JP6926913B2 - Pigment composition for color filter, coloring composition for color filter and color filter - Google Patents

Description

The present invention relates to a miniaturized α-type copper phthalocyanine pigment composition for a color filter, a coloring composition for a color filter using the same, and a color filter.

As the blue organic pigment used in the color filter, a copper phthalocyanine pigment is generally used.

Several polymorphs of crystals are known for copper phthalosinin, but the ones that are particularly useful as coloring materials are α-type, β-type, and ε-type. Among them, the α-type copper phthalocyanine pigment has a reddish color and a vivid color tone, and is a blue pigment used in a wide range of applications such as inks, paints, plastics, and printing. The conventional method for producing an α-type copper phthalocyanine pigment is an acid pacing method in which crude copper phthalocyanine synthesized by a method generally called the Wyler method is dissolved in 90% or more of concentrated sulfuric acid and then introduced into a large amount of water. , The acid slurry method in which a salt of crude copper phthalocyanine and sulfuric acid is prepared in 60 to 80% sulfuric acid and introduced into a large amount of water is the most common. Regarding the particles of the α-type copper phthalocyanine pigment obtained by these methods, the pigment particles obtained by the acid slurry method are relatively coarse particles. On the other hand, the pigment particles obtained by the acid pacing method are extremely fine, but the ink or the like produced by using this pigment has a drawback that the fluidity is inferior. Inks with poor fluidity are not suitable for use in color filters and are not preferable.

As an attempt to improve the fluidity of the α-type copper phthalocyanine pigment, a method of adding an organic solvent during acid pacing has been disclosed. Although the viscosity suitability is improved, the transparency, sharpness and contrast ratio are insufficient. Met. (Patent Document 1)

Most of the copper phthalocyanine pigments used in color filters so far are ε-type, and there is almost no method for obtaining fine α-type copper phthalocyanine for α-type. For the ε-type, a method for obtaining a fine ε-type copper phthalocyanine pigment by using a pigment derivative as described in Patent Documents 2 and 3 is known. On the other hand, α-type copper phthalocyanine used a pigment derivative as a crystal transfer inhibitor (Patent Document 4), but the ink using this pigment had high viscosity and could not be used for color filter applications.

Special Fair 6-43564 Japanese Unexamined Patent Publication No. 2013-203868 Japanese Unexamined Patent Publication No. 2008-185703 Japanese Unexamined Patent Publication No. 2008-274062

An object of the present invention is to provide a pigment composition containing an α-type copper phthalocyanine pigment having a small pigment particle size, a blue coloring composition for a color filter having a high contrast ratio and a low viscosity, and a color filter using the same. be.

As a result of diligent research to solve the above problems, the present inventors have shown the half-value width of a specific peak in the powder X-ray diffraction pattern shown by the diffraction intensity with respect to the diffraction angle 2θ measured by CuKα ray. However, it has been found that an α-type copper phthalocyanine satisfying a certain condition and a coloring composition containing a certain compound can solve the above-mentioned problems.

That is, the present invention shows a point showing the maximum diffraction intensity within the range of 2θ = 15.5 ° ± 0.15 ° in the powder X-ray diffraction diagram shown by the diffraction intensity with respect to the diffraction angle 2θ measured by CuKα rays. 2θ in A and A is Ax, 2θ is Ax or less, and the point showing the minimum diffraction intensity in the range of Ax-4.5 ° or more is the point where B, 2θ is Ax or more and Ax + 3.5 ° or less. The point indicating is C, the straight line connecting B and C is the baseline, the intersection of the perpendicular line drawn from A to the 2θ axis and the baseline is D, and the line passing through the midpoint of A and D and parallel to the baseline. The intersection of the curves AB is E, the line parallel to the baseline through the midpoint of A and D, the intersection of the curves AC is F, 2θ in E is Ex, 2θ in F is Fx, and Fx-Ex is the half price of A. The present invention relates to a pigment composition for a color filter containing an α-type copper phthalocyanine pigment and a pigment derivative, wherein the half-value width when the width is defined as G, and the half-value width G is 1.3 ° or more.

Further, in the embodiment of the present invention, the pigment derivative is a pigment composition for a color filter in which the pigment derivative is a compound represented by the general formula (1), and the compound represented by the general formula (1) is an α-type copper phthalocyanine. The present invention relates to the above pigment composition containing 10 to 50% by mass with respect to the total of the pigment and the compound represented by the general formula (1).

（ただし、Ｐは、無金属または金属フタロシアニン顔料の残基を表し、Ｌは、塩基性置換基、酸性置換基、または置換基を有していても良いフタルイミドメチル基を表し、ｎは１〜８の整数を表す。） General formula (1)

(However, P represents a residue of a metal-free or metallic phthalocyanine pigment, L represents a basic substituent, an acidic substituent, or a phthalimide methyl group which may have a substituent, and n represents 1 to 1. Represents an integer of 8.

Further, the embodiment of the present invention relates to a coloring composition for a color filter, which further comprises a binder resin and an organic solvent in the pigment composition.

（ただし、Ｐは、無金属または金属フタロシアニン顔料の残基を表し、ｂは１〜６の整数を示し、ｄは０〜６の整数を示し、ｆは１〜６の整数を示す。） Further, the present invention is a coloring composition for a color filter, further comprising a compound represented by the general formula (2), and the compound represented by the general formula (2) is contained in the pigment composition. The present invention relates to the above-mentioned coloring composition for a color filter, which comprises 1 to 30% by mass with respect to the total of the α-type copper phthalocyanine pigment and the compound represented by the general formula (2).
General formula (2)

(However, P represents a residue of a metal-free or metallic phthalocyanine pigment, b represents an integer of 1 to 6, d represents an integer of 0 to 6, and f represents an integer of 1 to 6.)

（ただし、Ｐは、無金属または金属フタロシアニン顔料の残基を表し、Ｘは置換基を有していても良いフタルイミドメチル基を表し、ｎは１〜８の整数を表す。） Further, in the present invention, the pigment derivative is a compound represented by the general formula (3), and the compound represented by the general formula (2) is 15 to 15 to the compound represented by the general formula (3). The present invention relates to the above-mentioned coloring composition for a color filter, which comprises 50% by mass.
General formula (3)

(However, P represents a residue of a metal-free or metallic phthalocyanine pigment, X represents a phthalimide methyl group which may have a substituent, and n represents an integer of 1 to 8.)

