JP2009251586A - Pigment dispersion composition, method for preparing pigment dispersion composition, colored polymerizable composition, color filter and method for manufacturing color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment dispersion composition excellent in pigment dispersibility and its stability and forming a colored film excellent in contrast, and to provide a colored polymerizable composition using the pigment dispersion composition and forming a colored film excellent in contrast and reduced in surface roughness. <P>SOLUTION: The pigment dispersion composition comprises a diketopyrrolopyrrole pigment, 0.1-30 parts by mass of a phthalimidoalkylated diketopyrrolopyrrole based on 100 parts by mass of the diketopyrrolopyrrole pigment, 0.1-20 parts by mass of a phthalimidoalkylated quinacridone based on 100 parts by mass of the diketopyrrolopyrrole pigment, and at least one organic solvent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a pigment dispersion composition, a method for producing the pigment dispersion composition, a colored polymerizable composition containing the pigment dispersion composition, a color filter using the colored polymerizable composition, and production of the color filter. Regarding the method.

  The color filter contains a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a photopolymerization initiator, an alkali-soluble resin, and other components to form a colored polymerizable composition, which is used. It is manufactured by forming a colored pattern by a photolithography method or the like.

  In recent years, the use of color filters in liquid crystal display (LCD) applications has tended to expand not only to monitors but also to televisions (TVs). With this trend of expanding applications, advanced color characteristics such as chromaticity and contrast. Has come to be required. In addition, in the image sensor (solid-state imaging device) application, a device having high color characteristics is also demanded.

  It is effective to use a pigment whose primary particle diameter is miniaturized to meet the above requirements. As a method for reducing the primary particle diameter of the pigment, for example, the pigment is combined with a water-soluble inorganic salt such as a synthetic resin that is solid and water-insoluble at room temperature, sodium chloride, and a water-soluble organic solvent that at least partially dissolves the synthetic resin. After kneading mechanically with a kneader or the like (hereinafter, kneading a mixture containing a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is called salt milling), and then washing with water, the water-soluble inorganic salt and the water-soluble organic There is a method for removing the solvent (see, for example, Patent Document 1). In this method, since the primary particle pulverization and crystal growth occur in parallel with each other, the final particle size distribution is narrow, and a pigment with a small surface area is obtained in spite of a small average particle size. This method is suitable for obtaining a pigment for a use in which a pigment having a diameter needs to be dispersed at a high concentration.

However, pigments made in this way cause severe aggregation in the drying process after desalting, and thus dispersibility and dispersion stability are often not good. It is difficult to obtain a pigment dispersion having excellent properties. If the dispersibility of the pigment is insufficient, fringes (jagged edges) and surface irregularities occur in the colored pattern formed by the polymerizable composition containing the pigment dispersion, and the chromaticity of the produced color filter In addition, there is a problem that the dimensional accuracy is lowered and the contrast is remarkably deteriorated.
Furthermore, when the dispersion stability of the pigment is poor, there is also a problem that the constituent components of the colored polymerizable composition cause aggregation with the passage of time, the viscosity increases, and the pot life becomes extremely short. In addition, when a color filter is produced using such a colored polymerizable composition, the uniformity of the film thickness in the coating process decreases, resulting in sensitivity fluctuations in the exposure process and alkali dissolution in the development process. Problems such as fluctuations in characteristics and non-uniformity are likely to occur. In particular, when slit coating (also referred to as die coating) is performed when forming a colored film of a colored polymerizable composition on a glass substrate in order to produce a color filter having a large area, streaks are applied to the coating surface. There is a problem in that the defects of the coating are likely to occur, the surface property of the coating is lowered, and this becomes a pixel defect of the color filter.
Therefore, as a method for improving the dispersibility and dispersion stability of the pigment, a method of adding rosin or a rosin derivative or a synthetic polymer compound during salt milling has been proposed (for example, see Patent Document 2).

For diketopyrrolopyrrole pigments, a method has been proposed in which atomization is promoted by adding a pigment derivative during salt milling to improve contrast (see, for example, Patent Document 3 and Patent Document 4).
However, according to the above-described prior art, when attention is paid only to the refinement of the pigment particles and the contrast of the image, a certain degree of improvement effect can be obtained. For this reason, there is a problem that the surface becomes rough when the development process, particularly the development, post-baking, and UV cleaning are repeated.
Japanese Patent Laid-Open No. 7-13016 JP-A-8-179111 JP 2001-220520 A JP 2007-31539 A

Then, this invention is made | formed in view of said point, and makes it a subject to achieve the following objectives.
That is, a first object of the present invention is to provide a pigment dispersion composition that is excellent in high pigment dispersibility and stability, and can form a colored film excellent in contrast, and a method for producing the same.
The second object of the present invention is to provide a colored polymerizable composition capable of forming a film having excellent contrast and capable of forming a color filter having a smooth surface.
A third object of the present invention is to provide a color filter having a high contrast and a smooth surface, and a method for producing the color filter.

Means for solving the above-mentioned problems are as follows.
That is, the pigment dispersion composition of the present invention includes a diketopyrrolopyrrole pigment, 0.1 to 30 parts by mass of a phthalimide alkylated diketopyrrolopyrrole, and the diketopyrrolopyrrole to 100 parts by mass of the diketopyrrolopyrrole pigment. It contains 0.1 to 20 parts by mass of a phthalimidoalkylated quinacridone and at least one organic solvent with respect to 100 parts by mass of a pyrrole pigment.

The average primary particle diameter of the diketopyrrolopyrrole pigment is preferably 10 nm to 30 nm.
The diketopyrrolopyrrole pigment used in the pigment dispersion of the present invention mechanically contains a diketopyrrolopyrrole pigment, a water-soluble inorganic salt, and a water-soluble organic solvent that does not substantially dissolve the water-soluble inorganic salt. A step of kneading, a step of removing the water-soluble inorganic salt and the water-soluble organic solvent, a step of drying the contacted diketopyrrolopyrrole pigment, and the diketopyrrolopyrrole pigment before the drying step. And a step of bringing the resin into contact with each other.
Here, the resin to be added is preferably a polymer compound having an acid value of 50 to 300 mgKOH / g.

  In the method for producing the pigment dispersion composition of the present invention, the diketopyrrolopyrrole pigment having an average primary particle size of 10 nm to 30 nm is 0.1 to 30 parts by mass with respect to 100 parts by mass of the diketopyrrolopyrrole pigment. Adding 0.1 to 20 parts by mass of phthalimide alkylated quinacridone to 100 parts by mass of phthalimidoalkylated diketopyrrolopyrrole and 100 parts by mass of the diketopyrrolopyrrole pigment, diketopyrrolopyrrole pigment, 0.1 to 30 parts by weight of phthalimide alkylated diketopyrrolopyrrole per 100 parts by weight of diketopyrrolopyrrole pigment and 0.1 to 20 parts by weight of phthalimidoalkylated quinacridone per 100 parts by weight of the diketopyrrolopyrrole pigment And a step of dispersing together with an organic solvent.

The colored polymerizable composition of the present invention contains the pigment dispersion composition of the present invention, a photopolymerizable compound, and a photopolymerization initiator, and preferably further contains an alkali-soluble resin.
The color filter of the present invention is preferably formed using the colored polymerizable composition of the present invention, and is particularly preferably an embodiment provided with a colored region formed of the colored polymerizable composition of the present invention. .
In addition, the color filter manufacturing method preferably uses the colored polymerizable composition of the present invention on a substrate, preferably forms a film by a coating method, exposes the formed film, and then uncured film. Is developed and removed.

The pigment dispersion composition of the present invention is obtained by dispersing a specific amount of phthalimide alkylated diketopyrrolopyrrole and phthalimide alkylated quinacridone in an organic solvent with respect to a diketopyrrolopyrrole pigment.
In the present invention, by using a phthalimide alkylated diketopyrrolopyrrole and a phthalimide alkylated quinacridone in combination with a diketopyrrolopyrrole pigment, a pigment dispersion composition having excellent dispersion stability and contrast, and excellent viscosity stability. A colored polymerizable composition capable of forming a color filter having high contrast and excellent surface smoothness, and a color filter having high contrast and excellent surface smoothness can be obtained.
In combination with phthalimidoalkylated diketopyrrolopyrrole and phthalimidoalkylated quinacridone, it exhibits a great synergistic effect on the stability improvement of diketopyrrolopyrrole pigments. And a colored film having excellent surface smoothness can be formed. Although the mechanism of this action is not clear, phthalimide alkylated pigment derivatives having two different mother nuclei strongly interact with different sites on the surface of the diketopyrrolopyrrole pigment, thereby causing unstable diketopyrrolopyrrole. Compared to the case where the surface is protected and each of them is used alone, these synergistic effects provide unexpectedly excellent stability. It seems that it is possible to form a colored film that is stably dispersed, has high contrast, and has excellent surface smoothness.

