JP2016180020A - C.i. pigment yellow 139 - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide C.I. pigment yellow 139 that gives high contrast when used for a color filter, and a pigment composition, coloring composition and color filter comprising the same.SOLUTION: A C.I. pigment yellow 139 has 0.75 or more as a half value width of a peak showing the maximal diffraction intensity within a range of 2θ=19.8±0.5° on a powder X-ray diffractogram in terms of diffraction intensity with respect to a Bragg angle 2θ measured via CuKα rays.SELECTED DRAWING: Figure 1

Description

  The present invention provides a novel C.I. I. Pigment Yellow 139, a pigment composition comprising the same, a method for producing the same, and a coloring composition.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. There is an increasing demand for higher quality and high color reproducibility.

  A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or fine filter segments are arranged vertically and horizontally. It is made up of those arranged in In general, it is often formed of three color filter segments of red, green, and blue. Each segment is as fine as several microns to several hundreds of microns, and is arranged in a predetermined arrangement for each hue. .

  Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 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 heat resistance and light resistance as a colorant is mainly used.

  The quality items required for the color filter include contrast and brightness. When a color filter with low contrast is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light must leak or be transmitted (ON state) ), The transmitted light attenuates, resulting in a blurred screen. Therefore, in order to realize a high-quality liquid crystal display device, it is essential to increase the contrast.

  Further, as described above, since the color liquid crystal device is used in a television, a personal computer monitor, and the like, the demand for a wide color reproduction region and high reliability is increased along with high contrast and high brightness for the color filter.

  As the demand for high color reproduction is increasing in color filters, there is a problem that the film thickness of the color filter becomes thick in order to improve color reproduction when conventional pigments are used. Therefore, reddish yellow and high coloring power C.I. I. Pigment Yellow 139 is drawing attention.

  C. I. Pigment Yellow 139 is a printing ink such as offset ink, gravure ink, inkjet ink, colorant such as plastic or paint, image recording material such as thermal transfer system or electrophotographic system, liquid crystal, plasma, organic electroluminescence (electroluminescence). It is widely used in various applications such as color filters used in image display devices such as devices and electronic paper, and image sensors such as CCDs.

  C. I. Pigment Yellow 139 is reddish yellow. C. has been mainly used so far. I. Pigment Yellow 138 had to be added in a large amount when adjusting Red or Green to the target hue. However, C.I. I. Pigment Yellow 139 may be C.I. I. Compared to Pigment Yellow 138, it is reddish, so it is possible to match the target hue with a small amount of Red or Green. For this reason, C.I. I. Pigment Yellow 139 has higher coloring power than other yellow pigments. However, C.I. I. Pigment Yellow 139 exhibits a high coloring power, but has a problem of low contrast when used in a color filter. In order to improve the contrast, it is necessary to reduce the primary particle diameter of the pigment and to reduce light scattering by the pigment.

As methods for refining the primary particle diameter of pigments, there have been proposed a method using fine salt or an acrylic resin in a solvent salt milling process, or a method of growing particles after dry pulverization (Patent Documents 1 and 2). 3).
However, C.I. produced by these known methods. I. Pigment Yellow 139 is not sufficiently refined, and C.I. which exhibits the high contrast required by these known methods. I. Pigment Yellow 139 was not obtained. Even when this pigment is used in a color filter, the contrast is low and it cannot meet the high demand performance from the market, and further miniaturization is required.

JP2007-238852 JP2009-256615A JP2004-35628

  The problem to be solved by the present invention is C.I. which gives high contrast when used in a color filter. I. Pigment Yellow 139 and a pigment composition, a coloring composition and a color filter containing the same are provided.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a half-width of a specific peak in a powder X-ray diffraction shows a large value greater than a certain value. I. It has been found that CI Pigment Yellow 139 can solve the above-mentioned problems, and has made the present invention.

That is, an embodiment of the present invention is an X-ray powder diffractogram represented by a diffraction intensity with respect to a Bragg angle 2θ measured by CuKα rays.
A peak showing the maximum diffraction intensity within the range of 2θ = 19.8 ± 0.5 ° is A,
2x in A is Ax,
B indicates a point showing the minimum diffraction intensity within a range of 2θ of Ax or less and Ax−1.0 ° or more.
A point indicating the minimum diffraction intensity within a range where 2θ is Ax or more and Ax + 1.8 ° or less is C,
The straight line connecting B and C is the baseline,
D, the intersection of the perpendicular line drawn from A to the 2θ axis and the baseline
E, the intersection of the line AB passing through the midpoint of A and D and parallel to the baseline, and the curve AB
F, the intersection of the line AC passing through the midpoint of A and D and parallel to the baseline, and the curve AC
2θ in E is Ex, 2θ in F is Fx,
When Fx-Ex is the half width of A,
The half width of A is 0.75 or more. I. Related to Pigment Yellow 139.

  In another embodiment of the present invention, the half width of A is 0.85 or more. I. Related to Pigment Yellow 139.

  An embodiment of the present invention is the above-mentioned C.I. I. Pigment Yellow 139 and a compound represented by the following general formula (1), I. The present invention relates to a pigment composition comprising 0.5 to 40% by mass of the compound represented by the general formula (1) with respect to 100 parts by mass of Pigment Yellow 139.

[In General Formula (1), X ₁ is a group represented by Formula (a). X ₂ is a group represented by the formula (b) or the formula (c). X ₃ is a group represented by formula (a), formula (b), formula (c) or formula (d). ]

[In Formula (a), Y ₁ is NH or O, and R ₁ is a divalent hydrocarbon group having 1 to 8 carbon atoms. R ₂ and R ₃ are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ₂ and R ₃ may be bonded to each other to form a ring. ]

[In Formula (b), Y ₂ is NH or O, and R ₄ is a group represented by Formula (2) or Formula (3) below. R ₅ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms.

[In Formula (c), Y ₃ is NH or O, and R ₆ is a group represented by the following Formula (2) or Formula (3). ]

[In formula (d), Y ₄ is NH or O, and R ₇ is H, a monovalent hydrocarbon group having 1 to 8 carbon atoms, or a group represented by the following formula (e). ]

[In Formula (e), R ₈ is a hydrocarbon group having 1 to 8 carbon atoms, and R ₉ is H or a hydrocarbon group having 1 to 8 carbon atoms. n is an integer of 1 to 3. ]

  An embodiment of the present invention is the above-mentioned C.I. I. Pigment Yellow 139 and a polyester resin comprising C.I. I. The present invention relates to a pigment composition comprising 5 to 30 parts by mass of a polyester resin with respect to 100 parts by mass of Pigment Yellow 139.

  An embodiment of the present invention is the above-mentioned C.I. I. Pigment Yellow 139, a pigment composition comprising a compound represented by the general formula (1) and a polyester resin, I. It is related with the said pigment composition which contains 0.5-40 mass% of compounds represented by General formula (1), and 5-30 mass parts of polyester resins with respect to 100 mass parts of pigment yellow 139.

  An embodiment of the present invention is a C.I. I. CI Pigment Yellow 139, a compound represented by the general formula (1) and / or a polyester resin are mixed to produce a solvent salt mill, which is a method for producing the above pigment composition. I. It is related with the manufacturing method of the said pigment composition which uses 0.5-40 mass parts and / or 5-30 mass parts of polyester resins for the compound represented by General formula (1) with respect to 100 mass parts of pigment yellow 139. .