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

Compared with the conventional α-type copper phthalocyanine pigment composition, the α-type copper phthalocyanine pigment composition of the present invention provides a dispersion having a very high contrast ratio and low viscosity when used in a coloring composition for a color filter. Be done.

FIG. 1 is a schematic view of a powder X-ray diffraction pattern near 2θ = 15.5 ± 0.15 °.

A: Point showing maximum diffraction intensity within the range of 2θ = 15.5 ± 0.15 ° B: Point showing minimum diffraction intensity within the range of Ax-4.5 ° or more C: Ax or more, Ax + 3 Point D showing the minimum diffraction intensity within the range of .5 ° or less: The intersection of the perpendicular line drawn from 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 curve AB 2θ at the intersection point Ex: E of the curve AC and the line passing through the midpoint of the intersection F: A and D and parallel to the baseline.
Fx: 2θ in F

Hereinafter, the present invention will be described in detail. The pigment composition of the present invention is obtained in a powder X-ray diffraction pattern shown by a diffraction intensity with respect to a diffraction angle of 2θ measured by CuKα rays.
The point showing the maximum diffraction intensity within the range of 2θ = 15.5 ° ± 0.15 ° is A,
2θ in A is Ax,
The point where 2θ shows the minimum diffraction intensity within the range of Ax or less and Ax-4.5 ° or more is B.
The point where 2θ shows the minimum diffraction intensity within the range of Ax or more and Ax + 3.5 ° or less is C.
Baseline the straight line connecting B and C,
The intersection of the perpendicular line drawn from A to the 2θ axis and the baseline is D,
The intersection of the line passing through the midpoint of A and D and parallel to the baseline and the curve AB is E,
The intersection of the line passing through the midpoint of A and D and parallel to the baseline and the curve AC is F,
2θ in E is Ex, 2θ in F is Fx,
A pigment containing an α-type copper phthalocyanine pigment and a pigment derivative, wherein the half width when Fx-Ex is the half width of A is G, and the half width G is 1.3 ° or more. It is characterized by being a composition. The half width G is 1.3 ° or more, preferably 1.34 ° or more, and more preferably 1.34 to 1.6 °.

The measurement method for obtaining the powder X-ray diffraction pattern and the calculation method for the full width at half maximum are based on the methods described in the examples.

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

<Α-type copper phthalocyanine>
The α-type phthalocyanine pigment used in the present invention is not particularly limited, but a commercially available α-type phthalocyanine pigment having a large particle size can be used. In addition, the manufacturing method described in JP-A-57-141453, PIGMENT HANDBOOK, Volume 1, pp. 667 (1988), and "Parthalocyanine-Chemistry and Function-" by Hirofusa Shirai and Nagao Kobayashi, pp. 55-62. It can be obtained by synthesizing phthalocyanine by a known production method described in (1997), dissolving it in 60 to 100% sulfuric acid, and then pretreating it by introducing it into a large amount of water.

<Pigment derivative>
The pigment derivative used in the present invention is preferably a pigment derivative represented by the general formula (1).

（ただし、Ｐ：無金属または金属フタロシアニン顔料の残基、Ｌ：塩基性置換基、酸性置換基、または置換基を有していても良いフタルイミドメチル基、
ｎ：１〜８の整数） General formula (1)

(However, P: residue of metal-free or metallic phthalocyanine pigment, L: phthalimide methyl group which may have a basic substituent, an acidic substituent, or a substituent,
n: an integer from 1 to 8)

As a specific example of L, a phthalimide methyl group which may have a substituent such as a phthalimide methyl group, a 4-nitrophthalimide methyl group, a 4-chlorophthalimide methyl group, a tetrachlorophthalimide methyl group, etc.
Carbamoyl group, sulfamoyl group, aminomethyl group, dimethylaminomethyl group, diethylaminomethyl group, dibutylaminomethyl group, piperidinomethyl group, dimethylaminopropylaminosulfonyl group, diethylaminopropylaminosulfonyl group, dibutylaminopropylaminosulfonyl group, morpholinoethylamino Sulfonyl group, dimethylaminopropylaminocarbonyl group, 4- (diethylaminopropylaminocarbonyl) phenylaminocarbonyl group, dimethylaminomethylcarbonylaminomethyl group, diethylaminopropylaminomethylcarbonylaminomethyl group, dibutylaminopropylaminomethylcarbonylaminomethyl group, etc. Basic substituents,
Sulfo Group, Sodium Sulfonato Group, Calcium Sulfonato Group, Aluminum Sulfonato Group, Dodecyl Ammonio Sulphonato Group, Octadecyl Ammonio Sulfonato Group, trimethyl Octadesyl Ammonio Sulfonato Group, Didimethyl Didecyl Ammonio Sulfonato Group, Carboxyl There are acidic substituents such as groups.

The compound represented by the general formula (1) can be used for both the acid pacing method and the salt milling treatment. It is presumed that it functions as a crystal transition inhibitor or a crystal growth inhibitor, and by containing the compound represented by the general formula (1), as a result, finer particles are promoted, so that the contrast ratio is improved and the viscosity is improved. Can be good. When used in the acid pacing method, the compound represented by the general formula (1) is preferably a compound having a neutral L, particularly a phthalimide methyl group. Further, as the compound represented by the general formula (1) when used in the salt milling treatment, a compound represented by the neutral or basic general formula (1) is preferable. Further, the phthalimide methyl group is preferable among the neutral Ls, the dialkylaminopropylaminosulfonyl group is preferable among the basic Ls, and the dimethylaminopropylaminosulfonyl group and the diethylaminopropylaminosulfonyl group are more preferable.