ADVANTAGE OF THE INVENTION According to this invention, the pigment dispersion composition which is excellent in high pigment dispersibility and its stability, and can form the colored film excellent in contrast, and its manufacturing method can be provided.
Moreover, according to this invention, the colored polymerizable composition which can form the film excellent in viscosity stability, excellent in contrast, and excellent in surface smoothness can be provided. This colored polymerizable composition is suitable for the production of a color filter.
Furthermore, according to the present invention, it is possible to provide a color filter having a high contrast and a smooth surface, and a method for producing the color filter.

  Hereinafter, the pigment dispersion composition of the present invention, the method for producing the pigment dispersion composition, the colored polymerizable composition, the color filter, and the method for producing the same will be described in detail.

<Pigment dispersion composition>
The pigment dispersion composition of the present invention comprises (A) a diketopyrrolopyrrole pigment, 0.1 to 30 parts by mass of (B) a phthalimidoalkylated diketopyrrolopyrrole with respect to 100 parts by mass of the diketopyrrolopyrrole pigment, 0.1 to 20 parts by mass of (C) phthalimidoalkylated quinacridone and (D) at least one organic solvent with respect to 100 parts by mass of the diketopyrrolopyrrole pigment, and as required Other components can also be contained.

[(A) diketopyrrolopyrrole pigment]
The diketopyrrolopyrrole pigment in the present invention (hereinafter sometimes referred to as “DPP pigment”) is a red-orange pigment having a structure represented by the following general formula (A), and has excellent light resistance, Has heat resistance.

In the general formula (A), X and Y each independently represent a hydrogen atom, an alkyl group, a cyano group, an aryl group, or a halogen group.
Here, the alkyl group is a saturated or unsaturated alkyl group, and the alkyl group and the aryl group may further have a substituent. Examples of the substituent that can be introduced into the alkyl group include a halogen atom, an alkenyl group, an aryl group, a hydroxyl group, and an alkoxy group. Examples of the substituent that can be introduced into the aryl group include a halogen atom, an alkyl group, An alkoxy group etc. are mentioned.

  A specific example of the DPP pigment represented by the general formula (A) is represented by a color index number. I. Pigment Red 254, 255, 264, and C.I. I. Pigment Orange 71. Among these, in the present invention, C.I. I. Pigment Red 254 can be particularly preferably used.

In order to obtain a high-contrast color filter, the particle size of the DPP pigment used in the present invention is preferably small and has a narrow distribution, and the average primary particle size is preferably 10 nm to 30 nm. By using particles in this range, a dispersion having excellent dispersion stability can be obtained, and a high-contrast colored cured film can be formed by using this dispersion.
Here, the particle diameter of the DPP pigment can be measured, for example, from an image obtained by photographing the pigment with a transmission electron microscope at a magnification of 100,000 times. Moreover, about an average particle diameter, the average value of the long diameter and short diameter of a particle | grain can be measured, for example, this can be performed about 500 particle | grains, and the average value can be made into an average particle diameter. The average primary particle diameter in the present invention is measured by this method.
A diketopyrrolopyrrole pigment having such an average primary particle size can be obtained by a known method such as a dry pulverization method, a wet pulverization method, a recrystallization method, an acid paste method, etc. In order to obtain fine particles, in the present invention, it is preferable to carry out refinement by salt milling. Hereinafter, the case where the diketopyrrolopyrrole pigment refined | miniaturized by salt milling is obtained is explained in full detail.

In the present invention, the finely diketopyrrolopyrrole pigment is
After mechanically kneading (salt milling) a diketopyrrolopyrrole pigment, a water-soluble inorganic salt, and a water-soluble organic solvent that does not substantially dissolve the water-soluble inorganic salt, the water-soluble inorganic salt and the water-soluble organic salt Removing the solvent and further drying;
Contacting the resin with the diketopyrrolopyrrole pigment before the drying;
It is preferably obtained by a method having
Here, the resin added after the salt milling and before the drying step is preferably a polymer compound having an acid value of 50 to 300 mgKOH / g.
When performing the salt milling treatment, additives such as a pigment dispersion aid, a plasticizer, and a surfactant may be used in combination with the above-described resin, as long as the effects of the present invention are not impaired. .
Each is described in detail below.

(DPP pigment)
The types of diketopyrrolopyrrole pigments used for salt milling are as described above. In order to obtain the above-mentioned preferable particle size after salt milling, the average primary particle size is preferably 20 nm to 300 nm, and preferably 25 nm to 200 nm as the particle size of the diketopyrrolopyrrole pigment before salt milling. More preferably, it is preferably 30 nm to 150 nm.

  In the present invention, the DPP pigment used for salt milling may be synthesized by a known method, or a commercially available product may be used. Specific product names include Irgafore Red BT-CF, Irgafore Red B-CF, IRGAZIN RED 2030, IRGAZIN DPP RED 80, IRGAZIN DPP RED BTR, IRGAZIN DPP RED BL, CROMOPHTAL RED 2030, CROMOPHLD Can be mentioned.

In the present invention, it is preferable to salt mill the DPP pigment alone, but salt milling can also be performed by combining the DPP pigment and another organic pigment.
Examples of organic pigments used in combination with DPP pigments include the following.
That is, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 270, 272, 279,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,

C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64,
C. I. Pigment Green 7, 10, 36, 37,
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 were changed to OH. Things, 80,
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,
C. I. Pigment Brown 25, 28,
C. I. Pigment Black 1, 7, etc.

In the present invention, the following pigments are more preferable as the organic pigment used in combination with the DPP pigment.
That is, C.I. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C. I. Pigment Orange 36
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, and 242.

  In the present invention, when other organic pigments are used in combination with the DPP pigment, if desired, the ratio of the DPP pigment can be arbitrarily changed according to the required hue. It is 0.1 mass% or more and less than 100 mass% with respect to all the organic pigments.

(Water-soluble inorganic salt)
The water-soluble inorganic salt used for salt milling is not particularly limited as long as it is soluble in water, and sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used. Alternatively, sodium sulfate is preferably used.

  The smaller the particle diameter of the water-soluble inorganic salt, the higher the effect of atomization can be obtained. However, since the small-sized inorganic salt is expensive, it is preferably 0.1 μm to 100 μm, more preferably 1 μm to 50 μm.

  The amount of the water-soluble inorganic salt used in the salt milling step is preferably 1 to 30 times, particularly 5 to 25 times the amount of all organic pigments including the DPP pigment, from the viewpoints of processing efficiency and production efficiency. As the quantity ratio of the inorganic salt to the organic pigment is larger, the refinement efficiency is higher. However, since the processing amount of one pigment is reduced, the above range is preferable.

(Water-soluble organic solvent)
The water-soluble organic solvent functions to wet the organic pigment and the inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the water-soluble inorganic salt to be used.
However, since the temperature rises during salt milling and the solvent easily evaporates, it is preferable to use a high boiling point solvent having a boiling point of 120 ° C. or higher from the viewpoint of safety.

  Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether. Acetate, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol Monoethyl ether, liquid polypropylene glycol or the like is used.

Moreover, a water-soluble organic solvent may be used independently and can also use 2 or more types together.
The addition amount of the water-soluble organic solvent is preferably 5% by mass to 80% by mass with respect to the water-soluble inorganic salt. More preferably, it is 10 mass%-60 mass% with respect to water-soluble inorganic salt, and optimally it is 15 mass%-50 mass% with respect to water-soluble inorganic salt.
When the addition amount is in the above range, uniform kneading is possible, the particle diameter is likely to be uniform, and the softness of the kneaded composition is maintained in an appropriate range for the treatment, and shearing force is appropriately applied during kneading. Therefore, a desired miniaturization effect can be obtained.
As the timing of addition of the water-soluble organic solvent in the salt milling step, all may be added at the beginning of the step, or may be added in divided portions.

(resin)
In the production of the refined diketopyrrolopyrrole pigment according to the present invention, the pigment and the water-soluble inorganic pigment are used in order to prevent strong agglomeration during drying of the refined diketopyrrolopyrrole pigment and to enable easy dispersion. After kneading a salt and the like to remove the water-soluble inorganic salt and the water-soluble organic solvent, the resin is preferably brought into contact with the diketopyrrolopyrrole pigment before being subjected to the drying step.
Here, bringing the resin into contact with the DPP pigment means that the resin is adhered to at least a part of the surface of the DPP pigment.

  The treatment of bringing the resin into contact with the DPP pigment may be performed in any step before drying. For example, in the initial stage or in the middle of the salt milling process (kneading), after the salt milling process, during the dispersion process after the salt milling, What is necessary is just to add a solid resin or a resin solution after a process etc.

The resin to be brought into contact with the DPP pigment is preferably a polymer compound having an acid value of 50 to 300 mgKOH / g. A soft powder pigment can be obtained by bringing a polymer compound having an acid value of 50 to 300 mgKOH / g into contact with the DPP pigment, and a fine DPP pigment having high dispersibility and dispersion stability can be obtained. Can do.
The polymer compound having an acid value of 50 to 300 mgKOH / g used in the present invention is preferably water-insoluble, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like are used.
As the natural resin, rosin is typical, and as the modified natural resin, rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof are used.
Examples of synthetic resins include epoxy resins, acrylic resins, maleic resins, butyral resins, polyester resins, melamine resins, phenol resins, polyurethane resins, and polyamide resins.

