phthalocyanine green, which is not a problem with current standards. . It is no exaggeration to say that halogenated phthalocyanine pigments have a large amount of halogen atoms in the pigment structure, and that there is no green color that does not contain any halogen atoms in the pigment or pigment composition. Therefore, development of products that meet new standards is desired.

  Under these circumstances, a copper phthalocyanine blue pigment containing no halogen and a yellow high-grade pigment containing no halogen are mixed and co-dispersed to obtain the desired green hue and to have light resistance and heat resistance. Attempts have also been made, but the hue is unclear only by co-dispersion by simple color mixing, especially in tests when using ink and paint, "white blur" is a problem, only the pigment composition ratio and dispersion conditions Then, it is difficult to solve.

  Patent Document 1 discloses a pigment composition that maintains a clear hue, high light resistance, and high heat resistance by using a blue aluminum phthalocyanine pigment containing no halogen and a green pigment containing halogen. Yes.

  In addition, the color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are vertically and horizontally constant. It consists of things arranged in an array. The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  On the color filter used in the color liquid crystal display device, a transparent electrode for driving the liquid crystal is generally formed by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. Has been. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to perform the formation process at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.

  In recent years, the use of liquid crystal display devices has been extended to various monitors and TVs, and further improvement in color reproducibility has been demanded. In order to meet this demand, provision of a color filter with high color purity and high color density is expected.

  Patent Document 2 discloses a coloring composition for a green color filter segment. When an aluminum phthalocyanine pigment is used as a main pigment, high brightness can be obtained with high chromaticity even with a relatively small content, and color density, color purity, and transparency. A technology that balances the above is disclosed.

  However, conventionally used pigment compositions containing aluminum phthalocyanine pigments are difficult to maintain the pigment crystal system with respect to heat resistance at 200 ° C. or higher, preferably 230 ° C. or higher, which is required for color filter applications. There was a problem that the spectral shape changed. As a result, it is very difficult to obtain a color filter having excellent coloring power and lightness, and the tendency becomes more prominent as the area becomes lighter when a coating film is formed.

JP 2003-4930 A JP 2004-333817 A

The object of the present invention is excellent in heat resistance and light resistance, satisfying color density, color purity and transparency, and does not contain or contain halogen atoms corresponding to health and safety and environmental pollution problems. It is to provide a coloring composition which is very small.
Moreover, the further subject of this invention is providing the photosensitive coloring composition for color filters and color filter which used said coloring composition.

  The subject is a coloring composition containing at least a thermoplastic resin (A) and a colorant (B) containing an aluminum phthalocyanine pigment, wherein the glass transition temperature (Tg) of the thermoplastic resin (A) is: Solved by a colored composition that is 70-170 ° C.

（式中、Ｒ₁はＨまたはＣＨ₃、Ｒ₂は炭素数２または３のアルキレン基、Ｒ₃は水素、またはベンゼン環を含んでいてもよい炭素数１〜２０のアルキル基、ｎは、１〜１５の整数である。） In the present invention, the thermoplastic resin (A) is selected from the group consisting of acrylic acid, methacrylic acid, methyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, and a monomer represented by the following formula (1). It is resin which has a structural unit derived from the at least 2 or more types of monomer chosen, It is related with the said coloring composition characterized by the above-mentioned.
Formula (1)

Wherein R ₁ is H or CH ₃ , R ₂ is an alkylene group having 2 or 3 carbon atoms, R ₃ is hydrogen, or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring, n is It is an integer from 1 to 15.)

  In addition, the present invention relates to the colored composition, wherein the thermoplastic resin (A) is a resin further having a structural unit derived from an N-substituted maleimide monomer.

  Moreover, this invention relates to the said coloring composition characterized by containing a thermosetting compound (C) further.

  The present invention also relates to a photosensitive coloring composition for a color filter, characterized by comprising the coloring composition further containing a photopolymerization initiator (D) and / or a photopolymerizable composition (E).

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

The coloring composition of the present invention exhibits a clear color tone, a wide color display area, and a high coloring power. Thus, various general paints for gravure inks, automobiles, woods, metals, etc., magnetic tape backcoat paints, and radiations It can be provided for uses such as curing ink, ink for inkjet printers, and ink for color filters.
Further, the coloring composition of the present invention and the photosensitive coloring composition for a color filter do not contain a halogen atom or are contained in a very small amount. It is useful for applications.

Hereinafter, the present invention will be described in detail.
In the present application, the case where “(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.

The colored composition of the present invention is a colored composition containing at least a thermoplastic resin (A) and a colorant (B) containing an aluminum phthalocyanine pigment, wherein the glass transition temperature of the thermoplastic resin (A) ( Tg) is 70 to 170 ° C.
<Thermoplastic resin (A)>
Examples of the thermoplastic resin (A) of the present invention include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, poly Vinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin, etc. Can be mentioned.

  As the thermoplastic resin (A) of the present invention, any of the above thermoplastic resins can be used as long as the glass transition temperature (Tg) satisfies the range of 70 to 170 ° C. When used as a composition, the spectral transmittance is preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist, it is preferable to use the alkali-soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

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

  Energy ray curable resins having ethylenically unsaturated active double bonds include reactive substitution of isocyanate groups, aldehyde groups, epoxy groups, etc. on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, etc. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a group or cinnamic acid is used. In addition, polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer are 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 (A) having both alkali-soluble performance and energy ray curing performance is also preferable as the photosensitive coloring composition for color filters.

The following are mentioned as a monomer which comprises the said thermoplastic resin (A). 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 ethoxypolyethylene 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. Acrylamide styrene, or styrenes 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;
Examples include vinyl acetates and fatty acid vinyls such as vinyl propionate.
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- Phenylenedimaleimide, 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-succin Midyl-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.

  A carboxyl group-containing ethylenically unsaturated monomer can also be used. Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

  Moreover, a hydroxyl-containing ethylenically unsaturated monomer can also be used. Examples of the hydroxyl group-containing ethylenically unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, or cyclohexane. And hydroxyalkyl (meth) acrylates such as dimethanol mono (meth) acrylate. Also, polyether mono (meth) acrylates obtained by addition polymerization of the above hydroxyalkyl (meth) acrylates with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) ester mono (meth) acrylate added with (poly) 12-hydroxystearic acid and the like.