In the present invention, the content of the compound represented by the general formula (1) is the sum of the compound represented by the general formula (1), the α-type copper phthalocyanine pigment and the compound represented by the general formula (1). It is preferably in the range of 10 to 50% by mass. Further, it is more preferably 15 to 40% by mass, further preferably 20 to 30% by mass. The compound represented by the general formula (1) used in the present invention is a compound represented by the general formula (1) when a pigment composition is produced by an acid pacing method or a salt milling treatment together with α-type copper phthalocyanine. As the content increases, the primary particle size of the obtained coloring composition becomes finer, and the contrast ratio of the color filter using the primary particle size can be improved. However, when the addition amount of the compound represented by α-type copper phthalocyanine exceeds 50% by mass in the coloring composition, a remarkable miniaturization effect is not obtained as the addition amount increases, and further, α-type copper phthalocyanine It is not preferable because the coloring power decreases as the content decreases.

The method for producing a pigment derivative used in the present invention is not particularly limited, but Moser and Thomas, "Phythalocyanine Compounds" (Moser and Thomas "Phthalocyanine Compounds") (1983), Shirai Shirai and Kobayashi Nagao, "Phythalocyanine-Chemistry and Function-". (1997), WO2016 / 16335 pamphlet, etc., and other known methods and other suitable methods are used.

<Pigment composition>
The pigment composition of the present invention can be subjected to salt milling or acid pacing. The primary particle size of the pigment composition is preferably 10 nm or more because the dispersion is good. Further, since a filter segment having a high contrast ratio can be formed, it is preferably 100 nm or less. The preferred range is 10 to 80 nm, and the particularly preferred range is 20 to 70 nm. The primary particle size of the pigment composition was determined by a method of directly measuring the size of the primary particles from an electron micrograph taken by a TEM (transmission electron microscope). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment composition were measured, and the average was taken as the particle size of the particles. Next, for 100 or more particles, the volume of each particle is obtained by approximating it to a cube having a obtained particle size, and the volume average particle size is defined as the average primary particle size.

Further, it is necessary to make fine particles while keeping the aspect ratio of the primary particles of the pigment composition small in order to maintain good dispersion. The aspect ratio of the primary particles of the pigment composition referred to in the present invention means the ratio obtained by dividing the length of the long side of the primary particles of the pigment composition measured by TEM by the length of the short side. It is preferably in the range of 1 to 2, and more preferably in the range of 1 to 1.5.

The salt milling treatment is a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent, or a mixture of a pigment, a compound represented by the general formula (1), a water-soluble inorganic salt and a water-soluble organic solvent. In a process of mechanically kneading while heating using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, or a sand mill, and then washing with water to remove water-soluble inorganic salts and water-soluble organic solvents. be. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment composition having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of price. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, most preferably 300 to 1000% by mass, based on the total mass of the pigment (100% by mass). Further, it is more preferable to use an inorganic salt having an average particle size of 0.5 to 50 μm. Such an inorganic salt can be easily obtained by finely pulverizing an ordinary inorganic salt.

The water-soluble organic solvent has a function of wetting the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 2-ethyl-1,3-hexanediol, diacetin , Triacetin, liquid polyprolen glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by mass, most preferably 50 to 500% by mass, based on the total mass of the pigment (100% by mass).

The kneading temperature is preferably 50 ° C. or higher, more preferably 60 ° C. to 100 ° C., and even more preferably 65 ° C. to 90 ° C. If the kneading temperature is less than 50 ° C., the primary particle size of the pigment composition may become too small and the viscosity may increase when the ink is used. On the other hand, if the kneading temperature exceeds 100 ° C., crystal transition to β-type may occur, which is not preferable.

The kneading time is preferably 2 to 24 hours from the viewpoint of balancing the particle size distribution of the primary particles of the salt milling-treated pigment composition and the cost required for the salt milling treatment.

By optimizing the conditions for salt milling the pigment composition, the pigment composition has a very fine primary particle size and a narrow particle size distribution range without crystal transition to the β-type crystal structure. You can get things.

The acid pacing method is a method for producing a treated pigment by co-dissolving an organic pigment in a strongly acidic solvent and taking out the solution in water. As the strongly acidic solvent, sulfuric acid, polyphosphoric acid, chlorosulfonic acid and the like can be used. Industrially, it is desirable to use sulfuric acid from the viewpoint of cost.
When preparing a strongly acidic solvent solution containing α-type copper phthalocyanine and the compound represented by the general formula (1), each powder may be added to the strongly acidic solvent and dissolved, or each of them may be dissolved as a strong acid. After dissolving in the sex solvent, each strong acid solvent solution may be mixed. The order of addition when each powder is added to the strongly acidic solvent is not limited.

The amount of the strongly acidic solvent needs to be increased or decreased depending on the concentration of the strongly acidic solvent, but is not particularly limited as long as it can completely dissolve them. For example, when 98% by mass of sulfuric acid is used, it is preferable to use 3 to 100 times by mass, more preferably 5 to 30% by mass, based on the total mass of α-type copper phthalocyanine and the compound represented by the general formula (1). It is double. When the amount of sulfuric acid is less than this range, it may be difficult to completely dissolve the α-type copper phthalocyanine and the compound represented by the general formula (1) at a low temperature. Moreover, even if it is used more than this range, there is no merit in giving quality, and productivity is lowered, which is uneconomical.

The temperature at which the α-type copper phthalocyanine and the compound represented by the general formula (1) are dissolved in a strongly acidic solvent is not particularly limited, but for example, when 98% by mass of sulfuric acid is used, the temperature is 3 ° C. or higher and 60 ° C. or lower. It is preferably 3 ° C. or higher and 40 ° C. or lower. If the temperature is less than 3 ° C., sulfuric acid will solidify and it will be difficult to stir uniformly, which is not preferable. Further, when it is dissolved at a temperature higher than the above temperature, α-type copper phthalocyanine and the compound represented by the general formula (1) may be decomposed.

In the present invention, the temperature at which a strongly acidic solvent solution of α-type copper phthalocyanine and the compound represented by the general formula (1) is mixed with water and precipitated is not particularly limited. However, although it depends on the type of compound represented by the general formula (1) used, in many cases, the particles tend to be finer at low temperatures than when precipitated at high temperatures, so the temperature is 0 ° C. or higher and 60. It is preferable to carry out at ° C or lower. As the water used at that time, any industrially usable water such as tap water, well water, and hot water can be used, but in order to reduce the temperature rise at the time of precipitation, pre-cooled water can be used. It is preferable to use.