The acid group present in the molecule of the polymer compound having an acid value of 50 to 300 mgKOH / g is not particularly limited, and examples thereof include a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, a phenol group, and a sulfonamide group. Particularly preferred acid groups are carboxylic acid groups.
The acid value is preferably 50 to 300 mgKOH / g, more preferably 50 to 250 mgKOH / g, and most preferably 70 to 250 mgKOH / g.
By adjusting the acid value within this range, excellent alkali solubility, anti-aggregation effect during drying, storage stability, and dispersibility are achieved in the fine DPP pigment.

  The molecular weight of the polymer compound having an acid value of 50 to 300 mgKOH / g is preferably 1000 or more and 50000 or less, more preferably 3000 or more and 30000 or less, and most preferably 4000 or more and 25000 or less in terms of weight average molecular weight. By adjusting the molecular weight within this range, excellent alkali solubility, anti-aggregation effect during drying, and dispersibility can be achieved in the fine DPP pigment.

(High molecular compound containing pigment adsorbing group)
Moreover, as a high molecular compound whose acid value is 50-300 mgKOH / g, the high molecular compound which has a pigment adsorbing group is also preferable.
Specifically, the polymer compound having a pigment adsorbing group is derived from one monomer selected from the group consisting of a monomer represented by the following general formula (1), a maleimide, and a maleimide derivative. The polymer preferably contains a polymer unit (hereinafter referred to as “specific polymer”). Especially, as a specific polymer, it is especially preferable that it is a polymer containing the polymer unit derived from the monomer represented by following General formula (1).

In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic group.

The alkyl group represented by R ¹ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
When the alkyl group represented by R ¹ has a substituent, the substituent is preferably, for example, an alkoxy group such as a hydroxy group, a methoxy group, an ethoxy group, or a cyclohexyloxy group. As this alkoxy group, a C1-C5 thing is preferable and a C1-C3 thing is preferable.

Specific examples of preferable alkyl group represented by R ¹ include, for example, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, Examples include 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, and 2-methoxyethyl group.
Among them, R ¹ is most preferably a hydrogen atom or a methyl group.

The divalent linking group represented by R ² in the general formula (1) is preferably an alkylene group or a divalent group containing an alkylene group. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, still more preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. Particularly preferred.
When this alkylene group has a substituent, examples of the substituent include a hydroxy group.
Specific examples of the preferable alkylene group represented by R ² include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.

The divalent group containing an alkylene group represented by R ² may be a group in which two or more of the above alkylene groups are linked via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom).
The divalent group containing an alkylene group represented by R ^2, the end towards which binds to Z in the alkylene group, -O -, - S -, - C (= O) O -, - CONH-, -C (= O) S-, -NHCONH-, -NHC (= O) O-, -NHC (= O) S-, -OC (= O)-, -OCONH-, and -NHCO- A hetero atom selected from or a partial structure containing a hetero atom may be bonded.

Specific examples of the nitrogen-containing heterocyclic structure constituting the nitrogen-containing heterocyclic group represented by Z in the general formula (1) include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrrole ring, an imidazole ring, and a triazole ring. , Tetrazole ring, indole ring, quinoline ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic urea structure, and cyclic imide structure The thing which has is mentioned.
These nitrogen-containing heterocyclic structures may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group, and an alkoxycarbonyl group. Is mentioned.

The nitrogen-containing heterocyclic group represented by Z is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and a nitrogen-containing heterocyclic structure having 6 to 12 carbon atoms. Particularly preferred is a group having
Specific examples of the nitrogen-containing heterocyclic structure having 6 or more carbon atoms include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic urea A structure and a cyclic imide structure are preferable, and a structure represented by the following general formula (2), (3) or (4) is particularly preferable.

In the general formula (2), X represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), -O-, -S-, -NR ^A- , and It is one selected from the group consisting of —C (═O) —. Here, R ^A represents a hydrogen atom or an alkyl group. When R ^A represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as X in the general formula (2), a single bond, a methylene group, —O—, or —C (═O) — is preferable, and —C (═O) — is particularly preferable.

In General Formula (4), Y and Z each independently represent —N═, —NH—, —N (R ^B ) —, —S—, or —O—. R ^B represents an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as Y and Z in the general formula (4), —N═, —NH—, and —N (R ^B ) — are particularly preferable. As a combination of Y and Z, a combination (imidazolyl group) in which one of Y and Z is —N═ and the other is —NH— is preferable.

  In general formula (2), (3), or (4), ring A, ring B, ring C, and ring D each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring. Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

Specifically, examples of the ring A and ring B in the general formula (2) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like.
Examples of the ring C in the general formula (3) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring.
Examples of the ring C in the general formula (4) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like.

  Among the structures represented by the general formula (2), (3) or (4), a benzene ring and a naphthalene ring are more preferable from the viewpoint of dispersibility and stability over time of the dispersion, and the general formula (2) or In (4), a benzene ring is more preferable, and in the general formula (3), a naphthalene ring is more preferable.

  In addition, the maleimide derivative in the present invention means a maleimide in which the N position is substituted with a substituent such as an alkyl group or an aryl group.

  Hereinafter, preferable specific examples (monomers M-1 to M-30) of the monomer represented by the general formula (1), maleimide, and maleimide derivatives are listed below, but the present invention is limited thereto. It is not a thing.

The specific polymer in the present invention includes only one type of polymer unit derived from one monomer selected from the group consisting of the monomer represented by the general formula (1), maleimide, and maleimide derivatives. It may be a thing and may contain 2 or more types.
Among the monomers represented by the general formula (1), maleimide, and maleimide derivatives, the monomer represented by the general formula (1) is preferable because of its high adsorptivity to the pigment.

In the specific polymer in the present invention, the content of the polymer unit derived from one monomer selected from the group consisting of the monomer represented by the general formula (1), maleimide, and maleimide derivative is heavy. When the total structural unit contained in the coalescence is 100% by mass, the content is preferably 5% by mass or more, and more preferably 10 to 50% by mass.
That is, in order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of pigment, or to effectively weaken the cohesive force of secondary aggregates, it is represented by the general formula (1). The content of polymerized units derived from one monomer selected from the group consisting of monomers, maleimides, and maleimide derivatives is preferably 5% by mass or more. Further, from the viewpoint of developability when producing a color filter with a photopolymerizable composition containing a pigment dispersion composition, the group consisting of the monomer represented by the general formula (1), maleimide, and maleimide derivatives The content of polymerized units derived from one more selected monomer is preferably 50% by mass or less.

It is preferable that the specific polymer in this invention contains the polymer unit derived from the monomer which has an acid group. When the specific polymer includes a polymer unit derived from a monomer having an acid group, when the pigment dispersion composition is applied to the photopolymerizable composition, the development removability of the unexposed area is excellent.
Monomers having an acid group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) monovalent polyvalent carboxylic acid mono [ (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monoacrylate Mono (meth) acrylates such as both terminal carboxy polymers methacrylate and the like.

The specific polymer in this invention may contain only 1 type of the polymer unit derived from the monomer which has an acid group, and may contain 2 or more types.
In the specific polymer, the content of polymerized units derived from the monomer having an acid group is preferably 50 mgKOH / g or more, and particularly preferably 50 to 300 mgKOH / g. That is, in terms of suppressing the formation of precipitates in the developer, the content of polymerized units derived from the monomer having an acid group is preferably 50 mgKOH / g or more. In order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of the pigment, or to effectively weaken the cohesive strength of the secondary aggregates, it is derived from a monomer having an acid group. The polymerization unit content is preferably 50 to 300 mgKOH / g.
In addition, when the specific polymer in this invention has an acid value of 50-300 mgKOH / g, the specific polymer can be used as a high molecular compound whose above-mentioned acid value is 50-300 mgKOH / g.

Moreover, the specific polymer in this invention may contain the polymer unit derived from a vinyl monomer further in the range which does not impair the effect.
Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

(Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.
Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

The preferred molecular weight of the specific polymer in the present invention is preferably in the range of 1000 to 50000 in terms of weight average molecular weight (Mw) and in the range of 400 to 30000 in terms of number average molecular weight (Mn). More preferably, the weight average molecular weight (Mw) is in the range of 3000 to 30000, and the number average molecular weight (Mn) is in the range of 1000 to 20000.
In particular, the weight average molecular weight (Mw) is most preferably in the range of 4000 to 20000, and the number average molecular weight (Mn) is preferably in the range of 1500 to 15000.
That is, from the viewpoint of effectively suppressing the formation of secondary aggregates, which are aggregates of primary particles of pigment, or effectively reducing the cohesive force of secondary aggregates, the weight average of the specific polymer The molecular weight (Mw) is preferably 1000 or more. From the viewpoint of developability when producing a color filter with a photopolymerizable composition containing a treated pigment, the weight average molecular weight (Mw) of the specific polymer is preferably 50000 or less.