  A phosphoric ester group-containing ethylenically unsaturated monomer can also be used. As the phosphoric ester group-containing ethylenically unsaturated monomer, for example, a monomer that can be obtained by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid. Is mentioned.

（式中、Ｒ₁はＨまたはＣＨ₃、Ｒ₂は炭素数２または３のアルキレン基、Ｒ₃は水素、またはベンゼン環を含んでいてもよい炭素数１〜２０のアルキル基、ｎは、１〜１５の整数である。） As long as the glass transition temperature (Tg) satisfies the range of 70 ° C to 170 ° C, the thermoplastic resin (A) of the present invention can be used without any particular limitation on the type and number of these monomers. Particularly preferred examples include at least two monomers selected from the group consisting of acrylic acid, methacrylic acid, methyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, and a monomer represented by the following formula (1). It is a resin having a derived structural unit.
Use of a resin having a structural unit derived from these monomers is preferable because the heat resistance and light resistance of a colored composition containing an aluminum phthalocyanine pigment are improved.
Formula (1)

Wherein R ₁ is H or CH ₃ , R ₂ is an alkylene group having 2 or 3 carbon atoms, R ₃ is hydrogen, or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring, n is It is an integer from 1 to 15.)

In formula (1), the alkylene group R ₂ contains 2 to 3 carbon atoms. Moreover, although carbon number of the alkyl group of R < ₃ > is 1-20, More preferably, it is 1-10. When the carbon number of the alkyl group of R ₃ is 1 to 10, the alkyl group becomes an obstacle and suppresses the approach between the resins and promotes adsorption / orientation to the pigment, but when the carbon number exceeds 10, The steric hindrance effect becomes high and shows a tendency to prevent even the adsorption / orientation of the benzene ring to the pigment. This tendency becomes more prominent as the carbon chain length of the alkyl group of R ₃ becomes longer. When the carbon number exceeds 20, the adsorption / orientation of the benzene ring is extremely reduced. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso) propyl group.

  These compounds include phenolic ethylene oxide (EO) modified (meth) acrylate, paracumylphenol EO or propylene oxide (PO) modified (meth) acrylate, nonylphenol EO modified (meth) acrylate, nonylphenol PO modified ( And (meth) acrylate. Of these compounds, EO or PO-modified (meth) acrylate of paracumylphenol forms not only the π-electron effect of the benzene ring, but also its steric effect, and forms a better adsorption / orientation plane for the pigment. can do.

  Further, it preferably has a structural unit derived from an N-substituted maleimide, and among them, cyclohexylmaleimide, methylmaleimide, ethylmaleimide, and 1,2-bismaleimideethane are preferable from the viewpoint of heat resistance, and cyclohexylmaleimide is particularly preferable.

  The glass transition temperature (Tg) of the thermoplastic resin (A) in the present invention is 70 to 170 ° C. When the temperature is less than 70 ° C., the heat resistance and light resistance deteriorate, and when the temperature exceeds 170 ° C., when used as a photosensitive coloring composition for a color filter, it is not preferable in that the developability is remarkably lowered in the development process. A more preferable range of the glass transition temperature (Tg) of the thermoplastic resin (A) is 90 ° C. to 170 ° C., and the use of the thermoplastic resin (A) of 90 ° C. or higher is superior in heat resistance and light resistance. The effect can be confirmed.

The glass transition temperature (Tg) of the thermoplastic resin (A) is calculated based on the glass transition temperature (Tg ^m ) of the constituent components of the thermoplastic resin (A) and the weight ratio (W ^m ) of each component. The glass transition temperature (Tg) of the thermoplastic resin (A) is calculated by the following equation (2) Gordon-Taylor equation.
Formula (2) Tg = ΣTg ^m × W ^m

The weight average molecular weight (Mw) of the thermoplastic resin (A) is preferably in the range of 10,000 to 100,000, more preferably 30,000 to 80,000, in order to disperse the colorant (B) preferably. Range. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.
Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are connected to four separation columns in series in the gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corporation. This is a polystyrene equivalent molecular weight measured using “TSK-GEL SUPER H5000”, “H4000”, “H3000”, and “H2000” manufactured by the company and using tetrahydrofuran as the mobile phase.

  When the thermoplastic resin (A) is used as a photosensitive coloring composition for a color filter, from the viewpoint of pigment dispersibility, developability, and heat resistance, a carboxyl that acts as a pigment adsorbing group and an alkali-soluble group during development. The balance of aliphatic groups and aromatic groups acting as affinity groups for groups, pigment carriers and solvents is important for pigment dispersibility, developability, and durability, and a resin having an acid value of 20 to 300 mgKOH / g is used. It is preferable. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  In addition to the thermoplastic resin (A) having a glass transition temperature (Tg) in the range of 70 ° C. to 170 ° C., the colored composition of the present invention includes a thermoplastic resin having a glass transition temperature (Tg) of less than 70 ° C. Other resins such as a thermosetting resin can be used in combination as long as the effects of the present invention are not impaired.

  The thermoplastic resin (A) can be used in an amount of 30 to 500% by weight based on the total weight of the colorant (B). If it is less than 30% by weight, the film formability and various resistances are insufficient, and if it exceeds 500% by weight, the pigment concentration is low and color characteristics cannot be expressed.

（式中、Ｘは、ヒドロキシル基、水素原子、塩素原子、臭素原子のいずれかを表す。また、Ｒ¹¹〜Ｒ¹⁴はそれぞれ独立に、ハロゲン原子または炭素数１〜４のアルキル基を表し、互いに同一でも異なっていてもよい。ｎ１１〜ｎ１４はそれぞれ独立に０〜４の整数である。）
なかでも、下記式（４）の構造を有するものが、有機溶剤中への分散が容易となるため好ましい。
また、さらにハロゲン原子を無くす意味でも好ましい。
式（４）

アルミニウムフタロシアニン顔料は、着色組成物の全量を基準として、５〜２０重量％が好ましい。 <Colorant (B) containing aluminum phthalocyanine pigment>
As the aluminum phthalocyanine pigment of the present invention, those having the structure of the following formula (3) can be used.
Formula (3)

(Wherein, X represents a hydroxyl group, a hydrogen atom, a chlorine atom or a bromine atom. R ^{11 to} R ¹⁴ each independently represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, They may be the same or different from each other, and n11 to n14 are each independently an integer of 0 to 4.)
Among these, those having the structure of the following formula (4) are preferable because they can be easily dispersed in an organic solvent.
Further, it is also preferable in the sense of eliminating halogen atoms.
Formula (4)

The aluminum phthalocyanine pigment is preferably 5 to 20% by weight based on the total amount of the coloring composition.