  An embodiment of the present invention is a coloring composition comprising at least a colorant, a binder resin, and an organic solvent, wherein the colorant is the above-described C.I. I. The present invention relates to a coloring composition containing Pigment Yellow 139 or the above pigment composition.

  Moreover, the embodiment of this invention is related with the said coloring composition which contains a photopolymerizable monomer and / or a photoinitiator further.

  An embodiment of the present invention also relates to a color filter comprising a filter segment formed from the above-described colored composition on a substrate.

  According to the present invention, finer C.I. I. Pigment Yellow 139 and a method for manufacturing the same are provided. As a result, it was possible to provide a coloring composition and a photosensitive coloring composition which showed high contrast and had excellent dispersibility and dispersion stability of the pigment.

1 shows C.I. produced in Example 3. FIG. I. It is a powder X-ray diffraction pattern of CI pigment yellow 139. FIG. 2 is a schematic diagram of a powder X-ray diffraction diagram around 2θ = 19.8 ± 0.5 °.

  Hereinafter, the present invention will be described in detail. Note that “CI” in this specification means a color index (CI). Further, “%” in the present specification means mass% unless otherwise specified.

C. in the present invention. I. Pigment Yellow 139 is a powder X-ray diffraction diagram represented by a diffraction intensity with respect to a Bragg angle 2θ measured by CuKα rays.
A peak showing the maximum diffraction intensity within the range of 2θ = 19.8 ± 0.5 ° is A,
2x in A is Ax,
B indicates a point showing the minimum diffraction intensity within a range of 2θ of Ax or less and Ax−1.0 ° or more.
A point indicating the minimum diffraction intensity within a range where 2θ is Ax or more and Ax + 1.8 ° or less is C,
The straight line connecting B and C is the baseline,
D, the intersection of the perpendicular line drawn from A to the 2θ axis and the baseline
E, the intersection of the line AB passing through the midpoint of A and D and parallel to the baseline, and the curve AB
F, the intersection of the line AC passing through the midpoint of A and D and parallel to the baseline, and the curve AC
2θ in E is Ex, 2θ in F is Fx,
When Fx-Ex is the half width of A,
The half width of A is 0.75 or more, more preferably 0.85 or more.

The measurement method for obtaining the powder X-ray diffraction diagram and the calculation method of the half width are based on the methods described in the examples.

  The half width (Δ2θ) obtained here corresponds to the size of the crystallite (= crystallinity). The smaller the crystallite is, the lower the crystallinity is and the finer the half width is, the larger the half width is. It becomes.

  Surprisingly, the half width of the peak showing the maximum diffraction intensity within the range of 2θ = 19.8 ± 0.5 ° is 0.75 or more. I. The inventors have found that when CI Pigment Yellow 139 is used, a color filter having an extremely high contrast can be produced. It was revealed that a color filter having a higher contrast can be produced when the half width is 0.85 or more. The half width may be 0.75 or more, preferably 0.85 or more, more preferably 1.1 or more, and further preferably 1.2 or more. Such C.I. I. A method for producing Pigment Yellow 139 will be described later.

  Examples of the compound used in the pigment composition of the present invention include those represented by the general formula (1). The hydrocarbon group in the general formula (1) is an aliphatic group, an aromatic group, a combination thereof, a straight chain, a branched chain, a cyclic structure or a combination thereof, a saturated bond, an unsaturated bond, or a combination thereof. And the like.

  Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, a cycloalkyl group, and an aryl group. Examples of the divalent hydrocarbon group include an alkylene group and an arylene group.

  Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like.

Examples of the alkenyl group include allyl group, 2-butenyl group, 2-pentenyl group, and 2-octenyl group.

Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a 2-norbornyl group.

  Examples of the aryl group include a phenyl group, a p-tolyl group, and a 3,5-xylyl group.

  Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, an octamethylene group, and a propylene group.

  Examples of the arylene group include a 1,3-phenylene group, a 1,4-phenylene group, a 2-methyl-1,4-phenylene group, and a 2,5-dimethyl-1,4-phenylene group.

  All of the above examples are specific examples of monovalent or divalent hydrocarbon groups having 1 to 8 carbon atoms. The hydrocarbon groups having 1 to 6 carbon atoms are carbon atoms having the above-described specific examples. Examples thereof include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, an alkylene group, and a phenylene group.

  The compound represented by the general formula (1) used in the present invention can be produced according to the methods described in JP-A-8-127749 and JP-A-11-199796. Examples of the compound represented by the general formula (1) include the following compounds A to K, but the compound represented by the general formula (1) is not limited to these examples.

  C. I. As the use ratio of Pigment Yellow 139 and the compound represented by the general formula (1), C.I. I. The compound represented by the general formula (1) with respect to Pigment Yellow 139 is preferably used in an amount of 0.5 to 40% by mass, more preferably 1 to 25% by mass, and further preferably 5 to 20% by mass. preferable.

  The polyester resin used in the pigment composition of the present invention is not particularly limited as long as it is a resin obtained by reacting a polyalcohol and a polyvalent carboxylic acid, but two or more hydroxyl groups and one or more mercapto groups in the molecule. A hydroxyl group in a polyol containing a vinyl polymer having two or more hydroxyl groups in one terminal region formed by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound having a tetracarboxylic dianhydride; A polyester resin obtained by reacting at least an acid anhydride in a polycarboxylic acid anhydride is preferable.

  Examples of the compound (a) having two or more hydroxyl groups and one or more mercapto groups in the molecule used in the present invention include 1-mercapto-1,1-methanediol, 1-mercapto-1,1- Ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 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-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3- Examples include propanediol.

Examples of the ethylenically unsaturated monomer (b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl. Alkyl (meth) acrylates such as (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, and lauryl (meth) acrylate;
Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2- Alicyclic alkyl (meth) acrylates such as methyl-2-adamantyl (meth) acrylate and 2-2 ethyladamantyl (meth) acrylate;
Heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate and 3-methyloxetanyl (meth) acrylate;
(Meth) acrylates having an aromatic substituent such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethylene oxide-modified (meth) acrylate, and paracumylphenoxyethylene oxide-modified (meth) acrylate;
Alkoxyalkylene (meth) acrylates such as methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxyethyl (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate;
(Meth) acrylamide, and N-substituted types such as N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and 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;
As well as mixtures thereof.

Moreover, as monomers that can be used in combination with the acrylic monomer, styrenes such as styrene and α-methylstyrene;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate and vinyl propionate;
As well as mixtures thereof.

The ethylenically unsaturated monomer may have an acidic functional group. For example, ethylenically unsaturated monomers having a carboxyl group such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid;
An ethylenically unsaturated monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; and
Examples thereof include an ethylenically unsaturated monomer having a carboxylic anhydride group such as maleic anhydride and itaconic anhydride. Among these, an ethylenically unsaturated monomer having a carboxyl group is particularly preferable. These ethylenically unsaturated monomers having an acidic functional group may be only one type or two or more types.

  The polycarboxylic acid anhydride used in the present invention contains at least a tetracarboxylic dianhydride. The two anhydride groups of tetracarboxylic dianhydride react with the hydroxyl group of the polyol, so that the carboxyl groups that serve as pigment adsorbing groups can be regularly arranged in the main chain of the polyester dispersant, which is advantageous for pigment dispersion. It is.