The specific polymer can be produced by a normal radical polymerization method using, for example, the monomer represented by the general formula (1) and another radical polymerizable compound as a copolymerization component. In general, a suspension polymerization method or a solution polymerization method is used.
Examples of the solvent used for synthesizing such a specific polymer include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy. Examples include ethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. It is done. These solvents may be used alone or in combination of two or more.

  In radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can also be used.

It is preferable to add 1% by mass to 80% by mass of the resin to be brought into contact with the DPP pigment in the pre-drying step in the production process of these fine DPP pigments with respect to the total organic pigment containing the DPP pigment. . A more preferable addition amount is 5% by mass to 60% by mass with respect to the total organic pigment containing the DPP pigment, and optimally 7% by mass to 35% by mass with respect to the total organic pigment containing the DPP pigment.
When the addition amount is in the range of 1% by mass to 80% by mass, a sufficient aggregation preventing effect during drying can be obtained, and a color filter having a preferable hue can be obtained.

(Pigment derivative)
In the present invention, a pigment derivative may be added during salt milling in order to promote the refinement of the diketopyrrolopyrrole pigment.
Preferred skeletons of pigment derivatives include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, diketopyrrolopyrrole pigments, benzoimidazolone pigments, and the like. Can be mentioned. In addition, light yellow aromatic polycyclic compounds such as naphthalene, anthraquinone, triazine, and quinoline are also included in the preferred skeleton. Among these skeletons, quinacridone pigments, diketopyrrolopyrrole pigments, and azo pigments are particularly preferable from the viewpoint of hue and the effect of promoting miniaturization.
Examples of pigment derivatives that can be added include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, and JP-A-8-295810. JP-A-11-199796, JP-A-2005-234478, JP-A-2003-240938, JP-A-2001-356210, JP-A-2001-220520, JP-A-2007-186681, etc. You can use what is described.
In the present invention, when a pigment derivative is added during salt milling, the pigment derivative is preferably used at a ratio of 0.1 to 20 parts by mass with respect to 100 parts by mass of the DPP pigment, It is more preferable to use within a range. When the content is in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the DPP pigment, an excellent refining effect is obtained.

  In the present invention, when a pigment derivative is added during salt milling, it is common to use a DPP pigment and a pigment derivative mixed in powder form before kneading. Good. The pigment derivative may be added all at once, or may be added in several divided portions.

  In the present invention, an example of a compound that can be used when a pigment derivative is added during salt milling is shown.

(Salt milling process and subsequent processes)
The salt milling step in the present invention includes a diketopyrrolopyrrole pigment, a water-soluble inorganic salt, a water-soluble organic solvent that does not substantially dissolve the water-soluble inorganic salt, and, if necessary, a resin (preferably an acid value). Is a step of mechanically kneading a polymer compound having a molecular weight of 50 to 300 mgKOH / g.
In this step, it can be carried out with any apparatus such as a kneader, a planetary mixer, or a continuous atomizer, but the temperature during atomization is preferably 10 ° C to 150 ° C, more preferably 20 ° C to 120 ° C. Optimally, 30 ° C. to 90 ° C. is preferable. When atomization is performed at 150 ° C. or higher, the particle growth rate may exceed the atomization rate, and the atomization may be difficult to proceed. Further, it is not preferable to atomize at 10 ° C. or lower because it becomes difficult to control due to the heat generated during atomization and the production stability is affected. The salt milling treatment can be performed for any time during which the desired particle size can be obtained, but is usually 2 hours to 24 hours, and 2 hours to 15 hours are preferable in consideration of productivity.

After the salt milling process as described above, a finely processed pigment is obtained by removing the water-soluble inorganic salt and the water-soluble organic solvent in the kneaded product.
First, after the salt milling process, it is common to perform a desalting treatment on the obtained kneaded product.
The desalting treatment can be performed using any known apparatus, but a method in which a kneaded product and warm water are put into a dispersion tank and stirred with a high-speed mixer or the like is common.
The dispersed pigment is generally filtered and washed. Although filtration and washing can be performed using any known apparatus, it is common to use a filter press, and it is preferable to use a filter press also in the present invention.

The pigment after desalting treatment and filtration is generally dried. Usually, an oven is often used for drying, but a spray drying method or a vacuum drying method can also be used. In particular, it is known that the spray-drying method can provide a pigment powder that is weakly agglomerated and easily dispersed.
The temperature for drying in the oven is usually 30 ° C to 150 ° C, preferably 30 ° C to 120 ° C, and most preferably 40 ° C to 90 ° C. If drying is performed at a temperature higher than 150 ° C., it may cause severe dry aggregation and may be difficult to disperse. Also, drying at a temperature lower than 30 ° C. is not preferable from the viewpoint of productivity because it takes a long time.
The moisture content in the treated pigment after drying is usually 0.01% to 10%, preferably 0.05% to 5%, and most preferably 0.05% to 3%.

Although the pigment dispersion composition of the present invention contains a DPP pigment, it is preferably composed of at least one of the above-mentioned fine DPP pigments.
The pigment dispersion composition of the present invention can be used in combination with other pigments or dyes as necessary. Specific examples of combinations are shown below.

For example, as a red pigment, at least one diketopyrrolopyrrole pigment (including the aforementioned fine DPP pigment), a bisazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment And the like can be used. In order to obtain a preferable hue, it is also preferable to use a combination of a diketopyrrolopyrrole pigment and an anthraquinone pigment. Preferred pigments as diketopyrrolopyrrole pigments are C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment Red 264 and the like, but C.I. I. Pigment Red 254 is preferred. Preferred examples of the anthraquinone pigment include C.I. I. Pigment red 89, C.I. I. Pigment Red 177 and the like, but C.I. I. Pigment Red 177 is preferably used.
The preferable content of the anthraquinone pigment is 0 to 200 parts by mass, optimally 0 to 120 parts by mass with respect to 100 parts by mass of the diketopyrrolopyrrole pigment.
In addition, from the viewpoint of hue, spectral characteristics, and contrast, C.I. I. Pigment red 254 and C.I. I. Pigment Red 177 and C.I. I. Pigment yellow 150 and C.I. I. Pigment yellow 139, C.I. I. It is also preferable to use a yellow pigment such as CI Pigment Yellow 138. Among these, C.I. I. Pigment red 254 and C.I. I. Pigment Red 177 and C.I. I. A combination using Pigment Yellow 150 is particularly preferable from the viewpoint of contrast.

  The pigment that can be used in combination is not particularly limited, and the series of known pigments described above in the section of the diketopyrrolopyrrole pigment can be used. Preferred combinations are as described above. The pigment that can be used in combination is preferably refined to the same extent as the refined DPP pigment from the viewpoint of contrast.

  There is no restriction | limiting in particular as dye which can be used together, The well-known dye currently used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.

  The chemical structure is pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

In the pigment dispersion composition of the present invention, only one DPP pigment may be used, or two or more DPP pigments may be used in combination.
The total content of the pigment including the DPP pigment in the pigment dispersion composition and other pigments optionally used in combination is 40 to 90 mass as a ratio of the pigment to the total solid content (mass) of the pigment dispersion composition. % Is preferable, and 50 to 80% by mass is more preferable. When the pigment content is within the above range, the color density is sufficient and it is effective to ensure excellent color characteristics.
Further, the DPP pigment is preferably contained in an amount of 50% by mass or more, more preferably 70% by mass or more with respect to all the pigments in the pigment dispersion composition of the present invention. All of the pigments may be one type or two or more types of DPP pigments.

[(B) phthalimidoalkylated diketopyrrolopyrrole and (C) phthalimidoalkylated quinacridone]
The pigment dispersion composition of the present invention comprises 0.1 to 30 parts by weight of (B) phthalimide alkylated diketopyrrolopyrrole and 100 parts by weight of (A) diketopyrrolopyrrole pigment. It contains 0.1 to 20 parts by weight of (C) phthalimidoalkylated quinacridone with respect to 100 parts by weight of ketopyrrolopyrrole pigment.

  (B) A phthalimidoalkylated diketopyrrolopyrrole is a diketopyrrolopyrrole in which at least one phthalimidoalkyl group is bonded to the diketopyrrolopyrrole. A typical phthalimidomethyl group as a phthalimidoalkyl group has the structure shown below.

  The phthalimidomethylated diketopyrrolopyrrole is a diketopyrrolopyrrole pigment derivative having a structure represented by the following general formula (B).

  In the general formula (B), X and Y each independently represent a hydrogen atom, an alkyl group, a cyano group, an aryl group, or a halogen group. n shows the substitution number of a phthalimidomethyl group and represents the integer of 1-3. X and Y in the general formula (B) have the same meanings as X and Y in the general formula (A), and preferred embodiments are also the same.