The coloring composition of the present invention may further contain a pigment as long as the effect of the present invention is not impaired, for example, in order to adjust the chromaticity.
Specific examples of pigments that can be used are shown by pigment numbers. The following “CI” means a color index (CI).

When the coloring composition of the present invention is used as a blue coloring composition, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 and the like can be used in combination. Furthermore, a purple pigment can be used in combination with the blue coloring composition.
Examples of purple pigments added to the blue coloring composition include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, etc. can be used. Especially, C.I. I. Pigment Violet 23 is preferable.

When a blue pigment is used in combination, the weight ratio of blue pigment / aluminum phthalocyanine pigment is preferably 90/10 to 10/90.
When the weight ratio of the aluminum phthalocyanine pigment is 90% by weight or more, a blue hue does not appear, and when it is 10% by weight or less, an attempt to obtain the desired chromaticity results in a thick film, which is not preferable.
When a purple pigment is used in combination, the weight ratio of purple pigment / aluminum phthalocyanine pigment is preferably 95/5 to 10/90. When the weight ratio of the aluminum phthalocyanine pigment is 90% by weight or more, the lightness of blue is low, and when it is 5% by weight or less, the hue of blue is not appropriate.

When the coloring composition of the present invention is used as a green coloring composition, C.I. I. Pigment Green 7, 10, 36, 37, 58 or the like can be used in combination. Furthermore, a yellow pigment can be used in combination with the green coloring composition.
Examples of the yellow pigment added to the green coloring composition include 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, 1 Or the like can be used 5,176,177,179,180,181,182,185,187,188,193,194,199. Especially, C.I. I. Pigment Yellow 138, 139, 150, and 185 are preferable.

When the pigment composition is used for green and the green pigment is used in combination, the weight ratio of green pigment / aluminum phthalocyanine pigment is preferably 70/30 to 95/5. When the weight ratio of the aluminum phthalocyanine pigment is 30% by weight or more, the lightness is low as green, and when it is 5% by weight or less, the amount of the aluminum phthalocyanine pigment having good coloring power is reduced, and when the desired chromaticity is attempted, the film becomes thicker. This is not preferable.
When a yellow pigment is used in combination, the weight ratio of yellow pigment / aluminum phthalocyanine pigment is preferably 60/40 to 80/20. When the weight ratio of the aluminum phthalocyanine pigment is 40% by weight or more, the lightness is low as green, and when it is 20% by weight or less, the hue as green does not appear.

<Miniaturization of pigment>
The pigment used in the colored composition of the present invention is preferably a finely processed pigment that has been subjected to salt milling.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt works as a crushing aid, and it is thought that the pigment is crushed using the high hardness of the inorganic salt during salt milling, thereby generating an active surface and causing crystal growth. Yes. Therefore, the crushing of the pigment and the crystal growth occur simultaneously during the kneading, and the primary particle diameter of the pigment obtained varies depending on the kneading conditions.

  In order to promote crystal growth by heating, the heating temperature is preferably 40 to 150 ° C. When the heating temperature is less than 40 ° C., crystal growth does not occur sufficiently, and the shape of the pigment particles becomes close to amorphous, which is not preferable. On the other hand, when the heating temperature exceeds 150 ° C., crystal growth proceeds excessively and the primary particle diameter of the pigment becomes large, which is not preferable as a colorant for the color filter coloring composition. The kneading time for the salt milling treatment is preferably 2 to 24 hours from the viewpoint of the balance between the particle size distribution of the primary particles of the salt milling treatment pigment and the cost required for the salt milling treatment.

  By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution in which the primary particle diameter is very fine and the distribution range is wide. It is preferable that the primary particle diameter calculated | required by TEM (transmission electron microscope) of the pigment used for the coloring composition of this invention is the range of 20-100 nm. When it becomes smaller than 20 nm, dispersion in an organic solvent becomes difficult. On the other hand, if it exceeds 100 nm, a sufficient contrast ratio cannot be obtained. A particularly preferable range is 25 to 85 nm.

  As the water-soluble inorganic salt used for the salt milling treatment, 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% by weight, and most preferably 300 to 1000% by weight, based on the total amount of pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent is not particularly limited as long as it functions to wet the pigment and the water-soluble inorganic salt and 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 performing the salt milling treatment, 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.

Further, the volume average primary particle diameter (MV) of the pigment is measured by measuring the short axis diameter and the long axis diameter of 100 primary particles of the pigment using a transmission electron microscope (TEM) photograph. The average of the shaft diameters is defined as the particle diameter (d) of the pigment particles, and then the volume (V) of each particle is determined assuming that each pigment is a sphere having the determined particle diameter. And calculated using the following formula (5).
Formula (5) MV = Σ (V · d) / Σ (V)

<Pigment dispersant>
When dispersing the pigment, a pigment dispersant such as a dye derivative, a resin-type pigment dispersant, or a surfactant can be used as appropriate. Since the pigment dispersant is excellent in pigment dispersion and has a large effect of preventing reaggregation of the pigment after dispersion, a color filter excellent in transparency can be obtained. The pigment dispersant can be used in an amount of 0.1 to 50 parts by weight with respect to 100 parts by weight of the pigment.

Examples of the pigment derivative include a compound in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced into an organic pigment (organic pigment, organic dye), anthraquinone, acridone or triazine. It is done.
In the present invention, a pigment derivative is particularly preferable, and the structure thereof is a compound represented by the following formula (6).
Formula (6) P-Ln
(However,
P: organic pigment residue, anthraquinone residue, acridone residue or triazine residue L: basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group n: an integer of 1 to 4 is there)
Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; Indoline pigments; isoindolinone pigments; quinophthalone pigments; selenium pigments; metal complex pigments.

Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. What is currently used can be used, These can be used individually or in mixture of 2 or more types.
The blending amount of the pigment derivative is preferably 1 part by weight or more, more preferably 3 parts by weight or more, and most preferably 5 parts by weight or more with respect to 100 parts by weight of the colorant (B) from the viewpoint of improving dispersibility. . Further, from the viewpoint of heat resistance and light resistance, it is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and most preferably 25 parts by weight or less with respect to 100 parts by weight of the colorant (B).