    Examples of the tetracarboxylic dianhydride used in the present invention include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3 , 5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3 -Aliphatic tetracarboxylic such as cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Dianhydride, pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3 ', 4,4'-benzophenone tetra Carboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene Tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′ , 4,4′-Tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4 ′ Bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxy) Phenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthal Acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4 '-Diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, 9,9-bis (3,4-dica Ruboxyphenyl) fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro- Aromatic tetracarboxylic dianhydrides such as 1-naphthalene succinic dianhydride and 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride Can be mentioned.

  The tetracarboxylic dianhydride used in the present invention 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. Tetracarboxylic dianhydride is preferable as a component of the polyester resin of the present invention from the viewpoint of pigment adsorptivity because it forms a dispersant having two carboxyl groups in one unit of polyester by reaction with polyol. .

  Furthermore, what is preferably used in the present invention is an aromatic tetracarboxylic dianhydride, more preferably a tetracarboxylic dianhydride having two or more aromatic rings, from the viewpoint of adsorptivity to the pigment. is there. Aromatic carboxylic acids have higher pigment adsorption capacity than aliphatic carboxylic acids, and carboxylic acids having two or more aromatic rings are skeletons suitable for pigment adsorption and have high heat resistance.

  Specific examples include aromatic tetracarboxylic dianhydrides represented by the following general formula (2) or general formula (3).

  General formula (2):

(In general formula (2), k is an integer of 1 or 2.)

General formula (3):

(In General Formula (3), Q ₁ is a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, General Formula (4) :

Or a group represented by the general formula (5):

It is group represented by these. )

  In addition, a compound having one carboxylic acid anhydride group in the molecule or a compound having three or more carboxylic acid anhydride groups is used in combination, that is, a polycarboxylic acid other than tetracarboxylic dianhydride contained in the polycarboxylic acid anhydride used in the present invention. Acid anhydrides can also be used.

  Polycarboxylic acid anhydrides other than tetracarboxylic dianhydrides contained in the polycarboxylic acid anhydrides used in the present invention are dicarboxylic acid anhydrides, tricarboxylic acid anhydrides, and anhydrides of compounds having 5 or more carboxylic acids. From the standpoint of adsorptivity to the pigment, a tricarboxylic acid anhydride in which two carboxyl groups are generated in one unit of the polyester resin by reaction with a polyol is preferable in the design of the polyester resin. The blending amount will be described later.

  Examples of the tricarboxylic acid anhydride include an aliphatic tricarboxylic acid anhydride or an aromatic tricarboxylic acid anhydride.

  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- 1,2-anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride, etc. are mentioned.

  Examples of the aromatic tricarboxylic acid include benzenetricarboxylic 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 Products), 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid anhydride, 3,4,4′-biphenyl tricarboxylic acid anhydride, 2,3,2 ′ -Biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, 3,4,4'-biphenyl Sulfonic tricarboxylic acid anhydrides.

  Of these, aromatic tricarboxylic acid anhydrides are preferably used in the present invention from the viewpoint of adsorptivity to pigments.

  C. I. As a use ratio of Pigment Yellow 139 and the polyester resin, C.I. I. It is preferable to contain 5-30 mass parts of polyester resins with respect to 100 parts of pigment yellow 139, It is more preferable to contain 10-25 mass parts, It is further more preferable to contain 15-20 mass parts.

  Solvent salt milling is preferred as the method for producing the pigment composition of the present invention. Solvent salt milling is a mixture of a pigment composition, a water-soluble inorganic salt, and a water-soluble organic solvent, heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading mechanically while cooling, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. A kneader having a high grinding effect (manufactured by Inoue Seisakusho Co., Ltd.) is desirable as the kneader. The water-soluble inorganic salt serves as a grinding aid, and the pigment composition is ground using the high hardness of the inorganic salt during solvent salt milling, thereby generating an active surface and crystal growth. It is thought to happen. Therefore, at the time of kneading, grinding and crystal growth of the pigment composition occur simultaneously, and the primary particle diameter of the pigment composition obtained varies depending on the kneading conditions.

The method for producing the pigment composition will be described more specifically.
First, (a) C.I. I. A small amount of (c) a water-soluble organic solvent is added as a wetting agent to a mixture of Pigment Yellow 139 and (b) a water-soluble inorganic salt, and after kneading strongly with a kneader or the like, the kneaded product is poured into water. Stir with a high speed mixer or the like to form a slurry. Here, examples of the kneader used in the solvent salt milling process include a two-roll, a three-roll, a ball mill, a tron mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single screw or a twin screw extruder. In the present invention, at the time of solvent salt milling, (d) the compound represented by the general formula (1) and / or (e) the polyester dispersant is used in combination with the organic solvent (c), thereby providing a finer pigment. Is obtained. Note that (d) the timing of adding the compound represented by the general formula (1) and (e) the polyester dispersant may be added in the initial stage of the solvent salt milling process, or may be added in divided portions. good.

  Next, the slurry is filtered and washed with water, and if necessary, dried to obtain a finer pigment. In addition, when using it disperse | distributing to an oil-based varnish, it is also possible to disperse | distribute the process pigment (it is called a filter cake) before drying to an oil-based varnish, removing water by the method generally called flushing. When dispersed in an aqueous varnish, the treated pigment does not need to be dried, and the filter cake can be dispersed in the varnish as it is.

  The internal temperature of the kneader can be operated at 20 to 150 ° C, but the internal temperature is preferably 20 to 80 ° C from the viewpoint of fine primary particles. More preferably, it is 45 degreeC-70 degreeC. When the heating temperature is 80 ° C. or lower, crystal growth hardly occurs and the primary particle diameter of the pigment composition can be reduced, and therefore it is preferable as a color filter colorant. The kneading time for the solvent 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 pigment composition subjected to the solvent salt milling treatment and the cost required for the solvent salt milling treatment.

  By optimizing the conditions for solvent salt milling of the pigment composition, it is possible to obtain a pigment composition having a sharp particle size distribution with a very fine primary particle size and a wide distribution range. .

  In the present invention, by adding the compound represented by the general formula (1) and / or the polyester resin to the pigment composition, a pigment composition with finer particles than ever can be obtained.

  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 mass, and 400 to 1500 parts by mass with respect to a total of 100 parts by mass of the compound represented by Pigment Yellow 139 and General Formula 1, from the viewpoints of processing efficiency and production efficiency. It is more preferable to use parts. The particle diameter of the water-soluble inorganic salt is not particularly limited, but is preferably 1 to 50 μm in volume-based median particle diameter (D50). When D50 is 50 μm or less, the processing time for making the crude pigment yellow 139 fine is short, and when D50 is 1 μm or more, less energy is required to obtain a water-soluble inorganic salt. The particle diameter of the water-soluble inorganic salt can be determined using a dry-type laser diffraction particle size distribution analyzer.

  The water-soluble organic solvent functions to wet the yellow colorant 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 wet pulverization and the solvent easily evaporates. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, monoacetin, diacetin, triacetin, tripropionin, tributyrin, 2-methylpentane-2.4-diol, 2.4-diethyl-1.5-pentanediol, 2-ethyl-1,3-hexanediol, 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 Bruno ethyl ether, polypropylene glycol of the liquid is used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 mass%, more preferably 50 to 500 mass%, based on the total mass of the yellow colorant (100 mass%).