(B) Phthalimide alkylated diketopyrrolopyrrole is easily produced by a known production method, for example, by reacting a diketopyrrolopyrrole red pigment with paraform and phthalimide or hydroxymethylphthalimide in sulfuric acid. This synthesis method is described in detail in Japanese Patent Application Laid-Open No. 62-149759, and the like can be referred to. Examples of the diketopyrrolopyrrole red pigment that can be used in this synthesis include C.I. I. Pigment Red 254, 255, 264, and C.I. I. Pigment Orange 71, 73 and the like, and C.I. I. Pigment Red 255 is preferably used.
(B) As phthalimidoalkylated diketopyrrolopyrrole, a mixture of phthalimidomethyl group-substituted phthalimidomethylated diketopyrrolopyrrole and non-phthalimidated diketopyrrolopyrrole red pigment can also be used. . Examples of the diketopyrrolopyrrole red pigment at this time include C.I. I. Pigment Red 254, 255, 264, and C.I. I. And diketopyrrolopyrrole pigments such as Pigment Orange 71 and 73.

  (C) Phthalimidoalkylated quinacridone is a quinacridone in which at least one phthalimidoalkyl group is bonded to a hydrogen atom on the quinacridone ring. A typical phthalimidomethyl group as a phthalimidoalkyl group has the structure shown below.

  Phthalimidomethylated quinacridone is a quinacridone pigment derivative having a structure represented by the following general formula (C).

  In the general formula (C), X and Y each independently represent a hydrogen atom, a methyl group or a chlorine atom. n shows the substitution number of a phthalimidomethyl group and represents the integer of 1-3.

Examples of (C) phthalimidoalkylated quinacridone that can be used in the present invention represented by the above structure include phthalimidomethylated unsubstituted quinacridone, phthalimidomethylated dimethylquinacridone, phthalimidomethylated dichloroquinacridone, and the like.
The (C) phthalimidoalkylated quinacridone contained in the pigment dispersion composition of the present invention may be used alone or in a mixture of two or more.
(C) The phthalimidoalkylated quinacridone can be easily produced by, for example, reacting a quinacridone-based red pigment with paraform and phthalimide or hydroxymethylphthalimide in sulfuric acid. This method is described in Japanese Patent Application Laid-Open No. 55-108466 and the like can be referred to.

  (C) As the phthalimidoalkylated quinacridone, a mixture of a phthalimidomethyl group-substituted phthalimidomethylated quinacridone and a non-phthalimidated quinacridone red pigment can also be used. Examples of the quinacridone red pigment at this time include C.I. I. Unsubstituted quinacridone pigments such as CI Pigment Violet 19; I. Dimethylquinacridone pigments such as C.I. Pigment Red 122; I. Pigment Red 202, C.I. I. Examples thereof include dichloroquinacridone pigments such as Pigment Red 209.

  The pigment dispersion composition of the present invention comprises 0.1 to 30 parts by mass of (B) phthalimidoalkylated diketopyrrolopyrrole, (A) diketopyrrolopyrrole system per 100 parts by mass of the (A) diketopyrrolopyrrole pigment. Although it is necessary to contain 0.1 to 20 parts by mass of (C) phthalimidoalkylated quinacridone per 100 parts by mass of pigment, a particularly preferred content of (B) phthalimidoalkylated diketopyrrolopyrrole is a diketopyrrolopyrrole system. The amount is 0.1 to 25 parts by mass, and most preferably 0.5 to 20 parts by mass per 100 parts by mass of the pigment. Further, the particularly preferable content of (C) phthalimidoalkylated quinacridone is 0.1 to 15 parts by mass per 100 parts by mass of diketopyrrolopyrrole pigment, and optimally 0.5 to 15 parts by mass. It is.

As a ratio of the addition amount of both, it is the range of each of the above contents, and the addition amount of (B) phthalimidoalkylated diketopyrrolopyrrole is equal to or greater than (C) phthalimidoalkylated quinacridone. ,preferable. By containing phthalimidoalkylated diketopyrrolopyrrole and phthalimidoalkylated quinacridone in this range, high pigment dispersibility, high contrast, and excellent surface smoothness of the color filter can be obtained.
In the present invention, (B) phthalimidoalkylated diketopyrrolopyrrole and (C) phthalimidoalkylated quinacridone may be used singly or in combination of two or more.

  In the preparation of the pigment dispersion composition of the present invention, (B) phthalimidoalkylated diketopyrrolopyrrole and (C) phthalimidoalkylated quinacridone may be added to (A) diketopyrrolopyrrole pigment at any timing. However, it is preferable to add at least partly after the diketopyrrolopyrrole is refined (preferably after the average primary particle size is 10 nm to 30 nm). Specifically, for example, addition to a kneaded product after completion of salt milling, addition during desalting dispersion, addition to pigment powder after dry pulverization, addition to pigment dispersion composition before dispersion, pigment dispersion The addition in the middle etc. are mentioned. Add at least some phthalimidoalkylated diketopyrrolopyrrole and phthalimidoalkylated quinacridone after diketopyrrolopyrrole refinement to obtain high pigment dispersibility, high contrast, and excellent surface smoothness of color filters Can do.

In the pigment dispersion composition of the present invention, in order to improve dispersion stability and obtain high contrast, a pigment derivative other than the above-mentioned (B) phthalimide alkylated diketopyrrolopyrrole and (C) phthalimide alkylated quinacridone is used in combination. It is also preferable.
Preferable pigment derivatives that can be used in combination include those having a portion having an affinity for the dispersant and capable of being adsorbed on the surface of the DPP pigment. By using a pigment derivative that has a site that can serve as an adsorption point for the dispersant and that can be adsorbed on the surface of the DPP pigment, the dispersant is easily adsorbed on the surface of the DPP pigment, and the DPP pigment is dispersed as fine particles. It can be dispersed in the composition, and its reagglomeration can also be prevented.

Preferable pigment derivatives that can be used in combination are specifically compounds in which an organic pigment is used as a base skeleton and an acidic group, basic group, or aromatic group is introduced as a substituent in the side chain. Specific examples of the organic pigment serving as a base skeleton include phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, and benzimidazolone pigments. A pigment derivative having a skeleton of a diketopyrrolopyrrole pigment and not included in the component (B) or a derivative having a skeleton of a quinacridone pigment and not included in the component (C) is also used as a pigment derivative. Yes.
In addition, the host skeleton also includes light yellow aromatic polycyclic compounds such as naphthalene-based, anthraquinone-based, triazine-based, and quinoline-based compounds that are not generally called pigments.
Among these, a preferable base skeleton is an azo pigment, and a pigment derivative having a base skeleton of a quinacridone pigment or a diketopyrrolopyrrole pigment and having a structure different from the essential component of the present invention is also preferred. It can be cited as a thing.

Examples of pigment derivatives that can be preferably used in the present invention include, for example, JP-A-3-153780, JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, and JP-A-2006-265528. JP, 8-295810, JP-A-11-199796, JP-A 2005-234478, JP-A 2003-240938, JP-A 2001-356210, JP-A 2007-186681, etc. The thing described in is mentioned.
In the present invention, when a pigment derivative other than (B) phthalimidoalkylated diketopyrrolopyrrole and (C) phthalimidoalkylated quinacridone is used in combination, the added amount of the other pigment derivative used in combination is a pigment dispersion composition in terms of mass. It is preferably 0.1 to 30 parts, more preferably 0.5 to 30 parts, and most preferably 100 parts of pigment (including diketopyrrolopyrrole pigment) contained therein. 1 to 25 parts. In this range, good dispersibility and high contrast can be obtained. When using other pigment derivatives other than the component (B) and the component (C), the total amount of other pigment derivatives should be 10 times or less the total amount of the components (B) and (C). Is preferred.

[(D) Organic solvent]
The pigment dispersion composition of the present invention contains at least one organic solvent.
Examples of the organic solvent (D) used for the preparation of the pigment dispersion composition of the present invention include 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethyl acetate, acetic acid Examples thereof include butyl, ethyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, xylene and the like.
An organic solvent is selected according to the use of a pigment dispersion composition, and only 1 type may be used in a composition and it may use 2 or more types together.
Further, the amount of the organic solvent added is appropriately selected according to the use of the pigment dispersion composition, etc., but when used for the preparation of a colored polymerizable composition described later, from the viewpoint of handling properties, the pigment is included. It can add so that solid content concentration may be 5-50 mass%.

[Other ingredients]
-Dispersant-
From the viewpoint of improving the dispersibility of the pigment to be contained, it is preferable to add a dispersant to the pigment dispersion composition of the present invention.
Examples of the dispersant that can be used in the present invention include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (Meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine and the like.
The polymer dispersant can be further classified into a linear polymer compound, a terminal-modified polymer compound, a graft polymer compound, and a block polymer compound based on its structure.

The polymer dispersant acts to adsorb on the surface of the pigment and prevent reaggregation. Therefore, a terminal-modified polymer compound, a graft polymer compound and a block polymer compound having an anchor site to the pigment surface can be mentioned as preferred structures.
Hereinafter, each of the block-type polymer compound, the graft-type polymer compound, and the terminal-modified polymer compound, which are polymer dispersants suitable for the present invention, will be described.