The method for mixing the strong acid solvent solution and water is not particularly limited, and any method may be used as long as the α-type copper phthalocyanine and the compound represented by the general formula (1) can be completely precipitated. For example, it can be precipitated by a method of injecting a strong acid solvent solution into ice water prepared in advance, or a method of continuously injecting into running water using an device such as an aspirator.

The pigment composition of the present invention can be obtained by filtering and washing the slurry obtained by the above method to remove acidic components, and then drying and pulverizing the slurry.

（ただし、Ｐは、無金属または金属フタロシアニン顔料の残基を表し、ｂは１〜６の整数を示し、ｄは０〜６の整数を示し、ｆは１〜６の整数を示す。） <Coloring composition>
The pigment composition can be used as a coloring composition together with a compound represented by the general formula (2), a resin-type pigment dispersant, a binder resin and an organic solvent. At that time, in addition to the pigment composition of the present invention, other colorants may be used in combination.
General formula (2)

(However, P represents a residue of a metal-free or metallic phthalocyanine pigment, b represents an integer of 1 to 6, d represents an integer of 0 to 6, and f represents an integer of 1 to 6.)

The compound represented by the general formula (2) in the coloring composition is preferably 1 to 30% by mass with respect to the total of the pigment in the pigment composition and the compound represented by the general formula (2). Further, it is more preferably 5 to 25% by mass, and most preferably 10 to 20% by mass.

（ただし、Ｐは、無金属または金属フタロシアニン顔料の残基を表し、Ｘは置換基を有していても良いフタルイミドメチル基を表し、ｎは１〜８の整数を表す。） In the coloring composition for a color filter of the present invention, it is preferable that the pigment derivative in the pigment composition is a compound represented by the general formula (3). The compound represented by the general formula (3) is a compound in which L of the general formula (1) is a phthalimide methyl group which may have a substituent.
General formula (3)

(However, P represents a residue of a metal-free or metallic phthalocyanine pigment, X represents a phthalimide methyl group which may have a substituent, and n represents an integer of 1 to 8.)

In the present invention, the content of the pigment composition containing the compound represented by the general formula (3) and the compound represented by the general formula (2) is higher than that of the compound represented by the general formula (3). The compound represented by the general formula (2) is preferably in the range of 15 to 50% by mass, more preferably 20 to 45% by mass, still more preferably 25 to 40% by mass.

<Resin-type pigment dispersant>
As the resin type pigment dispersant, those having a basic group, an acidic group, an aromatic group or the like in a block or at random in the main chain or the end of the linear resin and the main chain or the side chain of the comb-shaped resin are preferable. Specifically, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, and long Chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly (lower alkyleneimine) with polyesters having free carboxyl groups, and salts thereof are used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble. Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, phosphoric acid esters and the like are used. These can be used alone or in admixture of two or more.

Examples of commercially available resin-type pigment dispersants include various solvent dispersants such as SOLSPERSE 13240, 20000, 24000, 26000, 28000, 31000 and 76500 (all manufactured by Nippon Lubrizol Co., Ltd.), Disperbyk 110, 111, 160, 161 and 162. , 163, 164, 167, 170, 182, 2000, 2001, 2020, 2025, 2050, 2070, 2096, 2150, LPN6919 and other various Disperbyk dispersants (manufactured by Big Chemie), Ajisper PB711, PB411, PB111, PB814, Examples thereof include various azisper dispersants such as PB821 and PB822 (manufactured by Ajinomoto Fine-Techno Co., Ltd.) and Fuka dispersants such as EFKA46, 47, 4300, 4330 and 4340 (manufactured by BASF).

The resin-type dispersant used in the present invention preferably contains the following (S1) or (S2) as a resin-type dispersant having a carboxyl group.
(S1) A resin-type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic dianhydride.
(S2) A weight obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic dianhydride. A resin-type dispersant that is a coalescence.

[Resin type dispersant (S1)]
The resin-type dispersant (S1) can be produced by a known method such as WO2008 / 007776, Japanese Patent Application Laid-Open No. 2008-029901, and Japanese Patent Application Laid-Open No. 2009-155406. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal. For example, the ethylenically unsaturated monomer (r) is polymerized in the presence of the compound (q) having a hydroxyl group. It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since the number of terminal hydroxyl groups is preferably plural, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

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

[Resin type dispersant (S2)]
The resin-type dispersant (S2) can be produced by a known method such as JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, and for example, a compound having a hydroxyl group. By polymerizing the ethylenically unsaturated monomer (r) in the presence of a reaction product of the hydroxyl group of (q) and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. can get. Above all, in the presence of a reaction product of the hydroxyl group of the compound (q1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. It is preferably a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing the monomer (r1).

The difference between (S1) and (S2) is whether the introduction of the polymer moiety obtained by polymerizing the ethylenically unsaturated monomer (r) is performed first or later. The molecular weight and the like may differ slightly depending on various conditions, but theoretically the same can be obtained if the reaction conditions are the same as those of the raw material.

<Binder resin>
Examples of the binder resin contained in the coloring composition of the present invention include conventionally known thermoplastic resins and thermosetting resins.

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

When used as a coloring composition for a color filter, 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 is preferable. When used in the form of an alkali-developable colored resist, it is preferable to use an alkali-soluble vinyl-based resin copolymerized with an acidic group-containing ethylenically unsaturated monomer. Further, in order to further improve the photosensitivity, an energy ray-curable resin having an ethylenically unsaturated active double bond can also be used.

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

As an energy ray-curable resin having an ethylenically unsaturated active double bond, a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group is substituted with a reactive substituent such as an isocyanate group, a formyl group or an epoxy group. A resin is used in which a (meth) acrylic compound having a group or silicic acid is reacted to introduce a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the polymer. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Esterified ones are also used.

As the thermoplastic resin, those having both alkali-soluble performance and energy ray-curable performance are also preferable as the photosensitive coloring composition for a color filter.