  In the kneaded composition, if necessary, further additives such as dispersion aids, plasticizers, dispersants, surfactants, resins, or calcium carbonate, barium sulfate, and silica, which are generally used as extender pigments, etc. These inorganic pigments may be used in combination. Moreover, in order to adjust a hue, you may mix and process with another pigment.

  The pigment composition of the present invention can be used as a colored composition by forming a composition together with a binder resin and an organic solvent.

<Method for producing colored composition>
The coloring composition of the present invention is a mixture of the above-described pigment composition, binder resin, and organic solvent, and is finely dispersed using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. It can be dispersed and manufactured. Moreover, a yellow pigment, a red pigment, and a green pigment can be used for the coloring composition of this invention as needed. Moreover, the coloring composition of this invention can also be manufactured by mixing what disperse | distributed the coloring agent etc. finely in binder resin and the organic solvent separately.

When producing a yellow coloring composition using the pigment composition of the present invention, only the pigment composition may be used. 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, Yellow pigments such as 82,185,187,188,193,194,199,213 may be added.
In this case, the C.I. of the present invention based on the total amount of the colorant (the total amount of CI Pigment Yellow 139 of the present invention and other yellow pigments). I. The content of Pigment Yellow 139 varies depending on the required color characteristics, but is preferably 10% by mass or more from the viewpoint of obtaining sufficient brightness.

  When the color filter coloring composition produced using the pigment composition of the present invention is used as a red coloring composition, a red pigment can be added. Examples of the red pigment to be added 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, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 255, 264, 269, 270, 272, 273, 274, 276, 277, 278, Mention may be made of red pigments such as 279, 280, 281, 282, 283, 284, 285, 286 or 287. Other red dyes that can be used in the colorant include xanthene series, azo series (pyridone series, barbituric acid series, metal complex series, etc.), disazo series, anthraquinone series, and the like. Specifically, C.I. I. And salt forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338. Among them, C.I. I. It is preferable to use one or more selected from among CI Pigment Red 177, 242, 254, and 269. Red pigments and C.I. I. The mass ratio with Pigment Yellow 139 is preferably 100: 5 to 100: 80. If it is 100: 4 or less, it is difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. Further, when the ratio is 100: 81 or more, the coloring power may be lowered. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

  Moreover, when using the coloring composition for color filters manufactured using the pigment composition of this invention as a green coloring composition, a green pigment can be added. Examples of the green pigment to be added include C.I. I. Pigment Green 2, 7, 10, 36, 37, 58, etc. are used. Among them, C.I. I. It is preferable to use one or more selected from CI Pigment Green 7, 36, and 58. Green pigment and C.I. I. The mass ratio with Pigment Yellow 139 is preferably 100: 5 to 100: 200. If the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 to 450 nm, and the color purity may not be increased. On the other hand, if the ratio exceeds 100: 200, the dominant wavelength tends to be a long wavelength, and the deviation from the NTSC target hue may become large. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

  When the fine colorant is dispersed in a transparent resin using a dispersing machine such as a sand mill, the dispersed particles are dispersed in a state of dispersed particles composed of secondary particles in which a plurality of primary particles are collected. The particle size gradually decreases and eventually becomes dispersed in the form of primary particles, but the dispersed state is controlled by the size of the dispersed particles, and the average diameter of the dispersed particles is within the range of 50 nm to 150 nm. It is dispersed so that

  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 coloring composition for a color filter, it is required that a thin film is applied and the surface of the coating film is smooth, so that it has a low viscosity and a Newtonian flow. 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 colorant 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. A pigment dispersion with a very high contrast ratio can be obtained.

<Removal of coarse particles>
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. 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.

<Binder resin>
The binder resin (excluding the polyester resin) disperses, dyes, or penetrates the colorant, and examples thereof include a thermoplastic resin. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the colorant is fixed, heat resistance is improved, and fading (deterioration of spectral characteristics) 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.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin is used as a photosensitive coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and The balance of the aromatic group is important for the dispersibility, penetrability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin is preferably used in an amount of 20 parts by mass or more with respect to 100 parts by mass of the total mass of the colorant because the film formability and various resistances are good, and the colorant concentration is high and good color characteristics are obtained. Since it can express, it is preferably used in an amount of 1000 parts by mass or less.

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

Examples of the vinyl-based alkali-soluble resin copolymerized with 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.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (i) and (ii).

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

  Examples of the unsaturated ethylenic 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.

  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 also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

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

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

  Examples of unsaturated ethylenic monomers 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 unsaturated ethylenic 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.

<Solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the 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-butylal 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 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 Recall 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, methyl isobutyl Tons, methylcyclohexanol, acetate 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.

  The solvent can be used in an amount of 100 to 10000 parts by mass, preferably 500 to 5000 parts by mass with respect to 100 parts by mass of the colorant in the coloring composition.

<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 Ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate, methacrylic acid ester, (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 content of the photopolymerizable monomer is preferably 5 to 500 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 10 to 400 parts by mass from the viewpoint of photocurability and developability. .

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent 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 a benzoin compound such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p- Toxiphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis ( Trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl Triazine compounds such as-(4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoylo Shim)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound 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 photopolymerization initiator content is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 5 to 400 parts by mass from the viewpoint of photocurability and developability.

The colored composition of the present invention contains C.I. of the present invention depending on the hue of the filter segment to be formed. I. In addition to Pigment Yellow 139, other organic or inorganic colorants can be included. Examples of the organic colorant include dyes, organic pigments, natural pigments, and the like, and examples of the inorganic colorant include inorganic pigments. The inorganic pigment includes extender pigments. As the colorant, a colorant having high color developability and high heat resistance, particularly a colorant having high heat decomposition resistance is preferable, and an organic colorant is usually used, and an organic pigment is particularly preferable. Organic or inorganic colorants can be used alone or in admixture of two or more.
Below, the specific example of the organic pigment which can be used for the coloring composition of this invention is shown with a color index number.

In the case of forming a yellow filter segment from the colored composition of the present invention, 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, It can be used in combination with the yellow pigments such as 82,185,187,188,193,194,199,213.
In this case, the C.I. of the present invention based on the total amount of the colorant (the total amount of CI Pigment Yellow 139 of the present invention and other yellow pigments). I. The content of Pigment Yellow 139 varies depending on the required color characteristics, but is preferably 10% by mass or more from the viewpoint of obtaining sufficient brightness. When particularly high lightness is required, other yellow pigments are not used in combination, and C.I. I. It is preferable to use only pigment yellow 139.

In the case of forming a green filter segment from the colored composition of the present invention, C.I. I. Green pigments such as CI Pigment Green 7, 10, 36, 37 are used in combination.
In this case, the C.I. of the present invention based on the total amount of the colorant (the total amount of CI Pigment Yellow 139 of the present invention and the green pigment). I. The content of Pigment Yellow 139 is preferably 0.01 to 90% by mass, and particularly preferably 10 to 50% by mass. C. of the present invention. I. When the content of Pigment Yellow 139 is less than 0.01% by mass, it is too blue and the brightness is low, and when it exceeds 90% by mass, it shifts to yellowish green and the hue is not good.
In addition, C.I. I. A part of the pigment yellow 139 can be replaced with the other yellow pigment.