  Among these, it is more preferable to use a pigment derivative having a copper phthalocyanine structure as a base skeleton because the dispersibility of the colorant (B) is improved and the heat resistance and light resistance of the coloring composition are improved. . The pigment derivative having a copper phthalocyanine structure as a base skeleton can be added in an amount of 10 to 40% by weight based on the total amount of the aluminum phthalocyanine pigment.

  The resin-type pigment dispersant used as a pigment dispersant has a pigment-affinity part having the property of adsorbing to the pigment and a part compatible with the pigment carrier, and adsorbs to the pigment to give the pigment to the pigment carrier It works to stabilize dispersion. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Oil-based dispersants such as salts; water-soluble such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based or the like is used. These can be used alone or in admixture of two or more.

  Surfactants used as pigment dispersants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfone. Sodium acetate, monoethanolamine dodecyl sulfate, triethanolamine dodecyl sulfate, ammonium dodecyl sulfate, monoethanolamine stearate, sodium stearate, sodium dodecyl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphorus Anionic surfactants such as acid esters; polyoxyethylene oleyl ether, polyoxyethylene dodecyl ether, polyoxy Nonionic surfactants such as tylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotics such as alkyl quaternary ammonium salts and their ethylene oxide adducts Examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaines and alkylimidazolines, and these can be used alone or in admixture of two or more.

（式中、Ｒ₂₁〜Ｒ₂₄はそれぞれ独立に、ＣＨ₂ＯＣＨ₃、ＣＨ₂ＯＣ₄Ｈ₉、ＨまたはＣＨ₂ＯＨである。） <Thermosetting compound (C)>
The colored composition of the present invention further contains a thermosetting compound (C), which is preferable because heat resistance and light resistance are further improved. Examples of the thermosetting compound (C) include thermosetting resins such as epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins, and these thermosetting resins. Monomers and oligomers before heat polymerization of the functional resin. Especially, an epoxy resin and a melamine resin can be used more suitably, A melamine resin is more preferable especially, The melamine compound which has the methylol imino group represented by following formula (7), or its condensate is still more preferable.
Formula (7)

(In the formula, R _{21 to} R ₂₄ are each independently CH ₂ OCH ₃ , CH ₂ OC ₄ H ₉ , H or CH ₂ OH.)

  The thermosetting compound (C) is preferably added in an amount of 10 to 60 parts by weight with respect to 100 parts by weight of the colorant (B). If the amount is less than 10 parts by weight, the effect of improving heat resistance and light resistance is reduced, and if it exceeds 60 parts by weight, the developability deteriorates during alkali development, which is not preferable.

<Organic solvent>
Furthermore, in the coloring composition of the present invention, a pigment is sufficiently dispersed in a pigment carrier and applied on a transparent substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm to form a filter segment. A solvent can be included to facilitate the process.
Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. -1,3-propanediol, 3,5,5-trimethyl-2-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, N-methylpyrrolidone, o- Xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene Glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol mono Hexyl ether, ethylene glycol monomethyl ether Ter, 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, dip Pyrene 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, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, Isobutyl, propyl acetate, include dibasic acid esters such as, used alone or in combination.

<Photosensitive coloring composition for color filter>
The colored composition of the present invention can be used as a photosensitive colored composition for a color filter by further adding a photopolymerization initiator (D) and / or a photopolymerizable composition (E).
<Photopolymerization initiator (D)>
A photopolymerization initiator (D) or the like is added to the photosensitive coloring composition for a color filter of the present invention when the composition is cured by ultraviolet irradiation or a filter segment is formed by a photolithographic method. The blending amount when using the photopolymerization initiator (D) is preferably 5 to 200% by weight based on the total amount of the colorant (B), and 10 to 150 from the viewpoint of photocurability and developability. More preferably, it is% by weight.

As the photopolymerization initiator (D),
4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one An acetophenone photopolymerization initiator;
Benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal;
Benzophenone-based photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, and 4-benzoyl-4′-methyldiphenyl sulfide;
Thioxanthone photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone;
2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloro) Methyl) -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, and 2,4-trichloromethyl (4′-methoxystyryl) -6 Triazine photopolymerization initiators such as triazine;
A borate photopolymerization initiator; a carbazole photopolymerization initiator; an imidazole photopolymerization initiator; and an oxime ester photopolymerization initiator are used.

The above photopolymerization initiators are used alone or in combination of two or more, but as a sensitizer,
α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, Compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and 4,4′-diethylaminobenzophenone can also be used in combination.

  The blending amount when using the sensitizer is preferably 3 to 60% by weight based on the photopolymerization initiator (D) contained in the colored composition, from the viewpoint of photocurability and developability. More preferably, it is 5 to 50% by weight.

<Photopolymerizable composition (E)>
The photopolymerizable composition (E) includes a monomer or oligomer that is cured by irradiation with active energy rays to form a transparent resin.
Methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, and tricyclodecanyl Monofunctional (meth) acrylates such as (meth) acrylate;
Bifunctional (meth) acrylates such as polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate;
Trifunctional or more polyfunctional compounds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate Functional (meth) acrylate;
1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether, neopentyl glycol diglycidyl ether, and epoxy (meth) acrylate which is a reaction product of an epoxy compound such as phenol novolac resin and (meth) acrylic acid;
Various (meth) acrylic esters modified with polyester, polyurethane, isocyanurate, methylolated melamine, etc .; and (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, ( Examples include monomers other than (meth) acrylates such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile, and these may be used alone or in combination of two or more. It is not limited to these.

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

<Other ingredients>
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Moreover, in order to improve adhesiveness with a base material, 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 organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite. 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 (B) in the coloring composition.

  Examples of the silane coupling agent 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 ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane. The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the colorant (B) in the coloring composition.

<Method for producing colored composition>
The coloring composition of the present invention comprises a mixture of a thermoplastic resin (A), a colorant (B) containing an aluminum phthalocyanine pigment, and a thermosetting compound (C), a pigment dispersant, and a solvent as necessary. The pigment can be finely dispersed in a resin solvent liquid by using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor (pigment dispersion). When used as a photosensitive coloring composition for a color filter, it can be prepared as a photosensitive coloring composition for a solvent developing type or alkali developing type color filter. The coloring composition for a solvent developing type or alkali developing type color filter is prepared by adding a photopolymerizable composition (E), a photopolymerization initiator (D), and other resins, solvents, and pigment dispersions as necessary. An agent, an additive, etc. can be mixed and adjusted.
Moreover, the coloring composition containing 2 or more types of pigments can also be produced by mixing each pigment separately and finely dispersed in a resin and a solvent.