(Block type polymer compound)
Although it does not specifically limit as a block type high molecular compound used as a polymer dispersing agent, The block type high molecular compound which consists of a pigment adsorption block and the block which is not adsorbed to a pigment is mentioned.
Although it does not restrict | limit especially as a monomer which comprises a pigment adsorption block, For example, the monomer which has a functional group which can adsorb | suck to a pigment is mentioned. Specific examples include a monomer having an organic dye structure or a heterocyclic structure, a monomer having an acidic group, and a monomer having a basic nitrogen atom.
Hereinafter, a monomer having an organic dye structure or a heterocyclic structure, a monomer having an acidic group, and a monomer having a basic nitrogen atom, which are suitable as monomers constituting the pigment adsorption block will be described.

Examples of the monomer having an organic dye structure or a heterocyclic structure include, for example, phthalocyanine series, insoluble azo series, azo lake series, anthraquinone series, quinacridone series, dioxazine series, diketopyrrolopyrrole series, anthrapyridine series, ansanthrone series, Ron, flavanthrone, perinone, perylene, and thioindigo dye structures such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadi Azole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone Benzimidazolone, benzothiazole, succinimide, may phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, be mentioned a monomer having a heterocyclic structure anthraquinone.
More specifically, although not particularly limited, monomers having the following structures can be exemplified.

Examples of the monomer having an acidic group include a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, and a vinyl monomer having a phosphoric acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer.
Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used.
Furthermore, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used as the precursor of the carboxyl group.
Of these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.

  In addition, examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester), And phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester).

  Examples of the monomer having a basic nitrogen atom include vinylpyridine, vinylimidazole, vinyltriazole and the like as monomers having a heterocyclic ring, and (meth) acrylic acid ester as N, N-dimethylaminoethyl (meth) acrylate. N, N-dimethylaminopropyl (meth) acrylate, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylate, N, N-dimethylaminohexyl (meth) acrylate, (Meth) acrylic acid N, N-diethylaminoethyl, (meth) acrylic acid N, N-diisopropylaminoethyl, (meth) acrylic acid N, N-di-n-butylaminoethyl, (meth) acrylic acid N, N -Di-i-butylaminoethyl, morpholinoethyl (meth) acrylate, piperi (meth) acrylate Noethyl, 1-pyrrolidinoethyl (meth) acrylate, N, N-methyl-2-pyrrolidylaminoethyl (meth) acrylate, N, N-methylphenylaminoethyl (meth) acrylate, etc. As meta) acrylamides, N- (N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N′-dimethylaminoethyl) methacrylamide, N- (N ′, N′-diethylaminoethyl) acrylamide N- (N ′, N′-diethylaminoethyl) methacrylamide, N- (N ′, N′-dimethylaminopropyl) acrylamide, N- (N ′, N′-dimethylaminopropyl) methacrylamide, N- ( N ′, N′-diethylaminopropyl) acrylamide, N- (N ′, N′-diethylaminopropyl) meta Rilamide, 2- (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide , Morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide, etc., and styrenes include N, N-dimethylaminostyrene, N, N-dimethylaminomethylstyrene, etc. .

It is also possible to use a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group.
Specific examples include monomers having the following structure.

Furthermore, a monomer containing an ionic functional group can be used.
Examples of ionic vinyl monomers (anionic vinyl monomers, cationic vinyl monomers) include, as anionic vinyl monomers, alkali metal salts of vinyl monomers having the acidic group, organic amines (eg, triethylamine, dimethylaminoethanol, etc.) As a cationic vinyl monomer, the nitrogen-containing vinyl monomer is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom). Benzyl halides such as benzyl chloride and benzyl bromide; alkylsulfonic acid esters such as methanesulfonic acid (alkyl group: C1-18); arylsulfonic acid alkyl esters such as benzenesulfonic acid and toluenesulfonic acid (alkyl group: C1); -18); Dia sulfate Kill (alkyl group: C1 -4) that is quaternized with such, like dialkyl diallyl ammonium salts.

  The monomer having a functional group capable of adsorbing to the pigment as described above can be appropriately selected according to the type of pigment to be dispersed. These may be used alone or in combination of two or more. Good.

The monomer constituting the block that is not adsorbed by the pigment is not particularly limited. For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid Mention may be made of monomers having no pigment adsorbing group, such as diesters, (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, and (meth) acrylonitrile.
These monomers constituting the block that is not adsorbed by the pigment may be used alone or in combination of two or more.
Moreover, when applying to the pigment dispersion composition which needs an alkali image development process, you may use together the monomer which comprises the block which does not adsorb | suck to said pigment, and the vinyl monomer which has an acidic group.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid t-octyl, (meth) acrylic acid dodecyl, (meth) acrylic acid octadecyl, (meth) acrylic acid acetoxyethyl, (meth) acrylic acid phenyl, (meth) 4-hydroxybutyl acrylate, 2-methoxyethyl (meth) acrylate, (meth) a 2-ethoxyethyl laurate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, vinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, (meth ) 1-propenyl acrylate, allyl (meth) acrylate, 2-allyloxyethyl (meth) acrylate, propargyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth ) Diethylene glycol monoethyl ether acrylate, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene Glycol monoethyl ether, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth) acryl Trifluoroethyl acid, octafluoropentyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromo (meth) acrylate Examples thereof include phenyloxyethyl and (meth) acrylic acid γ-butyrolactone.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N- Methylo Acrylamide, N- hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, such as N- allyl (meth) acrylamide.

  Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.

Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
Examples of olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.
Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.
Examples of (meth) acrylonitrile include methacrylonitrile and acrylonitrile.

Examples of the vinyl monomer having an acidic group include a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, and a vinyl monomer having a phosphoric acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer.
Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used.
Furthermore, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride may be used as the precursor of the carboxyl group.
Of these, (meth) acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, and the like.

Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester), phosphorus And acid mono (1-methyl-2-acryloyloxyethyl ester).
Furthermore, a vinyl monomer containing a phenolic hydroxyl group or a vinyl monomer containing a sulfonamide group can be used as the vinyl monomer having an acidic group.

As a method for obtaining the block type polymer compound in the present invention, a conventionally known method can be used.
For example, living polymerization, iniferter method and the like are known. Furthermore, as another method, when radically polymerizing a monomer having a pigment adsorbing group or a monomer having no pigment adsorbing group, thiolcarboxylic acid, 2-acetylthioethyl ether, 10-acetylthiodecanethiol A polymer obtained by polymerizing a compound containing a thioester and a thiol group in the molecule, such as sodium hydroxide or ammonia, to give a polymer having a thiol group at one end Also known is a method of radical polymerization of the monomer component of the other block in the presence of the obtained polymer having a thiol group at one end. Among these, living polymerization is preferable.

  The weight average molecular weight of the block type polymer compound is not particularly limited, but is preferably in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight average molecular weight is 3,000 or more, a stabilizing effect can be obtained more effectively, and when the weight average molecular weight is 100,000 or less, it is more effectively adsorbed and has good dispersibility. Can be demonstrated.

  Commercially available products can also be used as the block polymer compound. Specific examples include “Disperbyk-2000, 2001” manufactured by BYK Chemie, “EFKA 4330, 4340” manufactured by EFKA, and the like.

(Graft type polymer compound)
The graft type polymer compound used as the polymer dispersant is not particularly limited, but a polyalkyleneimine described in JP-A-54-37082, JP-A-61-174939, etc. is reacted with a polyester compound. Preferable examples include compounds in which the side chain amino group of polyallylamine described in JP-A-9-169621 is modified with polyester, polyester polyol-added polyurethane described in JP-A-60-166318, and the like. Furthermore, as described in JP-A-9-171253 and Macromonomer Chemistry and Industry (IPC Publishing Department, 1989), a graft containing a polymerizable oligomer (hereinafter referred to as a macromonomer) as a copolymerization component is used. A suitable type of polymer compound can also be mentioned.

  Suitable examples of the branch part of the graft polymer compound include polystyrene, polyethylene oxide, polypropylene oxide, poly (meth) acrylic acid ester, polycaprolactone, and the like. Among these, a graft polymer compound having a structural unit represented by the following general formula (5) at the branch is more preferable.

In the general formula (5), R ⁷⁴ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, Q is a cyano group, an aryl group having 6 to 30 carbon atoms, or —COOR ⁷⁵ (where, R ⁷⁵ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an aryl group having 6 to 30 carbon atoms).

In general formula (5), the alkyl group represented by R ⁷⁴ may have a substituent, preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group. Examples of the substituent that can be introduced into the alkyl group include a halogen atom, a carboxyl group, an alkoxycarbonyl group, and an alkoxy group.
Specific examples of such an alkyl group include a methyl group, an ethyl group, a hexyl group, an octyl group, a trifluoromethyl group, a carboxymethyl group, and a methoxycarbonylmethyl group.
R ⁷⁴ is particularly preferably a hydrogen atom or a methyl group.