When forming a red filter segment from the colored composition of the present invention, a normal red pigment is used in combination.
Examples of red pigments include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 269, 270, 272, etc. can be used. In this case, the C.I. of the present invention based on the total amount of the colorant (the total amount of CI Pigment Yellow 139 of the present invention and the green pigment). I. The content of Pigment Yellow 139 is preferably 0.01 to 90% by mass, and particularly preferably 1 to 30% by mass.

  In addition, the coloring composition of the present invention has titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, etc. in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness. Inorganic colorants such as zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, chromium green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like can be included.

  When the coloring composition of the present invention contains two or more kinds of coloring agents, the coloring composition of the present invention mixes two or more kinds of coloring agents, and then the obtained coloring agent mixture is used as necessary. Along with the photopolymerization initiator, it can be produced by finely dispersing in a colorant carrier by a known method. In addition, the coloring composition of the present invention can be produced by mixing each colorant separately finely dispersed in a colorant carrier.

  Further, in the coloring composition of the present invention, the colorant is sufficiently dispersed in the colorant carrier, and applied to a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to make it easier to form, a solvent can be included. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone. , Ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent and the like, and these are used alone or in combination.

  In addition, the colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. 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 ethers such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite.

  The coloring composition of the present invention can be prepared in the form of inkjet ink, gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type colored resist material. The colored resist material is composed of C.I. of the present invention in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, a monomer, and a photopolymerization initiator. I. Pigment Yellow 139 and other colorants as required are dispersed.

C. of the present invention. I. Pigment Yellow 139 and other colorants used as required include a total of 1... In the coloring composition when the filter segment is formed by a photolithographic method. It is preferable to contain in the ratio of 5-7 mass%. Moreover, when forming a filter segment by a printing method, it is preferable to contain in the ratio of 1.5-40 mass% in total in a coloring composition. In any case, the colorant is preferably contained in the final filter segment in a proportion of 10 to 40% by mass, more preferably 20 to 40% by mass, with the remainder from the resinous binder provided by the colorant carrier. Become substantial.

  The colored composition of the present invention is prepared by means of centrifugal separation, sintered filter, membrane filter, or the like. The coarse particles are 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more. It is preferable to remove the mixed dust.

Next, the color filter of the present invention will be described.
The color filter of the present invention comprises at least one red filter segment, at least one blue filter segment, at least one green filter segment, wherein the at least one red filter segment comprises a red pigment. Formed using the composition.
The color filter of the present invention further includes at least one red filter segment, at least one blue filter segment, and at least one green filter segment, wherein the at least one green filter segment includes a green pigment. It is formed using the coloring composition.

The blue filter segment can be formed using a normal blue coloring composition. The blue coloring composition is a C.I. I. Instead of CI Pigment Yellow 139, for example, C.I. I. This is a composition obtained using a blue pigment such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60 or the like. Blue coloring compositions include C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 32, and 42 can be used in combination.

The color filter of this invention can be manufactured by forming the filter segment of each color on a transparent substrate using the coloring composition of this invention by the printing method or the photolithographic method.
As the transparent substrate, a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.

  The formation of each color filter segment by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as the above various printing inks. Therefore, the color filter manufacturing method is low-cost and excellent in mass productivity. ing. 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 forming each color filter segment by a photolithography method, the colored composition prepared as the solvent developing type or alkali developing type colored resist material is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, etc. By a coating method, coating is performed so that the dry film thickness is 0.2 to 5 μm. 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 an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to 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 material, a water-soluble or alkali-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, 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 transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there.
The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate.

    The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. Unless otherwise specified, “parts” and “%” represent “parts by mass” and “mass%”, respectively. In addition, “yellow colorant” in the following examples corresponds to “pigment composition”.

  The compounds A to K were used as the compound represented by the general formula (1) used in the present invention. In addition, the following compounds L and M were used as comparative compounds.

<Manufacture of colorant (pigment composition)>
[Example 1]
Production of Yellow Colorant 1 C.I. I. 100 parts of Pigment Yellow 139 (BASF's “Pariol Yellow D1819-ZP”), sometimes abbreviated as Y139), 1 part of Compound A, 1200 parts of sodium chloride as a water-soluble inorganic salt, and as a water-soluble organic solvent 120 parts of diethylene glycol was charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 12 hours, and wet pulverized (solvent salt milling). The obtained kneaded composition was poured into 3000 parts of warm water, stirred for 1 hour to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried overnight at 80 ° C. to obtain 98 parts of pigment. A yellow colorant 1 as a composition was obtained.

[Comparative Example 1]
Yellow colorant 6
BASF “Pariotor Yellow D1819-ZP” was used as the yellow colorant 6.

[Comparative Example 2]
Yellow colorant 7
As a pigment, C.I. I. 100 parts of Pigment Yellow 139 (BASF Corporation “Pariotor Yellow D1819-ZP”), sometimes abbreviated as Y139), 1200 parts of sodium chloride as a water-soluble inorganic salt, and 120 parts of diethylene glycol as a water-soluble organic solvent A 1 gallon kneader (manufactured by Inoue Seisakusho) was charged, kneaded at 60 ° C. for 12 hours, and wet pulverized (solvent salt milling). The obtained kneaded composition was poured into 3000 parts of warm water, stirred for 1 hour to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried overnight at 80 ° C. to obtain 98 parts of pigment. A yellow colorant 7 as a composition was obtained.

[Examples 2 to 25, Comparative Examples 3 to 6]
Production of yellow colorants 2 to 5 and 8 to 31 Yellow colorants 2 to 31 were obtained in the same manner as in Example 1 except that the materials and preparation amounts shown in Table 1 were changed. In the table, the half width of each 2θ peak and the specific surface area in the X-ray diffraction spectrum of the obtained colorant (pigment composition) are shown.

  The polyester resin used in the present invention was produced by the following method.

<Manufacture of polyester resin>
The manufacturing method of the polyester resin used for this invention is demonstrated. Prior to the production of the polyester resin, a method for measuring the weight average molecular weight of the polyester resin and a method for measuring the acid value will be described.

(Measurement method of weight average molecular weight)
The weight average molecular weight is determined by using two separation columns “TSK-GEL SUPER HZM-N” connected in series in gel permeation chromatography (GPC) “HLC-8220GPC” (manufactured by Tosoh Corporation). It is the polystyrene conversion value measured using tetrahydrofuran (THF) for the phase.

(Measurement method of acid value)
The acid value was measured according to a JIS standard measuring method (JIS K 5601-2-1: 1999).

  The polyester resin used for this invention was manufactured in accordance with the method described in Unexamined-Japanese-Patent No. 2010-223388 and Unexamined-Japanese-Patent No. 2009-155406. Below, the manufacturing method of a polyester resin is demonstrated concretely by a manufacture example.

[Production Example 1]
Production of Polyester Resin (S1) 80.0 parts of methyl methacrylate and 20.0 parts of t-butyl acrylate were charged into a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., and a solution prepared by dissolving 0.1 part of 2,2′-azobisisobutyronitrile (AIBN) in 45.7 parts of cyclohexanone was added to 6.0 parts of thioglycerol. Reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. At this time, the weight average molecular weight was 4300. Next, 9.7 parts of pyromellitic dianhydride (PMA: manufactured by Daicel Chemical Industries, Ltd.), 70 parts of cyclohexanone, and 1,8-diazabicyclo- [5.4.0] -7-undecene (DBU: as catalyst) 0.2 parts) was added and reacted at 120 ° C. for 7 hours. The reaction was completed after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After completion of the reaction, the non-volatile content was adjusted to 50% by mass to obtain a polyester dispersant S1 having an acid value of 43 mgKOH / g and a weight average molecular weight of 8,100.