  Thus, when the pigment whose average primary particle diameter is refined to 100 nm or less is dispersed in the resin using a disperser such as a sand mill, the pigment is dispersed in the form of dispersed particles composed of a plurality of secondary particles. The dispersed particles gradually become smaller with the progress of the dispersed state, and finally become dispersed in the state of primary particles, but the dispersed state is controlled by the size of the dispersed particles. In which the average diameter is in the range of 50 nm to 150 nm.

  As the dispersion progresses, the dispersed particle diameter becomes smaller, the transparency increases, and the contrast ratio rises. Therefore, the smaller the dispersed particle diameter is, the better the contrast ratio can be obtained from about 300 nm. On the other hand, when the dispersion progresses and the dispersed particle size becomes small, the viscosity of the dispersion increases and the thixotropic property tends to increase. When used as a photosensitive coloring composition for a color filter, it is required to have a low viscosity and a Newtonian flow because it is required to be coated with a thin film and to have a smooth coating surface. For this reason, it is preferable to suppress the dispersed particle size to about 100 nm in consideration of the viscosity and thixotropic property preferable for normal use. Thus, by using a pigment having an average primary particle size of 100 nm or less and controlling the degree of dispersion so that the average particle size of the dispersed particles is in the range of 50 nm to 150 nm, the increase in viscosity and thixotropic property are minimized. Thus, a pigment dispersion having a very high contrast ratio can be obtained.

  The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention includes a filter segment on a substrate, and can include, for example, a black matrix and red, green, and blue filter segments. The filter segment, after applying the photosensitive coloring composition for color filter by spin coating method or die coating method, by irradiating active energy rays such as ultraviolet rays to cure the portion that becomes the filter segment, and then developing, Formed on a substrate.

The color filter coloring composition produced according to the present invention is used to form a blue or green filter segment, and the other color filter segments are a red photosensitive coloring composition and a green photosensitive coloring that are conventionally used. The composition can be formed using a blue photosensitive coloring composition.
As each color photosensitive coloring composition other than the photosensitive coloring composition for a color filter in the present invention, usual photosensitive coloring compositions containing each color pigment, the resin, the photopolymerizable composition (E), and the like. Can be formed.

  The red filter segment can be formed using a normal red coloring composition containing a red pigment and a pigment carrier. Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, Red pigments such as 281, 282, 283, 284, 285, 286, or 287 are used. Further, a basic dye or a salt-forming compound of an acid dye exhibiting a red color can also be used.

  The red coloring composition includes C.I. I. Pigment orange 43, 71, 73 or the like 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, or may be used in combination of a yellow pigment 214, and the like.

  When a green filter segment other than the present invention is used, it can be formed using a normal green coloring composition containing a green pigment and a pigment carrier. Examples of the green pigment include C.I. I. Pigment Green 2, 7, 10, 36, 37, 58, etc. are used.

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

  When a blue filter segment other than the present invention is used, for example, C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. The blue photosensitive coloring composition includes C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.

  The magenta color filter segment can be formed using a normal magenta color coloring composition including a magenta color pigment and a pigment carrier. Examples of the magenta coloring composition include C.I. I. Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 192, 202, 207, 209, C.I. I. Pigment Violet 19 or the like is used.

  The yellow filter segment can be formed using a normal yellow coloring composition containing a yellow pigment and a pigment carrier. As a yellow pigment, the pigment illustrated as a yellow pigment which can be used together with a red pigment or a green pigment can be used.

  As the substrate for the color filter, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali aluminoborosilicate glass having high transmittance for visible light, and resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. Is used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

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.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase the UV exposure sensitivity, after applying and drying the colored composition material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Ultraviolet exposure can also be performed after forming.

  If the black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast of the liquid crystal display panel can be further increased. 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 a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed on the color filter 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 for a liquid crystal display mode in which colorization is performed using a color filter.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “part” means “part by weight”.
In the following examples, the number average molecular weight and the weight average molecular weight were determined by connecting four separation columns in series in the gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corporation. This is a molecular weight in terms of polystyrene measured using “TSK-GEL SUPER H5000”, “H4000”, “H3000”, and “H2000” manufactured by Tetrahydrofuran as a mobile phase.
Further, the volume average primary particle diameter (MV) of the pigment is measured by measuring the short axis diameter and the long axis diameter of 100 primary particles of the pigment using a transmission electron microscope (TEM) photograph. The average of the shaft diameters is defined as the particle diameter (d) of the pigment particles, and then the volume (V) of each particle is determined assuming that each pigment is a sphere having the determined particle diameter. And calculated using the following formula (5).
Formula (5) MV = Σ (V · d) / Σ (V)

  First, the manufacturing method of the refinement | purification processing pigment used for the Example and the comparative example, the synthesis method of a thermoplastic resin (A), and the manufacturing method of a yellow pigment dispersion are shown.

<Method for producing refined pigment>
(Production of refined pigment (PB-1); chloroaluminum phthalocyanine)
Production of an aluminum phthalocyanine pigment (chloroaluminum phthalocyanine) having a structure in which X is a chlorine atom and n11 to n14 are each 0 in formula (3) was performed according to the following procedure. A glass 4-necked flask was charged with 60.0 parts of phthalonitrile, 300 parts of 1-chloronaphthalene, and 15.6 parts of aluminum chloride, and stirred under reflux for 6 hours. Thereafter, heating was stopped, the mixture was allowed to cool to about 200 ° C., filtered while hot, and washed by sprinkling with 600 parts of hot toluene and 300 parts of acetone. The obtained wet cake was dispersed in 250 parts of toluene and stirred and refluxed for 3 hours. The mixture was again filtered while hot, sprinkled and washed with 600 parts of hot toluene and 300 parts of acetone, dispersed in 1500 parts of ion-exchanged water, and heated and stirred at 60 to 70 ° C. for 60 minutes. Filtration, washing with water and vacuum drying at 50 ° C. gave a blue solid aluminum phthalocyanine pigment (AlPc—Cl) having the desired structure.
This (AlPc-Cl pigment 50 parts, sodium chloride 150 parts, and diethylene glycol 25 parts were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 120 ° C. The mixture was poured into warm water, stirred for 1 hour while heating to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night to obtain a refined pigment (PB-1 The volume average primary particle diameter of the obtained pigment was 26 nm.