In general formula (5), the aryl group represented by Q may have a substituent, preferably an aryl group having 6 to 20 carbon atoms, and particularly preferably an aryl group having 6 to 12 carbon atoms. . Examples of the substituent that can be introduced into the aryl group include a halogen atom, an alkyl group, an alkoxy group, and an alkoxycarbonyl group.
Specific examples of such aryl groups include phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxy. Examples thereof include a phenyl group, a decyloxyphenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a methoxycarbonylphenyl group, an ethoxycarbonylphenyl group, and a butoxycarbonylphenyl group.
Among such aryl groups, an unsubstituted aryl group, or an aryl group substituted with a halogen atom, an alkyl group, or an alkoxy group is preferred, and in particular, an unsubstituted aryl group or an aryl group substituted with an alkyl group Is preferred.

When Q in the general formula (5) is —COOR ⁷⁵ , the alkyl group represented by R ⁷⁵ may have a substituent, and is preferably an alkyl group having 1 to 12 carbon atoms, particularly a carbon atom. A C1-C8 alkyl group is preferable. Examples of the substituent that can be introduced into the alkyl group include a halogen atom, an alkenyl group, an aryl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group, and a carbamoyl group.
Specific examples of such alkyl groups include methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl. Group, 2-chloroethyl group, 2-bromoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 2-bromopropyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl Group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, cyclohexyl Group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, bicyclo [3.2.1] oct-2-yl group, 1-adamantyl group, dimethylaminopropyl group, acetylaminoethyl group, N, N-dibutyl An aminocarbamoylmethyl group etc. are mentioned.
Among such alkyl groups, an unsubstituted alkyl group, or an alkyl group substituted with a halogen atom, an aryl group, or a hydroxyl group is preferable, and an unsubstituted alkyl group is particularly preferable.

When Q in the general formula (5) is —COOR ⁷⁵ , the aryl group represented by R ⁷⁵ may have a substituent, and is preferably an aryl group having 6 to 20 carbon atoms, particularly a carbon atom. The aryl group of several 6-12 is preferable.
Examples of the substituent that can be introduced into the aryl group include a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, and an acylamino group.
Specific examples of such aryl groups include phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxy. Phenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodeciloylamidophenyl group, Etc.
Among such aryl groups, an unsubstituted aryl group or an aryl group substituted with a halogen atom, an alkyl group, or an alkoxy group is preferable, and an aryl group substituted with an alkyl group is particularly preferable.

Of such R ⁷⁵ , a hydrogen atom and an alkyl group having 1 to 22 carbon atoms are preferable, and a hydrogen atom and an alkyl group having 1 to 12 carbon atoms are particularly preferable.

  Specific examples of the branch part of the graft polymer compound having the structural unit represented by the general formula (5) in the branch part include polymethyl (meth) acrylate and poly-n-butyl (meth) acrylate. , Poly-i-butyl (meth) acrylate, poly (methyl (meth) acrylate-co-benzyl (meth) acrylate), poly (methyl (meth) acrylate-co-styrene), poly (methyl (meth) acrylate-co -(Meth) acrylic acid), poly (methyl (meth) acrylate-co-acrylonitrile) and the like.

Any known method may be used for the synthesis of the graft polymer compound having the structural unit represented by the general formula (5) at the branch.
Specific examples include copolymerization of a macromonomer having a structural unit represented by the general formula (5) and an ethylenically unsaturated monomer copolymerizable with the macromonomer.

  Among the macromonomers having the structural unit represented by the general formula (5), preferred are those represented by the following general formula (6).

In General Formula (6), R ⁷⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and W is a single bond, a linking group shown below, or a divalent group shown below. A linking group constituted by an arbitrary combination is represented, and A represents a group having a structural unit represented by the general formula (5).

In the linking group, Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, or a hydroxyl group, and Z ³ represents a hydrogen atom, carbon An alkyl group having 1 to 18 atoms or an aryl group having 6 to 20 carbon atoms is represented.

  Specific examples of the macromonomer represented by the general formula (6) include those shown below.

  A in the specific structure of the macromonomer has the same meaning as A in the general formula (6).

  As such macromonomer available as a commercial product, one-end methacryloylated polymethyl methacrylate oligomer (Mn = 6,000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.) and one-end methacryloylated poly -N-butyl acrylate oligomer (Mn = 6,000, trade name: AB-6, manufactured by Toa Gosei Chemical Co., Ltd.), single-end methacryloylated polystyrene oligomer (Mn = 6,000, trade name: AS-6, Toa Gosei Chemical Co., Ltd.).

  The molecular weight of the macromonomer is preferably a polystyrene-equivalent number average molecular weight (Mn) of 1,000 to 20,000, and more preferably 2,000 to 15,000. When the number average molecular weight is within the above range, the steric repulsion effect as a dispersant can be more effectively obtained.

  As the ethylenically unsaturated monomer copolymerizable with the macromonomer described above, it is preferable to use the “monomer constituting the pigment adsorption block” in order to improve the dispersibility and dispersion stability of the pigment. . Further, as the other copolymerization component, the “monomer constituting a block that is not adsorbed to the pigment” may be copolymerized.

  The weight average molecular weight of the graft polymer compound is not particularly limited, but is preferably in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight average molecular weight is 3,000 or more, a stabilizing effect can be obtained more effectively, and when the weight average molecular weight is 100,000 or less, it is more effectively adsorbed and has good dispersibility. Can be demonstrated.

  Commercially available products of the graft polymer include “Solsperse 24000, 28000, 32000, 38500, 39000, 55000” manufactured by Lubrizol, “Disperbyk-161, 171, 174” manufactured by BYK Chemie, and the like.

(Terminal-modified polymer compound)
Examples of the terminal-modified polymer compound used as the polymer dispersant include polymers having functional groups at the ends of the polymers described in JP-A-9-77994, JP-A-2002-273191, and the like. A compound can be mentioned.

The method for synthesizing the polymer compound having a functional group at the end of the polymer is not particularly limited, and examples thereof include the following methods and methods combining these.
1. 1. A method of synthesizing by polymerization (for example, radical polymerization, anionic polymerization, cationic polymerization, etc.) using a functional group-containing polymerization initiator Synthesis by radical polymerization using functional group-containing chain transfer agent

  The functional group introduced here is an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or a hydrocarbon group having 4 or more carbon atoms. , A site selected from an alkoxysilyl group, an epoxy group, an isocyanate group, a hydroxyl group, and an ionic functional group. Moreover, you may be a functional group which can be induced | guided | derived to these adsorption sites.

  1 above. Examples of the polymerization initiator (functional group-containing polymerization initiator) capable of introducing a functional group at the polymer terminal used in the synthesis method of 2,2′-azobis (2-cyanopropanol), 2,2 ′ -Azobis (2-cyanopentanol), 4,4'-azobis (4-cyanovaleric acid), 4,4'-azobis (4-cyanovaleric acid chloride), 2,2'-azobis [2- (5 -Methyl-2-imidazolin-2-yl) propane], 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2- (3,4,5) , 6-tetrahydropyrimidin-2-yl) propane], 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}, 2,2′-azobis [ 2-Methyl-N- (2-hydride Kishiechiru) - propionamide] and the like, and derivatives thereof.

  2. Examples of the chain transfer agent (functional group-containing chain transfer agent) that can be used in the synthesis method in which a functional group can be introduced into a polymer terminal include, for example, mercapto compounds (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercapto). Propionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N -(2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3 -Mercapto-1,2-propanediol, 1-merca To-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, benzenethiol, toluenethiol, mercaptoacetophenone, naphthalenethiol, naphthalenemethane Thiol, etc.), disulfide compounds which are oxidants of these mercapto compounds, and halogen compounds (for example, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.).

  As a monomer used for polymerizing a polymer compound having a functional group at the end of the polymer, for example, the above-mentioned “monomer constituting a block that is not adsorbed to the pigment” can be used as a radical polymerizable monomer.

  The molecular weight of the terminal-modified polymer compound is preferably a weight average molecular weight of 1,000 to 50,000. When the number average molecular weight is 1,000 or more, the steric repulsion effect as a dispersant can be more effectively obtained, and when it is 50,000 or less, the steric effect is more effectively suppressed and the pigment is obtained. The adsorption time can be further shortened.

  Examples of commercially available terminal-modified polymer compounds include “Solsperse 3000, 17000, 27000” manufactured by Lubrizol.

  In the present invention, the dispersant is preferably a graft-type polymer compound or a terminal-modified polymer compound. Among these, a graft-type polymer compound containing a copolymer unit derived from a monomer having an organic dye structure or a heterocyclic structure is preferable. As the molecular compound and terminal group, a terminal-modified polymer compound having an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, or a urethane group is particularly preferable.

In the present invention, a dispersion resin can be used if necessary. By using the dispersion resin, the dispersion stability and storage stability of the treated pigment are improved.
As specific examples of the dispersion resin used in the present invention, a resin having a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, or the like is preferable.
Examples of the polymer having a carboxylic acid in the side chain include, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer as described in JP-A-53836, JP-A-59-71048, There are partially esterified maleic acid copolymers and the like, and similarly there are acidic cellulose derivatives having a carboxylic acid in the side chain.