[Production Examples 2 to 8]
Polyester resins (S2 to S8) were synthesized in the same manner as in Production Example 1 except that the materials and preparation amounts described in Production Table 2 were changed to obtain polyester resins S2 to S8, respectively.

[Example 26]
Production of yellow colorant 32 C.I. I. 100 parts of Pigment Yellow 139 (BASF Corporation “Pariol Yellow D1819-ZP”), which may be abbreviated as Y139), 5 parts of polyerter resin S1 in terms of solid content, 1200 parts of sodium chloride as a water-soluble inorganic salt, and As a water-soluble organic solvent, 120 parts of diethylene glycol was charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 12 hours, and wet pulverized (solvent salt milling). The obtained kneaded composition was poured into 3000 parts of warm water, stirred for 1 hour to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried overnight at 80 ° C. to obtain 98 parts of pigment. A yellow colorant 32 as a composition was obtained.

[Examples 27 to 36, Comparative Examples 7 to 8]
Production of yellow colorants 33 to 44 Yellow colorants 33 to 44 were obtained in the same manner as in Example 26 except that the materials and preparation amounts shown in Table 3 were changed. In the table, the half width of each 2θ peak and the specific surface area in the X-ray diffraction spectrum of the obtained colorant (pigment composition) are shown.

[Example 37]
Production of yellow colorant 45 C.I. I. 100 parts of Pigment Yellow 139 (BASF Corporation “Pariotorero D1819-ZP”), which may be abbreviated as Y139), 1 part of Compound A, 7 parts of Polyerter resin S1, 1200 parts of sodium chloride as a water-soluble inorganic salt In addition, 120 parts of diethylene glycol as a water-soluble organic solvent was charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 12 hours, and wet pulverized (solvent salt milling). The obtained kneaded composition was poured into 3000 parts of warm water, stirred for 1 hour to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried overnight at 80 ° C. to obtain 98 parts of pigment. A yellow colorant 45 as a composition was obtained.

[Examples 38 to 60, Comparative Examples 9 to 10]
Production of yellow colorants 46 to 70 Yellow colorants 46 to 70 were obtained in the same manner as in Example 30, except that the materials and preparation amounts shown in Table 4 were changed. In the table, the half width of each 2θ peak and the specific surface area in the X-ray diffraction spectrum of the obtained colorant (pigment composition) are shown.

[Evaluation method]
<Measurement of X-ray diffraction spectrum>
The obtained pigment or pigment composition was subjected to X-ray diffraction spectrum measurement under the following conditions.
Apparatus: Rigaku X-RAY DIFFRACTOMETER RINT-2100 (manufactured by Rigaku Corporation)
X-ray source: CuKα
Sampling width: 0.02 °
Divergent slit: 1 °
Scattering slit: 1 °
Receiving slit: 0.3mm
Voltage: 40 kV
Current: 40 mA
Measurement range: 5.0 ° to 40.0 °
Step angle: 0.02 °
Step time: 1.2 seconds

<Half width>
About the obtained X-ray-diffraction spectrum, the half value width of the peak was calculated | required by performing data processing on the following conditions. Here, the half width is a value of a Bragg angle defined by a peak width at an intensity position that is ½ of the X-ray diffraction intensity at a certain 2θ peak.

The half width was obtained as follows. First, the X-ray diffraction intensity of 2θ = x was smoothed by the B-spline method. Next, at the peak value for which the half width is to be calculated (for example, 2θ = 19.8 ± 0.5 °), the peak indicating the maximum diffraction intensity is A,
2x in A is Ax,
B indicates a point showing the minimum diffraction intensity within a range of 2θ of Ax or less and Ax−1.0 ° or more.
A point indicating the minimum diffraction intensity within a range where 2θ is Ax or more and Ax + 1.8 ° or less is C,
The straight line connecting B and C is the baseline,
D, the intersection of the perpendicular line drawn from A to the 2θ axis and the baseline
E, the intersection of the line AB passing through the midpoint of A and D and parallel to the baseline, and the curve AB
F, the intersection of the line AC passing through the midpoint of A and D and parallel to the baseline, and the curve AC
2θ in E is Ex, 2θ in F is Fx,
Fx−Ex was defined as the half width of A (Δ2θ).
In addition, the half value width was calculated for 2θ = 9 ± 0.5 °, 12 ± 0.5 °, 19.8 ± 0.5 °, and 26 ± 0.5 ° as target peak values. .

<Specific surface area>
The BET specific surface area of the pigment or pigment composition was measured according to JIS Z 8830-1990 (Method for measuring specific surface area of powder by gas adsorption) in the nitrogen adsorption method.

<Weight average molecular weight of binder resin>
The weight average molecular weight (Mw) of the resin was measured by gel permeation chromatography (GPC) equipped with an RI detector (manufactured by Tosoh Corporation). When measuring by GPC, it measured at 23 degreeC using the TSKgel column (made by Tosoh Corporation) and using tetrahydrofuran (THF) as a developing solvent. Measured in terms of polystyrene. The molecular weight is a polystyrene equivalent value.
The weight average molecular weight of the resin was measured under the following conditions.
Tetrahydrofuran (THF) was added to the specimen and allowed to stand for 12 hours, and then the THF solution of the specimen was filtered, and the molecular weight of the specimen dissolved in the filtrate was measured. The measurement was performed by gel permeation chromatography (GPC), and the molecular weight was calculated from a calibration curve prepared with standard polystyrene. GPC apparatus: HLS-8120 GPC column manufactured by Tosoh Corporation Co., Ltd .: TSK Guardcolumn SuperH-HT / SK-GEL / SuperHM-M three-linked flow rate: 1.0 ml / min (THF) manufactured by Tosoh Corporation

<Method for producing binder resin solution>
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Was added to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, and the temperature was raised to 80 ° C. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

<Preparation of yellow coloring composition>
[Example 101]
(Preparation of yellow coloring composition 1)
After stirring and mixing a mixture consisting of the following components uniformly, using a zirconia bead having a diameter of 0.5 mm, the mixture was dispersed for 5 hours in an Eiger mill (Eiger Japan “Mini Model M-250 MKII”). The mixture was filtered through a 5 μm filter to produce a yellow coloring composition 1.
Yellow colorant 1 12.0 parts Acrylic resin solution 1 8.0 parts Propylene glycol monomethyl ether acetate 80.0 parts

[Examples 102 to 160, Comparative Examples 101 to 110]
(Preparation of yellow colored compositions 2 to 70)
Except having changed the yellow coloring agent 1 into the yellow coloring agents 2-70, respectively, it carried out similarly to Example 101 and produced the yellow coloring compositions 2-70, respectively.

<Evaluation of coloring composition>
The contrast ratio, viscosity, and color characteristics of the obtained colored composition (1-70) were evaluated by the following methods. Table 5 shows the evaluation results.