Examples of the monomer constituting the thermoplastic resin include the following. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-Ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) (Meta) acrylates such as acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyethylene glycol (meth) acrylate, or (meth) acrylamide, N, N -Dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or (meth) acrylamides such as acryloylmorpholin, styrene, or α-methylstyrene Examples thereof include styrenes such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, vinyl ethers such as isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate and vinyl propionate.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimide propionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Kumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimaleimide, N, N'-1,4- Phenylened maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide Examples thereof include N-substituted maleimides such as hexanoate, N- [4- (2-benzoimidazolyl) phenyl] maleimide, and 9-maleimide acrydin.

On the other hand, examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin. Of these, epoxy resins and melamine resins are more preferably used from the viewpoint of improving heat resistance.

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

Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined by connecting four separation columns in series in gel permeation chromatography "HLC-8120GPC" manufactured by Tosoh Corporation, and using Tosoh as a filler in order. It is a polystyrene-equivalent molecular weight measured using tetrahydrofuran, "H4000", "H3000", and "H2000" manufactured by TSK-GEL SUPER Co., Ltd. as a mobile phase.

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

The binder resin is preferably used in an amount of 20 to 500 parts by mass with respect to 100 parts by mass of the pigment composition.

<Organic solvent>
In the coloring composition for a color filter of the present invention, the coloring agent is sufficiently dispersed and permeated into the coloring agent carrier, and coated on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. Organic solvents can be included to facilitate the formation of filter segments.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, and the like. 2-Heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl -1,3-butanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m -Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-Dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene Glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl Ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether , Dipropylene glycol methyl ether acetate, Dipropylene glycol monoethyl ether , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol Monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol , N-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like.

These organic solvents may be used alone or in admixture of two or more. Further, the organic solvent is used in an amount of 500 to 4000 parts by mass with respect to 100 parts by mass of the coloring composition in order to adjust the coloring composition to an appropriate viscosity and to form a filter segment having a desired uniform film thickness. Is preferable.

<Other colorants>
In the pigment composition, in order to adjust the chromaticity or the like, the following pigments or dyes may be used in combination as other colorants in addition to the above pigment compositions as long as the effects of the present invention are not impaired.

Other pigments that can be used in colorants include, for example, 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, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, Red pigments such as 279, 280, 281, 282, 283, 284, 285, 286, or 287 can be mentioned. Examples of the red dye that can be used in other colorants include xanthene type, azo type (pyridone type, barbituric acid type, metal complex type, etc.), disazo type, anthraquinone type and the like. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene-based acid dyes such as Acid Red 52, 87, 92, 289, and 338.

In addition, C.I. I. Pigment Orange 43, 71, or 73 and / or other orange pigments and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, Yellow pigments such as 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or 231 can be used in combination. Examples of orange dyes and / or yellow dyes include quinoline dyes, azo dyes (pyridone dyes, barbituric acid dyes, metal complex dyes, etc.), disazo dyes, methine dyes, and the like.

In addition, C.I. I. Pigment Green 7, 10, 36, 37, 58, 62, 63 and other green pigments can be used in combination.

In addition, C.I. I. Pigment Blue 15: 3, 15: 4, 15: 6, 16, 60 and other blue pigments can be used in combination.

In addition, C.I. I. Acid Violet 15, 17, 19, 21, 24, 25, 38, 49, C.I. I. Basic Violet 1, 2, 3, 4, 14, C.I. I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 22, 24, 26, 75, 83, 90, 93, 100, C.I. I. Triphenylmethane-based or triarylmethane-based dyes such as Basic Blue 1, 5, 7, 11, 26, 81 or 83 can be used in combination. Of the organic dyes, acid dyes can have high heat resistance, light resistance, and solvent resistance by forming chlorides and sulfonamides.

In addition, C.I. I. Pigment Violet 1, 19, 23, 27, 32, 42 and other purple pigments can be used in combination.

<Dispersion of coloring composition>
In the coloring composition of the present invention, a pigment composition is kneaded together with a compound of the general formula (2) and a resin-type pigment dispersant in a coloring composition carrier composed of the binder resin and an organic solvent, and a two-roll mill. It can be manufactured by finely dispersing using various dispersion means such as a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual bead mill, or an attritor. Further, in the coloring composition of the present invention, the pigment composition and other coloring agents and the like may be dispersed in the coloring composition carrier at the same time, or those dispersed separately in the coloring composition carrier may be mixed. The carrier means a composition composed of a binder resin and an organic solvent.
At this time, it is preferable that the pigment composition is salt-milled and / or acid-paced, as described above.

Further, when the pigment composition is dispersed in the coloring composition carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained.

<Resin type dispersant and surfactant>
The resin-type dispersant has a pigment-affinitive moiety having a property of adsorbing to the coloring composition and a moiety compatible with the coloring composition carrier, and adsorbs to the pigment composition to disperse in the coloring composition. It works to stabilize. Specific examples of the resin-type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and alkyl polycarboxylic acids. Amine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products of these, amides formed by the reaction of poly (lower alkyleneimine) with polyesters having free carboxyl groups, and Oily dispersants such as salts, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resins, water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide-added compounds, phosphoric acid ester-based, etc. are used, and these can be used alone or in admixture of two or more. However, it is not necessarily limited to these.

Commercially available resin-type dispersants include Disperbyk-103, 108, 110, 111, 140, 161, 162, 163, 164, 170, 171, 174, 180, 182, 184, 185, 2000 manufactured by Big Chemie Japan. , 2001, 2025, 2050, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, etc., SOLSPERSE-13240, 13650, 13940, 16000, manufactured by Japan Lubrizol. 17000, 18000, 20000, 21000, 24000SC, 24000GR, 26000, 27000, 28000, 32000, 32500, 32550, 32600, 34750, 35100, 36600, 38500, 41000, 53095, 55000, 76500, etc. 4550, 4560, Efka FA-4665, 4666, Efka PA-4400, 4401, 4403, Efka PX-4300, 4310, 4320, 4330, 4340, etc. Can be mentioned.

Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalin sulfonate, and alkyldiphenyl ether disulfone. Anionic surface activity of sodium acid, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, etc. Agents: Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate. Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkyl imidazoline, which may be used alone or in combination of two. The above can be mixed and used, but the present invention is not necessarily limited to these.

When a resin-type dispersant or a surfactant is added, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the pigment composition.