(Production of refined pigment (PB-2); hydroxyaluminum phthalocyanine)
Production of an aluminum phthalocyanine pigment (hydroxyaluminum phthalocyanine) having a structure represented by the formula (4) was performed according to the following procedure. 30 parts of the (AlPc-Cl) pigment before kneader synthesis synthesized in the production of the finely treated pigment (PB-1) was gradually dissolved in 1200 parts of concentrated sulfuric acid while maintaining the temperature at about 5 ° C., and this temperature was maintained for 1 hour. Stir. This was added to 6000 parts of ice water with stirring so that the temperature did not exceed 5 ° C., and further stirred for 1 hour after the end of the addition. After filtration and washing with water, it was redispersed in 6500 parts of ion exchange water and filtered again. After washing with water, the wet cake was redispersed in 2500 parts of 4% aqueous ammonia and stirred under reflux for 6 hours. After filtration, the cake was washed with ion-exchanged water and then vacuum-dried at 50 ° C. to obtain a blue solid aluminum phthalocyanine pigment (AlPc—OH) having the desired structure.
50 parts of this (AlPc-OH) pigment, 150 parts of sodium chloride, and 25 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 6 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. A refined pigment (PB-2) was obtained. The obtained pigment had a volume average primary particle size of 28 nm.

(Production of refined yellow pigment (PY-1))
Metal complex yellow pigment C.I. I. 50 parts of Pigment Yellow 150 (LANXESS "E4GN"), 250 parts of sodium chloride, and 25 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C for 6 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. Then, a refined yellow pigment (PY-1) was obtained. The obtained pigment had a volume average primary particle size of 28 nm.

<Method for synthesizing thermoplastic resin (A)>
(Preparation of resin solution (A-1))
233 parts of propylene glycol monomethyl ether acetate was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device, and the temperature was raised to 80 ° C. From the tube, 25 parts of cyclohexylmaleimide, 20 parts of methacrylic acid, 15 parts of 2-hydroxyethyl methacrylate, 10 parts of methyl methacrylate, a compound represented by the following formula (8) (paracumylphenol ethylene oxide modified acrylate; Aronix M110 manufactured by Toagosei Co., Ltd.) )) A mixture of 30 parts and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a resin solution having a weight average molecular weight (Mw) of 40000.
After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution (A-1).
The calculated glass transition point (Tg) of this resin was 107 ° C.
Formula (8)

(Preparation of resin solution (A-2))
233 parts of propylene glycol monomethyl ether acetate was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device, and the temperature was raised to 80 ° C. From the tube, 15 parts of cyclohexylmaleimide, 13 parts of methacrylic acid, 15 parts of 2-hydroxyethyl methacrylate, 30 parts of methyl methacrylate (Paccumylphenol ethylene oxide-modified acrylate; Aronix M110 manufactured by Toagosei Co., Ltd.) ) A mixture of 27 parts and 1.33 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a resin solution having a weight average molecular weight (Mw) of 41500.
After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution (A-2).
The calculated glass transition point (Tg) of this resin was 98 ° C.

(Preparation of resin solution (A-3))
233 parts of propylene glycol monomethyl ether acetate was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device, and the temperature was raised to 80 ° C. From a tube, a mixture of 24 parts of styrene, 24 parts of acrylic acid, 26 parts of methyl methacrylate, 26 parts of butyl methacrylate, and 1.33 parts of 2,2′-azobisisobutyronitrile was dropped over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a resin solution having a weight average molecular weight (Mw) of 40000.
After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution (A-3).
The calculated glass transition point (Tg) of this resin was 82 ° C.

(Preparation of resin solution (A-4))
233 parts of propylene glycol monomethyl ether acetate was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device, and the temperature was raised to 80 ° C. From the tube, 20 parts of methacrylic acid, 15 parts of 2-hydroxyethyl methacrylate, 10 parts of methyl methacrylate, 30 parts of a compound represented by the following formula (8) (paracumylphenol ethylene oxide-modified acrylate; Aronix M110 manufactured by Toagosei Co., Ltd.) A mixture of 25 parts of benzyl methacrylate and 1.33 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a resin solution having a weight average molecular weight (Mw) of 23,000.
After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution (A-4).
The calculated glass transition point (Tg) of this resin was 72 ° C.

(Preparation of resin solution (A-5))
233 parts of propylene glycol monomethyl ether acetate was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device, and the temperature was raised to 80 ° C. From a tube, a mixture of 15 parts of methacrylic acid, 15 parts of 2-hydroxyethyl methacrylate, 75 parts of benzyl methacrylate and 1.33 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a resin solution having a weight average molecular weight (Mw) of 28000.
After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution (A-5).
The calculated glass transition point (Tg) of this resin was 65 ° C.

(Preparation of resin solution (A-6))
233 parts of propylene glycol monomethyl ether acetate was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device, and the temperature was raised to 80 ° C. From the tube, 13 parts of methacrylic acid, 14 parts of 2-hydroxyethyl methacrylate, 25 parts of the compound represented by the above formula (8) (paracumylphenol ethylene oxide modified acrylate; Aronix M110 manufactured by Toagosei Co., Ltd.), 25 parts of benzyl methacrylate, A mixture of 23 parts of butyl methacrylate and 1.33 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was further continued for 3 hours to obtain a resin solution having a weight average molecular weight (Mw) of 32,000.
After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution (A-7).
The calculated glass transition point (Tg) of this resin was 53 ° C.

  Table 1 shows an outline of the thermoplastic resin (A) used in Examples and Comparative Examples.