(Contrast evaluation)
The obtained colored composition was placed on a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm, using a spin coater, changing the number of revolutions, and after heat treatment at 230 ° C., x = 0.420 in a C light source. Three coated substrates were prepared so as to be. Drying conditions were 5 minutes at 60 ° C. and 20 minutes at 230 ° C. after coating. The contrast ratio was measured, and the contrast at x = 0.420 in the C light source was determined from the three points of data by the primary correlation method. It was.

A method for measuring the contrast ratio of the coating film will be described.
(Measurement method of contrast ratio (CR) of coating film)
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the dried coating film of the colored composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing planes of the polarizing plate and the polarizing plate are parallel, light is transmitted through the polarizing plate, but if the polarizing plane is perpendicular, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dried coating film of the colored composition, scattering by the pigment particles occurs, resulting in deviation in a part of the polarization plane. When the amount of light transmitted through the plate is reduced and the polarizing plate is perpendicular, part of the light is transmitted through the polarizing plate. This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.
(Contrast ratio (CR)) = (Brightness when parallel) / (Brightness when direct)

  Accordingly, when scattering occurs due to the pigment in the coating film, the brightness when parallel is reduced and the brightness when perpendicular is increased, the contrast ratio is lowered. A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

(Evaluation of color characteristics)
Similar to the evaluation of contrast, three coated substrates are prepared, and the chromaticity is measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The lightness (Y) and y at 420 were obtained by the primary correlation method.

(Evaluation of viscosity)
The viscosity of the coloring composition was measured at 25 ° C. using an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.).

  According to Table 5, the X-ray half width at 19.8 ± 0.5 ° is 0.75 or more, the contrast ratio is good, and the X-ray half width is 0.85 or more. On the other hand, all of Comparative Examples 101 to 110 in which the X-ray half width at 19.8 ± 0.5 ° was smaller than 0.75 resulted in inferior to the contrast ratio of the example of the present invention.

<Production method of fine pigment>
(Preparation of red fine pigment [A1-2])
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“CROMOPHTAL RED A2B” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red fine pigment [A1-2] were obtained. The specific surface area of the red fine pigment [A1-2] was 70 m ² / g, and the average primary particle size by TEM observation was 54 nm.

(Preparation of blue fine pigment)
Phthalocyanine blue pigment C.I. I. 200 parts of Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of blue fine pigment-2 were obtained. The specific surface area of the blue fine pigment 2 was 80 m ² / g, and the average primary particle size by TEM observation was 50 nm.

(Production of green fine pigment)
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a green fine pigment were obtained. The specific surface area of the green fine pigment was 75 m ² / g, and the average primary particle size by TEM observation was 51 nm.

(Production of purple fine pigment)
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a violet fine pigment were obtained. The specific surface area of the purple fine pigment was 95 m ² / g, and the average primary particle size by TEM observation was 45 nm.

<Preparation of red coloring composition>
(Preparation of colorant P-1)
The following mixture 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) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A pigment dispersion (P-1) was produced by filtration using a filter.
Red fine pigment [A1] 11.0 parts (CI Pigment Red 254)
Acrylic resin solution 1 40.0 parts Propylene glycol monomethyl ether acetate 48.0 parts Resin type dispersant 1.0 part ("EFKA4300" manufactured by BASF)

(Preparation of pigment dispersion (P-2 to 4))
Hereinafter, pigment dispersions (P-2 to 4) were produced in the same manner as the pigment dispersion (P-1) except that the pigments were changed to the pigments shown in Table 6.

<Method for producing blue and green resist materials>
(Preparation of blue resist material)
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a blue resist material.
Pigment dispersion (P-2) 48.0 parts Pigment dispersion (P-4) 12.0 parts Acrylic resin solution 1 11.0 parts Trimethylolpropane triacrylate 4.2 parts ATMPT ")
1.2 parts of photopolymerization initiator ("Irgacure 907" manufactured by BASF)
Sensitizer 0.4 part ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
Ethylene glycol monomethyl ether acetate 23.2 parts

[Example 201]
(Preparation of red resist material R1-1)
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a resist material (R1-1).
Red coloring composition (P-1) 50.0 parts Yellow coloring composition (Coloring composition 1) 10.0 parts Acrylic resin solution 1 11.6 parts Trimethylolpropane triacrylate 3.6 parts (manufactured by Shin-Nakamura Chemical Co., Ltd.) "NK ester ATMPT")
1.2 parts of photopolymerization initiator ("Irgacure 907" manufactured by BASF)
Sensitizer 0.4 part (Hodogaya Chemical Industries "EAB-F")
Ethylene glycol monomethyl ether acetate 23.2 parts

[Examples 202 to 260, Comparative Examples 201 to 210]
(Production of red resist materials R1-1 to 70)
Except having changed the coloring composition 1 into the coloring compositions 2-70, it carried out like Example 201 and produced red resist material R1-1-70.

[Example 301]
(Preparation of green resist material R2-1)
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a green resist material.
Pigment dispersion (P-3) 45.0 parts Yellow pigment dispersion (Coloring composition 1) 15.0 parts Acrylic resin solution 1 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (manufactured by Shin-Nakamura Chemical Co., Ltd.) "NK ester ATMPT")
Photopolymerization initiator: 1.2 parts ("Irgacure 907" manufactured by BASF)
Sensitizer: 0.4 parts ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
Ethylene glycol monomethyl ether acetate: 23.2 parts

[Examples 302 to 360, Comparative Examples 301 to 310]
(Preparation of green resist materials R2-2 to 2-70)
Except having changed the coloring agent 1 into the coloring agents 2 to 70, it carried out like Example 301 and produced green resist material R2-2 to 2-70.

[Evaluation of red resist material (R1-1 to R1-70)]
The color characteristics (lightness) and contrast ratio of the red resist materials (R1-1 to R1-70) obtained in Examples 201 to 260 and Comparative Examples 201 to 210 were measured by the following methods.

(Evaluation of color characteristics)
Each resist material was coated on a glass substrate so that the red resist material had a thickness x = 0.640 in a C light source, and the substrate was heated at 230 ° C. for 20 minutes. Thereafter, the brightness of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The results are shown in Table 7.

(Contrast ratio evaluation)
The contrast ratio was measured using the same substrate on which the color characteristics were measured. The results are shown in Table 7.

  From Table 7, the contrast ratio of the colorant having a X-ray half-value width of more than 0.75 at 19.8 ± 0.5 ° is good, and the resist material having a value of more than 0.85 is very good. Met. On the other hand, Comparative Examples 201 to 210 using a colorant whose X-ray half width at 19.8 ± 0.5 ° is smaller than 0.75 are inferior to the contrast ratio of the example of the present invention. became.

[Evaluation of green resist materials (R2-1 to R2-70)]
The color characteristics (brightness) and contrast ratio of the green and red resist materials (R2-1 to R2-70) obtained in Examples 301 to 370 and Comparative Examples 301 to 310 were measured by the following method.

(Evaluation of color characteristics)
Each resist material was coated on a glass substrate so that the red resist material had a thickness x = 0.640 in a C light source, and the substrate was heated at 230 ° C. for 20 minutes. Thereafter, the brightness of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The results are shown in Table 8.

(Contrast ratio evaluation)
The contrast ratio was measured using the same substrate on which the color characteristics were measured. The results are shown in Table 8.

From Table 8, the resist material using the colorant whose X-ray half width at 19.8 ± 0.5 ° exceeds 0.75 has a good contrast ratio, and the resist material exceeding 0.85 is very good. Met. On the other hand, Comparative Examples 301 to 310 using coloring materials having an X-ray half width at 19.8 ± 0.5 ° smaller than 0.75 are inferior to the contrast ratio of the example of the present invention. became.