The coloring composition of the present invention can be used as a photosensitive coloring composition by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

<Photopolymerizable monomer>
The photopolymerizable monomer used in the coloring composition of the present invention contains a monomer or oligomer that is cured by ultraviolet rays, heat, or the like to produce a transparent resin, and these may be used alone or in combination of two or more. Can be used. The blending amount of the monomer is preferably 5 to 400 parts by mass, and more preferably 10 to 300 parts by mass from the viewpoint of photocurability and developability with respect to 100 parts by mass of the coloring composition.

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 ( Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, 1,6-Hexanediol Diglycidyl Ether Di (Meta) Acrylate, Bisphenol A Diglycidyl Etherdi (Meta) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (Meta) acrylic acid ester, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol tri Examples thereof include, but are not limited to, vinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.

<Photopolymerization initiator>
In the coloring composition for a color filter of the present invention, when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithography method, a photopolymerization initiator or the like is added to perform solvent-development type or alkali-development type coloring. It can be adjusted in the form of a resist material. When using the photopolymerization initiator, the blending amount is preferably 5 to 200% by mass based on the total amount of the colorant (total of α-type copper phthalocyanine pigment and other colorants), and is photocurable and From the viewpoint of developability, it is more preferably 10 to 150% by mass.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-. Hydroxycyclohexylphenylketone, 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) -butane-1-one; benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4' -Methyldiphenyl sulfide, or benzophenone compounds such as 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 Thioxanthone compounds such as −diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-( p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6- Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4- Triazine compounds such as trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) )], Or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6- Oxime-based compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone-based compounds such as 9,10-phenanthrene quinone, camphorquinone, and ethylanthraquinone, borate compounds, and carbazole. A system compound, an imidazole system compound, a titanosen system compound, or the like is used.

These photopolymerization initiators can be used alone or in admixture of two or more at any ratio, if necessary. These photopolymerization initiators may be 5 to 200% by mass based on the total amount of the colorants (total of the pigment composition and other colorants) in the color filter coloring composition (100% by mass). It is preferably 10 to 150% by mass from the viewpoint of photocurability and developability.

<Sensitizer>
Further, the coloring composition for a color filter of the present invention may contain a sensitizer.

Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, acrydin derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives, Azulene derivative, azulenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, α-Acyloxy ester , Acylphosphine oxide, methylphenylglycolate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3', or 4,4' -Tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone and the like can be mentioned.

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

Two or more sensitizers may be used in any ratio as required. When the sensitizer is used, the blending amount is preferably 3 to 60% by mass based on the total mass of the photopolymerization initiator contained in the coloring composition (100% by mass), and is photocurable. From the viewpoint of developability, it is more preferably 5 to 50% by mass.

<Oxygen-reducing amine compound>
Further, the coloring composition for a color filter of the present invention may contain an oxygen-reducing amine compound having a function of reducing dissolved oxygen.

Examples of such oxygen-reducing amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-benzoate. Examples thereof include dimethylaminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

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

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

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

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used.

Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include ester.

Examples of the chaotic surfactant added as a supplement to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as a supplement to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like, and examples of the amphoteric surfactant include alkyl betaine such as alkyldimethylaminoacetic acid betaine, alkyl imidazoline and the like, and fluorine-based and silicone-based surfactants.

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

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

Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples thereof include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10% by mass based on the colorant (A) in the coloring composition (100% by mass).

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

<Removal of coarse particles>
The coloring composition for a color filter of the present invention has coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably 0.5 μm or more of coarse particles by means of centrifugation, sintering filter, membrane filter, or the like. And it is preferable to remove the mixed dust. As described above, it is preferable that the coloring composition for a color filter does not substantially contain particles having a size of 0.5 μm or more. More preferably, all particles are substantially 0.3 μm or less. Further, here, the measurement was performed using a particle size distribution measuring device "Nano-S (Sysmex Corporation)" using a dynamic light scattering method.

<Color filter>
The color filter of the present invention comprises at least one red filter segment, at least one blue filter segment, and at least one green filter segment, wherein at least one blue filter segment uses the coloring composition of the present invention. Is formed.

The red filter segment can be formed using a conventional red coloring composition containing a red pigment. The red coloring composition includes, for example, 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, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 207, 208, 210, 221, 242, 246, 254, 255, 264, 270, 272, 273, 274. Red pigments such as 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287 are used. Further, a salt-forming compound of a basic dye or an acid dye that exhibits a red color can also be used.

Further, the red coloring composition includes C.I. I. Pigment Orange 38, 43, 71, or 73 and other orange pigments and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, Yellow pigments such as 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or 231 can be used in combination. Further, a salt-forming compound of a basic dye or an acid dye exhibiting orange and / or yellow can also be used.

The green filter segment can be formed using a conventional green coloring composition containing a green pigment. Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58, 62, 63 and the like are used. Further, a yellow pigment can be used in combination with the green coloring composition. Examples of the yellow pigment that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, Yellow pigments such as 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or 231 can be mentioned. It is also possible to use a salt-forming compound of a basic dye or an acid dye that exhibits yellow color in combination.

<Manufacturing method of color filter>
The color filter of the present invention can be manufactured by a printing method or a photolithography method.

The formation of the filter segment by the printing method can be patterned only by repeating printing and drying of the coloring composition containing the coloring composition for the color filter of the present invention prepared as a printing ink. It is low cost and has excellent mass productivity. Further, with the development of printing technology, it is possible to print a fine pattern having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted with a dispersant or an extender pigment.

When the filter segment is formed by the photolithography method, a photosensitive coloring composition containing the blue coloring composition of the present invention prepared as the solvent-developed or alkali-developed colored resist is spray-coated or spun on a transparent substrate. Apply so that the dry film thickness is 0.2 to 5 μm by a coating method such as coating, slit coating, or roll coating. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to manufacture a color filter. be able to. Further, in order to promote the polymerization of the colored resist material, heating can be applied as needed. According to the photolithography method, a color filter having higher accuracy than the above printing method can be manufactured.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. In order to increase the UV exposure sensitivity, the colored resist material is applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. After that, ultraviolet exposure can 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 methods, but the blue coloring composition for a color filter of the present invention can be used in any method. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. .. Further, the transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

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

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples according to the conventional method. However, the present invention is not limited to the scope of these examples. In the examples, "parts" represents "parts by mass" and "%" represents "% by mass".