表１中の略語について以下に示す。
ＡＡ：アクリル酸、MAA：メタクリル酸、ＭＭＡ：メチルメタクリレート
ＢＭＡ：ブチルメタクリレート、ＨＥＭＡ：2-ヒドロキシエチルメタクリレート
ＢｚＭＡ：ベンジルメタクリレート、ＣＨＭＩ：シクロヘキシルマレイミド
Ｍ１１０：パラクミルフェノールエチレンオキサイド変性アクリレート 式（８）
S：スチレン

Abbreviations in Table 1 are shown below.
AA: acrylic acid, MAA: methacrylic acid, MMA: methyl methacrylate BMA: butyl methacrylate, HEMA: 2-hydroxyethyl methacrylate BzMA: benzyl methacrylate, CHMI: cyclohexylmaleimide M110: paracumylphenol ethylene oxide modified acrylate Formula (8)
S: Styrene

<Method for producing yellow pigment dispersion>
(Preparation of yellow pigment dispersion (DY-1))
After stirring and mixing a mixture having the following composition with a disper, using a zirconia bead having a diameter of 0.5 mm, it is dispersed for 4 hours using an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) as a media type wet disperser. After that, a pigment content of 50% and a solid content of 20% were prepared.
Refined yellow pigment (PY-1) 10.0 parts Resin solution (A-1) 50.0 parts Propylene glycol monomethyl ether acetate 40.0 parts

[Example 1]
After stirring and mixing a mixture having the following composition with a disper, using a zirconia bead having a diameter of 0.5 mm, it is dispersed for 4 hours using an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) as a media type wet disperser. After that, it was prepared to have a pigment content of 50% and a solid content of 20% to obtain an aluminum phthalocyanine pigment dispersion (DB-1).
Aluminum phthalocyanine pigment (PB-2) 10.0 parts Resin solution (A-1) 50.0 parts Propylene glycol monomethyl ether acetate 40.0 parts

[Examples 2 to 9, Comparative Examples 1 and 2]
Pigment dispersions (DB-1 to 11) were prepared in the same manner as in Example 1 except that the composition and blending amount (parts by weight) shown in Table 2 were changed.

Abbreviations in Table 2 are shown below.
Pigment derivative 1; copper phthalocyanine pigment derivative formula (9) shown in formula (9) CuPc-SO ₃ H. (CH ₃ ) ₂ N (C ₁₈ H ₃₇ ) ₂
(In the formula, CuPc is a copper phthalocyanine pigment residue.)
Pigment derivative 2; copper phthalocyanine pigment derivative formula (10) shown in formula (10) CuPc-SO ₂ NH (CH ₂ ) ₃ N (C ₂ H ₅ ) ₂
(In the formula, CuPc is a copper phthalocyanine pigment residue.)
Melamine compound: “MW-30” manufactured by Sanwa Chemical Co. (solid content: 100%)

<Heat and light resistance evaluation>
[Spectral shape evaluation]
The colored compositions obtained in Examples 1 to 9 and Comparative Examples 1 and 2 were placed on a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm, using a spin coater, and y (C) = 0.29. Then, it was coated at a film thickness to be, and then dried at 70 ° C. for 20 minutes to obtain a coated substrate.
The obtained coated substrate and the transmission spectrum after heat treatment at 230 ° C. for 1 hour were measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). From the obtained transmission spectrum (T), an absorption spectrum (Abs) was calculated from the following formula (11).

Formula (11) Abs = −log (T)

Peak value around 630 nm due to aluminum phthalocyanine pigment before and after heat treatment at 230 ° C. (A ₆₃₀ ; before heat treatment, A ′ ₆₃₀ ; after heat treatment) and peak value around 670 nm (A ₆₇₀ ; before heat treatment, A ′ ₆₇₀ ; after heat treatment) Was used to calculate a parameter representing the degree of spectral shape change from the following equations (12) and (13).
Formula (12) _R630 = _A'630 / _A630
Formula (13) _R670 = _A'670 / _A670
The closer the R ₆₃₀ value calculated here is to 1, the more steep spectral shape is maintained, which is advantageous in terms of brightness. In addition, the smaller the value of R _670, the more the index indicates that the crystal system is maintained. Each was evaluated in three stages according to the following criteria.
(Lightness evaluation; R ₆₃₀ )
○: 85% or more Δ: 75% or more and less than 85% ×: less than 75% (heat resistance evaluation; R ₆₇₀ )
○: 100% or more and less than 150% △: 150% or more and less than 200% ×: 200% or more

[Color difference evaluation]
The colored compositions obtained in Examples 1 to 9 and Comparative Examples 1 and 2 were placed on a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm, using a spin coater, and y (C) = 0.29. And then dried at 70 ° C. for 20 minutes, then heated at 230 ° C. for 1 hour and allowed to cool, and then the chromaticity of the obtained coating film was measured by a microspectrophotometer (“OSP-” manufactured by Olympus Optics). [L * (1), a * (1), b * (1)] were measured using SP100 ").
(Heat resistance evaluation)
Further, the chromaticity [L * (2), a * (2), b * (2)] after heat treatment at 250 ° C. for 1 hour is measured, and the color difference ΔE * ab is obtained by the following equation (14). It was.
Formula (14)
ΔE * ab = [[L * (2) −L * (1)] ² + [a * (2) −a * (1)] ² + [b * (2) −b * (1)] ² ] ^1/2
(Light resistance evaluation)
Similarly, a coated substrate was prepared, and the chromaticity [L * (2), a * (2), b * (2)] after irradiation with ultraviolet rays using a 470 W / m ² xenon lamp was measured. The color difference ΔE * ab was obtained from the above equation (14).
The above results are shown in Table 3.

As in the examples, when a resin having a Tg of 70 ° C. or higher was used, good results were obtained in both heat resistance and light resistance. Furthermore, when a resin having a Tg of 90 ° C. or higher was used, both heat resistance and light resistance were very good. When a resin having a Tg of 70 ° C. or lower was used as in the comparative example, the spectrum changed greatly, and the heat resistance and light resistance were very poor.
When a resin having a high Tg is used as in the examples, the temperature at which liquefaction is increased, liquefaction of the resin in the post-baking process is suppressed, and diffusion of the aluminum phthalocyanine pigment accompanying the disappearance of the crystal system is prevented. Conceivable. As a result of maintaining the crystal system, changes in the spectral shape are suppressed, and heat resistance and light resistance are improved.
Moreover, by adding the melamine compound which is a thermosetting compound (C), the film hardening by heat | fever occurred, and it became a result with very favorable heat resistance and light resistance.
Further, Examples 8 and 9 in which the pigment derivative was used in combination had almost no spectral shape change and no color difference change, and excellent results were obtained.