A color filter was produced using the obtained resist material.

(Example 401: Color filter (CF-1))
A black matrix is patterned on a glass substrate, and a red resist material (R1-57) is formed on the substrate by a spin coater in a C light source (hereinafter also used for green and blue) x = 0.640 It was applied to a thickness to form a colored film. The film was irradiated with ultraviolet rays of 300 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, and then the substrate was washed with ion-exchanged water, and this substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. Using the same method, green resist material (R2-57) is applied to a thickness such that y = 0.600, and blue resist material is applied to a thickness such that y = 0.06. A blue filter segment was formed to obtain a color filter (CF-1).

(Production of liquid crystal display device)
A transparent ITO electrode layer was formed on the obtained color filter, and a polyimide alignment layer was formed thereon. A polarizing plate was formed on the other surface of this glass substrate. On the other hand, a TFT array and a pixel electrode were formed on one surface of another (second) glass substrate, and a polarizing plate was formed on the other surface. The two glass substrates prepared in this way are arranged facing each other so that the electrode layers face each other, and are aligned using spacer beads while keeping the distance between the two substrates constant, and an opening for injecting a liquid crystal composition The periphery was sealed with a sealant so as to leave After injecting the liquid crystal composition from the opening, the opening was sealed. The liquid crystal display device thus produced was combined with a backlight unit to obtain a liquid crystal panel.

(Comparative Example 401: Color filter (CF-2))
Hereinafter, a primary color filter (CF-2) and a liquid crystal display device were produced in the same manner as the color filter (CF-1) except that the resist material was changed to the resist material shown in Table 9. The blue resist material was fixed.

[Evaluation of color filter (CF-1 to 2)]
Thereafter, in the obtained liquid crystal display device, a light source is emitted to display a color image, and in the primary color filter, the brightness of the red, green, and blue filter segment portions is measured with a microspectrophotometer ("OSP-" manufactured by Olympus Optical Co., Ltd.). SP200 "), and the brightness of white display in the color filter was determined from the obtained brightness. In addition, the contrast ratio of the red, green, and blue filter segment portions was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.), and white display in the color filter was obtained from the obtained contrast ratio. The contrast ratio was determined. The practical performance of the white display contrast ratio is required to be 6500 or more, and preferably 6500 or more. Table 9 shows the evaluation results of the color filter.

In Example 10, the contrast ratio of white display is higher than that of Comparative Example 401 including a colorant whose X-ray half width at 19.8 ± 0.5 ° is less than 0.75, and satisfies practical performance. there were.

From the above, C.I. X-ray half width at 19.8 ± 0.5 ° exceeds 0.75. I. By using Pigment Yellow 139 colorant, it is possible to obtain a coloring composition and a color filter for red and green color filters having an excellent contrast ratio.

A: Peak B showing the maximum diffraction intensity within the range of 2θ = 19.8 ± 0.5 ° B: Point C showing the minimum diffraction intensity within the range of Ax−1.0 ° or more C: Range of Ax + 1.8 ° or less The point D: which shows the minimum diffraction intensity in FIG. 6A: the intersection of the perpendicular line drawn from the A to the 2θ axis and the baseline E: the line passing through the midpoint of A and D and parallel to the baseline, and the intersection F: A of the curve AB An intersection Ex of the line AC passing through the midpoint of D and parallel to the base line Ex: 2θ at E
Fx: 2θ in F

Claims (9)

In the powder X-ray diffraction diagram indicated by the diffraction intensity for the Bragg angle 2θ measured by CuKα rays,
A peak showing the maximum diffraction intensity within the range of 2θ = 19.8 ± 0.5 ° is A,
2x in A is Ax,
B indicates a point showing the minimum diffraction intensity within a range of 2θ of Ax or less and Ax−1.0 ° or more.
A point indicating the minimum diffraction intensity within a range where 2θ is Ax or more and Ax + 1.8 ° or less is C,
The straight line connecting B and C is the baseline,
D, the intersection of the perpendicular line drawn from A to the 2θ axis and the baseline
E, the intersection of the line AB passing through the midpoint of A and D and parallel to the baseline, and the curve AB
F, the intersection of the line AC passing through the midpoint of A and D and parallel to the baseline, and the curve AC
2θ in E is Ex, 2θ in F is Fx,
When Fx-Ex is the half width of A,
The half width of A is 0.75 or more. I. Pigment Yellow 139.   The half width of A is 0.85 or more. I. Pigment Yellow 139. The C.I. of claim 1 or 2. I. Pigment Yellow 139 and a compound represented by the following general formula (1), I. The pigment composition which contains 0.5-40 mass% of compounds represented by General formula (1) with respect to 100 mass parts of pigment yellow 139.

[In General Formula (1), X ₁ is a group represented by Formula (a). X ₂ is a group represented by the formula (b) or the formula (c). X ₃ is a group represented by formula (a), formula (b), formula (c) or formula (d). ]

[In Formula (a), Y ₁ is NH or O, and R ₁ is a divalent hydrocarbon group having 1 to 8 carbon atoms. R ₂ and R ₃ are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ₂ and R ₃ may be bonded to each other to form a ring. ]

[In Formula (b), Y ₂ is NH or O, and R ₄ is a group represented by Formula (2) or Formula (3) below. R ₅ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms.

[In Formula (c), Y ₃ is NH or O, and R ₆ is a group represented by the following Formula (2) or Formula (3). ]

[In formula (d), Y ₄ is NH or O, and R ₇ is H, a monovalent hydrocarbon group having 1 to 8 carbon atoms, or a group represented by the following formula (e). ]

Wherein (e), R ₈ is a divalent hydrocarbon group having 1 to 8 carbon atoms, R ₉ is H or a hydrocarbon group having 1 to 8 carbon atoms. n is an integer of 1 to 3. ]   The C.I. of claim 1 or 2. I. Pigment Yellow 139 and a polyester resin comprising C.I. I. A pigment composition comprising 5 to 30 parts by mass of a polyester resin with respect to 100 parts by mass of Pigment Yellow 139.   The C.I. of claim 1 or 2. I. Pigment Yellow 139, a pigment composition comprising a compound represented by the general formula (1) and a polyester resin, I. The pigment composition according to claim 3 or 4, comprising 0.5 to 40% by mass of a compound represented by the general formula (1) and 5 to 30 parts by mass of a polyester resin with respect to 100 parts by mass of Pigment Yellow 139. object. C. I. A method for producing a pigment composition according to any one of claims 3 to 5, wherein Pigment Yellow 139 is mixed with a compound represented by the general formula (1) and / or a polyester resin, and solvent salt milling is performed. I. The manufacturing method of the pigment composition which uses 0.5-40 mass parts and / or 5-30 mass parts of polyester resins for the compound represented by General formula (1) with respect to 100 mass parts of pigment yellow 139.   A coloring composition comprising at least a coloring agent, a binder resin, and an organic solvent, wherein the coloring agent is C.I. I. A coloring composition comprising Pigment Yellow 139 or the pigment composition according to any one of claims 3 to 5.   8. The colored composition according to claim 7, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.   9. A color filter comprising a filter segment formed from the colored composition according to claim 7 or 8 on a substrate.

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