(Diffraction intensity with respect to diffraction angle 2θ)
The obtained pigment or pigment composition was subjected to powder X-ray diffraction diagram measurement under the following conditions.
Equipment: Rigaku X-RAY DIFFRACTIMETER RINT-2100
(Manufactured by Rigaku Co., Ltd.)
X-ray source: CuKα
Sampling width: 0.02 °
Divergence slit: 1 °
Scattering slit: 1 °
Light receiving slit: 0.3 mm
Voltage: 40kV
Current: 40mA
Measuring range: 5.0 ° to 40.0 °
Step angle: 0.02 °
Step time: 1.2 seconds

(Full width at half maximum)
The half width of the peak was obtained by performing data processing on the obtained powder X-ray diffraction pattern under the following conditions. Here, the full width at half maximum is a value of a diffraction angle defined by a peak width at an intensity position that is 1/2 intensity of the X-ray diffraction intensity at a certain peak of 2θ.

The half width was calculated 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 full width at half maximum is to be calculated (for example, 2θ = 15.5 ° ± 0.15 °), the point showing the maximum diffraction intensity is indicated by A.
2θ in A is Ax,
The point where 2θ shows the minimum diffraction intensity within the range of Ax or less and Ax-4.5 ° or more is B.
The point where 2θ shows the minimum diffraction intensity within the range of Ax or more and Ax + 3.5 ° or less is C.
Baseline the straight line connecting B and C,
The intersection of the perpendicular line drawn from A to the 2θ axis and the baseline is D,
The intersection of the line passing through the midpoint of A and D and parallel to the baseline and the curve AB is E,
The intersection of the line passing through the midpoint of A and D and parallel to the baseline and the curve AC is F,
2θ in E is Ex, 2θ in F is Fx,
When Fx-Ex was the half width of A, the half width was G.

(Aspect ratio of pigment or pigment composition)
With a transmission electron microscope (TEM), three photographs (for three fields of view) in which the primary particles of the pigment composition can be confirmed are taken, and the minor axis diameter and the major axis diameter of the primary particles of each pigment composition are measured. It was calculated by the following formula. The closer the aspect ratio is to 1, the closer the crystal state of the particles is to a square, which is preferable.
(Aspect ratio) = (major axis diameter) / (minor axis diameter)

The following compounds A to C were used as the compounds of the general formula (1) as the pigment derivatives used in the present invention. The method for producing the acrylic resin and the resin-type pigment dispersant used in Examples and Comparative Examples will be described below.

<Example of Production of Acrylic Resin Solution> A thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer were attached to a separable 4-port flask, 250 g of propylene glycol monomethyl ether acetate was charged, and the mixture was stirred while replacing nitrogen to raise the temperature to 120 ° C. A mixed solution of 0.78 mol (137.4 g) of benzyl methacrylate, 0.22 mol (18.9 g) of methacrylic acid, and 271 g of propylene glycol monomethyl ether acetate was added dropwise from the dropping tube over 2 hours. Two hours after the completion of the dropping, a solution in which 0.6 part of 2,2'-azobisisobutyronitrile was dissolved in methoxypropyl acetate was added, and the reaction was continued for another 1 hour. An acrylic resin solution having a non-volatile content of 30% was obtained. The weight average molecular weight measured by GPC was 18,000.

<Production example of resin-type pigment dispersant>
(Production Example of Resin-Type Pigment Dispersant A) 100 parts of methyl methacrylate, 100 parts of n-butyl acrylate, and 40 parts of methoxypropyl acetate are charged in a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer. Replaced with nitrogen gas. The inside of the reaction vessel is heated to 80 ° C., 12 parts of 3-mercapto-1,2-propanediol is added, and then 0.2 parts of 2,2'-azobisisobutyronitrile is divided into 20 portions 30 times. It was added every minute and reacted at 80 ° C. for 12 hours, and it was confirmed by solid content measurement that 95% of the reaction was carried out. Next, 30 parts of pyromellitic anhydride, 190 parts of methoxypropyl acetate, and 0.40 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added, and the reaction was carried out at 120 ° C. for 7 hours. I let you. After confirming by titration that 98% or more of the acid anhydride was half-esterified, the reaction was terminated, and an aromatic carboxyl group having an acid value of 42 mgKOH / g per solid content and a number average molecular weight (Mn) of 4,100 was obtained. A resin-type pigment dispersant A having a solid content of 50% was obtained.

(Example 1-1)
90 parts of α-type copper phthalocyanine pigment, 10 parts of compound A as a pigment derivative, 1000 parts of sodium chloride, and 200 parts of diethylene glycol were charged in a dual-arm kneader and kneaded at 70 ° C. for 8 hours. After kneading, the mixture was taken out into warm water, stirred for 1 hour, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried to obtain a pigment composition 1. The obtained pigment composition 1 was measured for the diffraction intensity with respect to the diffraction angle 2θ measured by CuKα rays with a powder X-ray diffractometer. As a result of obtaining the half width at 2θ from the value obtained by the measurement, G = 1.31 °. The aspect ratio was 1.6.

(Examples 1-2 to 14, Comparative Examples 1-1 to 4)
The α-type copper phthalocyanine pigment and the compound as a pigment derivative were kneaded in the same manner as in Example 1-1 except that the composition was changed to the composition shown in Table 1. The obtained kneading composition was post-treated in the same manner as in Example 1-1 to obtain Pigment Compositions 2 to 18 and Pigment 1. The diffraction intensity of the obtained pigment composition or pigment with respect to the diffraction angle 2θ measured by CuKα rays was measured with a powder X-ray diffractometer. The average primary particle size was also calculated in the same manner. Table 1 shows the half-value width of each 2θ peak in the X-ray diffraction pattern of the obtained pigment or pigment composition and the aspect ratio of the pigment or pigment composition.