<Preparation of photosensitive coloring composition>
[Example 10]
A mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1 μm filter to prepare an alkali development type photosensitive blue coloring composition (RB-1).
Pigment dispersion (DB-1) 60.0 parts Resin solution (A-1) 15.0 parts Trimethylolpropane triacrylate 3.0 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photoinitiator ("Irgacure 907" manufactured by Ciba Japan) 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Cyclohexanone 20.4 parts

[Examples 11 to 20, Comparative Examples 3 to 5]
Except having changed into a composition and compounding quantity as shown in Table 4, it carried out similarly to Example 10, and produced the alkali image development type photosensitive coloring composition (RB-2-12, RG-1, 2).

Abbreviations in Table 4 are shown below.
Melamine compound: “MW-30” manufactured by Sanwa Chemical Co. (solid content: 100%)
Photopolymerizable composition (E); trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator (D); “Irgacure 907” manufactured by Ciba Japan
・ Sensitizer: “EAB-F” manufactured by Hodogaya Chemical Co., Ltd.

<Measurement of halogen content>
The halogen atom content in the alkali-developable photosensitive coloring compositions prepared in Examples and Comparative Examples was measured by ICP emission spectroscopy (inductively coupled plasma emission analyzer “SPS4000” manufactured by SII Nanotechnology). .

<Heat and light resistance evaluation>
[Spectral shape evaluation]
The alkaline development type photosensitive coloring composition obtained in Examples 10 to 20 and Comparative Examples 3 to 5 was coated on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater. A coated substrate was obtained in which the product was y (c) = 0.29 with a C light source, and the photosensitive green coloring composition was y (c) = 0.69. Next, after drying at 70 ° C. for 20 minutes, using an ultra-high pressure mercury lamp, UV exposure was performed with an integrated light amount of 150 mJ, and development was performed with an alkali developer to obtain a coated substrate.
The obtained coating film substrate and a transmission spectrum after heat treatment at 230 ° C. for 1 hour were measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). Examples 1 to 9, Comparative Example 1, Evaluation similar to 2 was performed.

[Color difference evaluation]
The alkaline development type photosensitive coloring composition obtained in Examples 10 to 20 and Comparative Examples 3 to 5 was coated on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater. The product was a C light source and y (c) = 0.29, and the photosensitive green coloring composition was y (c) = 0.69. Next, after drying at 70 ° C. for 20 minutes, using an ultra-high pressure mercury lamp, UV exposure was performed with an integrated light amount of 150 mJ, development was performed with an alkaline developer, and then heated at 230 ° C. for 1 hour and allowed to cool to obtain. [L * (1), a * (1), b * (1)] was measured for the chromaticity of the coating film using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.).
(Evaluation of heat resistance and light resistance)
Evaluation similar to Examples 1-9 and Comparative Examples 1 and 2 was performed.
The results are shown in Table 5.

Even if it uses an alkali development type photosensitive coloring composition, it is the result similar to a pigment dispersion, and Examples 10-20 which are the alkali development type photosensitive coloring composition of this invention are the characteristics excellent in heat resistance and light resistance. showed that.
Moreover, the measurement result of the halogen atom amount of the photosensitive coloring composition of this invention became 500 ppm or less about all the photosensitive coloring compositions about the bromine atom. Moreover, about chlorine atom, all became 500 ppm or less except having become 5000 ppm or less by RB-3.

<Production of color filter>
Next, a black matrix is patterned on a glass substrate, and the pigment used in the coloring composition in the photosensitive blue coloring composition (RB-1) is formed on the substrate by a spin coater. I. Pigment Red 254 / C.I. I. Pigment Red 177 = 5.1 parts / 0.9 parts except that the photosensitive red coloring composition produced in the same manner as in Example 10 was used in a C light source (hereinafter also used for green and blue) x = 0 .670, y = 0.330 was applied to form a colored film. Next, the film was irradiated with 300 mJ / cm ² of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, spray development is performed with an alkali developer composed of a 2% by weight aqueous sodium carbonate solution to remove unexposed portions, and then the substrate is washed with ion-exchanged water. The substrate is heated at 230 ° C. for 20 minutes to form a red filter segment. did.
Similarly, in the photosensitive blue coloring composition (RB-1) so that the photosensitive green coloring composition (RG-1) obtained in Example 13 was x = 0.205 and y = 0.640. The pigment used in the coloring composition is C.I. I. Pigment Blue 15: 6 / C.I. I. Pigment Violet 23 = 3.6 parts / 2.4 parts were used, except that x = 0.149 and y = 0.048 were obtained using the blue photosensitive coloring composition prepared in the same manner as in Example 10. Each film was applied to a different thickness to form a green filter segment and a blue filter segment to obtain a color filter.
Further, using the same photosensitive coloring composition as described above, a red filter segment of x = 0.640, y = 0.330, a green filter segment of x = 0.214, y = 0.600 in a C light source, x = 0.150, y = 0.06 were applied to the film thickness so as to be a blue filter segment to obtain a color filter.
When the photosensitive coloring composition for a color filter in the present invention is used, a color filter having a green filter segment having excellent color density, color purity, transparency, heat resistance and light resistance in a wide chromaticity range is produced. It was possible.

Claims (6)

  A coloring composition containing at least a thermoplastic resin (A) and a colorant (B) containing an aluminum phthalocyanine pigment, wherein the glass transition temperature (Tg) of the thermoplastic resin (A) is 70 to 170 ° C. The coloring composition characterized by being. The thermoplastic resin (A) is at least two or more selected from the group consisting of acrylic acid, methacrylic acid, methyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, and a monomer represented by the following formula (1) The colored composition according to claim 1, which is a resin having a structural unit derived from the monomer.
Formula (1)

Wherein R ₁ is H or CH ₃ , R ₂ is an alkylene group having 2 or 3 carbon atoms, R ₃ is hydrogen, or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring, n is It is an integer from 1 to 15.)   The colored composition according to claim 2, wherein the thermoplastic resin (A) is a resin further having a structural unit derived from an N-substituted maleimide monomer.   Furthermore, a thermosetting compound (C) is contained, The coloring composition in any one of Claims 1-3 characterized by the above-mentioned.   The photosensitive coloring composition for a color filter comprising the coloring composition according to any one of claims 1 to 4, further comprising a photopolymerization initiator (D) and / or a photopolymerizable composition (E). .   A color filter comprising a filter segment formed using the photosensitive coloring composition for a color filter according to claim 5.