(Comparative Example 1-5)
92 parts of α-type copper phthalocyanine, 8 parts of compound C, 700 parts of sodium chloride, and 150 parts of diethylene glycol were charged in a 1500-volume dual-arm kneader and kneaded at 70 ° C. for 10 hours. After kneading, the mixture was taken out into 3500 parts of a 1% sulfuric acid aqueous solution at 70 ° C., kept warm for 1 hour, and then filtered, washed with water and dried to obtain a pigment composition 19. The obtained pigment composition 19 was measured for diffraction intensity with respect to a diffraction angle of 2θ measured by CuKα rays with a powder X-ray diffractometer. As a result of obtaining the half width at 2θ from the value obtained by the measurement, G = 0.80 °. The aspect ratio was 2.3.

(Example 2-1)
The mixture consisting of the following components is stirred and mixed so as to be uniform, and then dispersed for 1 hour with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm. The colored composition 1 was prepared by filtering with a filter having a pore size of 5 μm.
Pigment Composition 1 12.0 parts Compound B 1.8 parts Acrylic resin solution 5.0 parts Resin-type pigment dispersant A 3.0 parts Propylene glycol monomethyl ether acetate 78.2 parts

(Examples 2-2 to 23, Comparative Examples 2-1 to 5)
The coloring compositions 2 to 28 were prepared in the same manner as in Example 2-1 except that the pigment composition 1 was changed to the pigment composition 2 to 19 or the pigment 1 and the amount of the compound B was changed to the composition shown in Table 2. Made.

(Evaluation of coloring composition)
The contrast ratio and viscosity of the obtained coloring composition (1-28) were evaluated by the following methods. Table 2 shows the evaluation results.

(Evaluation of contrast ratio)
The obtained coloring composition was placed on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm at different rotation speeds using a spin coater, and after heat treatment at 230 ° C., y = around 0.15 in a C light source. Three coating substrates were prepared so as to be. The drying conditions were 60 ° C. for 5 minutes and 230 ° C. for 20 minutes after application, and the contrast ratio was measured for each, and the contrast ratio at y = 0.15 in the C light source was measured by the first-order correlation method from the data of 3 points. I asked.

Further, 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 a liquid crystal display passes through a polarizing plate, is polarized, passes through a dry coating film of a coloring composition applied on a lath substrate, and reaches the polarizing plate. If the polarizing plate and the polarizing planes of the polarizing plate are parallel, light passes through the polarizing plate, but if the polarizing planes are orthogonal to each other, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dry coating film of the coloring composition, scattering by pigment particles or the like occurs and a part of the polarizing surface is displaced. When the polarizing plates are parallel, the polarized light is polarized. The amount of light transmitted through the plate is reduced, and when the polarizing plates are orthogonal, part of the light is transmitted through the polarizing plate. This transmitted light was measured as the brightness on the polarizing plate, and the ratio (contrast ratio) between the brightness when the polarizing plates were parallel and the brightness when the polarizing plates were orthogonal was calculated.
(Contrast ratio (CR)) = (Brightness when parallel) / (Brightness when orthogonal)
The contrast ratio was evaluated according to the following criteria.

⊚: 13000 to 15000 (extremely good)
◯: 1000 to 12999 (good)
Δ: 5000 to 9999 (slightly good)
×: 4999 or less (defective)

Therefore, when scattering occurs due to the pigment in the coating film, the brightness when parallel is reduced and the brightness when orthogonal is increased, so that 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. At the time of measurement, a black mask having a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

(Evaluation of viscosity)
The viscosity of the coloring composition was measured at 20 rpm and 25 ° C. using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Since the sample having a viscosity exceeding 30 mPa · s cannot be measured at the above rotation speed, it was measured at 10 rpm.
Viscosity was evaluated according to the following criteria.

◯: Less than 16 mPa · s (good)
Δ: 16 to 30 mPa · s (slightly good)
×: Exceeds 30 mPa · s (defective)

It was confirmed that the coloring composition prepared by using the pigment composition of the present invention has a low viscosity and a high contrast ratio when a color filter is prepared.

Claims (3)

A color filter pigment composition containing an α-type copper phthalocyanine pigment and a pigment derivative, a compound represented by the general formula (2), a binder resin, and an organic solvent. hand,
In the powder X-ray diffraction pattern, the pigment composition for a color filter is shown by the diffraction intensity with respect to the diffraction angle 2θ measured by CuKα ray.
The point showing the maximum diffraction intensity within the range of 2θ = 15.5 ° ± 0.15 ° is A,
2θ in A is Ax,
The point where 2θ shows the minimum diffraction intensity within the range of Ax or less and Ax-4.5 ° or more is B.
The point where 2θ shows the minimum diffraction intensity within the range of Ax or more and Ax + 3.5 ° or less is C.
Baseline the straight line connecting B and C,
The intersection of the perpendicular line drawn from A to the 2θ axis and the baseline is D,
The intersection of the line passing through the midpoint of A and D and parallel to the baseline and the curve AB is E,
The intersection of the line passing through the midpoint of A and D and parallel to the baseline and the curve AC is F,
2θ in E is Ex, 2θ in F is Fx,
When Fx-Ex is the half width of A, the half width is G, and the half width G is 1.3 ° or more.
The pigment derivative is a compound represented by the general formula (3).
Compound represented by the general formula (3) is, relative to the total of the compound represented by α-type copper phthalocyanine pigment of the general formula (3), Ri Na comprise 20-50% by weight,
The compound represented by the general formula (2) is characterized by containing 1 to 30% by mass with respect to the total of the α-type copper phthalocyanine pigment in the pigment composition and the compound represented by the general formula (2). for a color filter coloring composition.
General formula (3)

(However, P represents a residue of a metal-free or metallic phthalocyanine pigment, X represents a phthalimide methyl group which may have a substituent, and n represents an integer of 1 to 8.)

General formula (2)

(However, P represents a residue of a metal-free or metallic phthalocyanine pigment, b represents an integer of 1 to 6, d represents an integer of 0 to 6, and f represents an integer of 1 to 6.) With respect to the compound represented by Formula (3), the general formula (2) is represented by the compounds according to claim 1 for a color filter colored composition wherein it contains 15 to 50 wt%. A color filter comprising a filter segment formed from the coloring composition for a color filter according to claim 1 or 2.

Images