  These include, for example, monomers having a carboxyl group such as (meth) acrylic acid, (anhydrous) maleic acid, crotonic acid, itaconic acid, fumaric acid, styrene, α-methylstyrene, methyl (meth) acrylate, ( (Meth) ethyl acrylate, (meth) propyl acrylate, (meth) acrylate isopropyl, (meth) butyl acrylate, (meth) acrylate isobutyl, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) acrylate, Allyl glycidyl ether, ethyl acrylate glycidyl, crotonic acid glycidyl ether, (meth) acrylic acid chloride, benzyl (meth) acrylate, phenyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylol acrylamide, N, N di Polymer obtained by copolymerizing one or more copolymerization components such as til acrylamide, N-methacryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl acrylamide, maleimide, N-phenylmaleimide Is mentioned. Among them, preferred is a (meth) acrylic resin containing at least (meth) acrylic acid or (meth) acrylic acid alkyl ester as a constituent monomer, and a (meth) acrylic resin containing (meth) acrylic acid and styrene is also suitable. . These acrylic copolymer components are not limited to the above.

These dispersion resins can also have an ethylenic double bond added to the side chain. By imparting a double bond to the side chain, photocurability is enhanced, and resolution and adhesion can be further improved.
Examples of the synthesis means for introducing an ethylenic double bond include the methods described in JP-B-50-34443 and JP-B-50-34444. Specifically, a method of reacting a compound having both a glycidyl group, an epoxycyclohexyl group, and a (meth) acryloyl group with a carboxyl group or a hydroxyl group, acrylic acid chloride, and the like can be given. For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (meth) By using a compound such as acrylic acid chloride or (meth) allyl chloride and reacting with a resin having a carboxyl group or a hydroxyl group, a resin having a polymer group in the side chain can be obtained.

  In particular, a resin obtained by reacting (3,4-epoxycyclohexyl) methyl (meth) acrylate is preferable. Specific examples of these compounds include the NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing Polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co. Ltd.), Biscoat R-264, and KS resist 106 (both in Osaka). Organic Chemical Industry Co., Ltd.), Cyclomer P Series, Plaxel CF200 Series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (Daicel UCB Co., Ltd.), and the like.

Further, it is also possible to use a polymer obtained by a copolymerization reaction of at least a monomer represented by the following general formula (7) and at least an acid group-containing monomer (including the above-described copolymerization component). it can.
General formula (7)
_{^{H 2 C = CRC (= O}} ) OCR 4 R 5 C (= R 3) = CR 2 R 1

In the general formula (7), R represents a hydrogen atom or a methyl group, and R ^{1 to} R ⁵ each independently represents a group selected from a hydrogen atom, a halogen atom, a cyano group, an alkyl group, and an aryl group.

Specific examples of the halogen atom include Cl, Br, and I.
The alkyl group may be linear, branched, or cyclic, and examples thereof include a methyl group, an n-propyl group, an iso-propyl group, and a tert-butyl group, and those having 1 to 7 carbon atoms. preferable.
Examples of the aryl group include a phenyl group, a furyl group, and a naphthyl group.

  Among the above, as the dispersion resin, a copolymer of (meth) acrylic acid and (meth) acrylic acid ester is preferable because various monomers can be selected and solubility and acid value can be controlled. The preferred range of the weight average molecular weight of these dispersed resins measured by gel permeation chromatography (GPC) is 1,000 to 80,000, more preferably 3,000 to 50,000, most preferably 3, 000-20.000. By setting it to 80,000 or less, good dispersibility and fluidity of the liquid can be obtained, and good developability can be obtained.

  These dispersion resins can be used not only when dispersing the pigment when preparing the pigment dispersion composition, but also when adding the colored polymerizable composition described later.

The added amount of the dispersant is preferably 0.5 to 100% by mass, more preferably 3 to 100% by mass, and particularly preferably 5 to 80% by mass with respect to the pigment.
When the amount of the dispersant is within this range, a sufficient pigment dispersing effect can be obtained. However, the optimum addition amount of the dispersant is appropriately adjusted depending on the combination of the pigment and the solvent to be used.
More specifically, if a polymer dispersant is used, the amount used is preferably 5% by mass to 100% by mass with respect to the pigment, and 10% by mass to 80% by mass. A range is more preferred.

  Further, in the pigment dispersion composition of the present invention, a surfactant or the like can be used in addition to the above dispersant for the purpose of improving dispersibility.

  By preparing a colored polymerizable composition using the pigment dispersion composition of the present invention and applying it to the production of a color filter, a color filter having high contrast and excellent surface smoothness can be obtained.

(Preparation of pigment dispersion composition)
The pigment dispersion composition of the present invention can be prepared by passing through a mixing and dispersing step of mixing and dispersing using various mixers and dispersers.
The mixing and dispersing step preferably comprises kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.
In the method for producing a pigment dispersion composition of the present invention, first, (A) a diketopyrrolopyrrole pigment is refined, and when its average primary particle size is in the range of 10 nm to 30 nm, Of the diketopyrrolopyrrole and (C) the phthalimidoalkylated quinacridone, at least a part, preferably the whole, is added, and then (A) a diketopyrrolopyrrole pigment (B) It is preferable to carry out a step of dispersing) phthalimidoalkylated diketopyrrolopyrrole and (C) phthalimidoalkylated quinacridone together with an organic solvent. (A) Before the average primary particle diameter of the diketopyrrolopyrrole pigment is in the range of 10 nm to 30 nm, (B) phthalimidoalkylated diketopyrrolopyrrole and (C) a part of (C) phthalimidoalkylated quinacridone are added. However, it is more preferable that the total amount of the predetermined addition amount be added after the average primary particle diameter of the (A) diketopyrrolopyrrole pigment is in the range of 10 nm to 30 nm and the refining is completed.
In addition, it is preferable that all of the predetermined addition amounts of (B) phthalimidoalkylated diketopyrrolopyrrole and (C) phthalimidoalkylated quinacridone are added at the time of starting the dispersion. A part of the amount added may not be added. In that case, for example, the remaining amount can be added during the dispersion.

  The production method of the present invention will be specifically described. For example, among the predetermined addition amounts of (A) diketopyrrolopyrrole pigment, (B) phthalimidoalkylated diketopyrrolopyrrole, and (C) phthalimidoalkylated quinacridone, At least a part, further mixed here with a dispersing agent used together as necessary, and further pre-dispersed with a homogenizer or the like, an organic solvent, and a media stirring using zirconia beads or the like The pigment dispersion composition of the present invention can be prepared by finely dispersing using a type disperser (for example, a disperse mat manufactured by GETZMANN).

In the present invention, when a fine dispersion treatment is performed using a media agitating type disperser, a medium having an average particle diameter of 0.01 mm or more and 0.2 mm or less is intended for mild dispersion without damaging the dispersion in a short time Is preferably used. Here, the average particle diameter in the present invention refers to the equivalent circle diameter of the media, and is obtained from the average value of the longest diameter and the shortest diameter of 100 media. Specifically, the medium can be magnified and photographed with a stereomicroscope, and the particle size can be obtained from the image.
In the present invention, it is preferable to perform preliminary dispersion in order to crush coarse particles in advance before dispersion with a medium of 0.01 mm or more and 0.2 mm or less. In the preliminary dispersion, since the purpose is to pulverize coarse particles, it is preferable to use a medium having a larger size, preferably a medium having an average particle size of 0.3 mm or more and 1.0 mm or less, and more preferably. The media is 0.4 mm or more and 1.0 mm or less.
The dispersion time may be set to an optimum time depending on the apparatus used, the amount of the pigment dispersion composition, and the like, but is usually about 1 to 24 hours.
For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964), Japanese Patent Application Laid-Open No. 2007-16206, and the like.

  Since the obtained pigment dispersion composition is excellent in the dispersibility and dispersion stability of the diketopyrrolopyrrole pigment, various uses containing the diketopyrrolopyrrole pigment as a colorant, for example, a colored polymerizable composition described below It can be suitably used for products.

<Coloring polymerizable composition>
The colored polymerizable composition of the present invention comprises the above-described pigment dispersion composition of the present invention, a photopolymerizable compound, and a photopolymerization initiator, and preferably further contains an alkali-soluble resin. Depending on, other components may be included.
Hereinafter, each component contained in the colored polymerizable composition of the present invention will be described in detail.

(Pigment dispersion composition)
The colored polymerizable composition of the present invention is constituted by using at least one kind of the above-described pigment dispersion composition of the present invention. The details of the pigment dispersion composition of the present invention constituting the colored polymerizable composition are as described above.
The content of the pigment dispersion composition in the colored polymerizable composition of the present invention is such that the pigment content is in the range of 5 to 70% by mass with respect to the total solid content (mass) of the colored polymerizable composition. The amount is preferable, and an amount in the range of 15 to 60% by mass is more preferable. When the content of the pigment dispersion composition is within this range, the color density is sufficient and effective in securing excellent color characteristics.

[Photopolymerizable compound]
The colored polymerizable composition of the present invention contains at least one photopolymerizable compound.
The photopolymerizable compound that can be used in the present invention is an addition-polymerizable compound having at least one ethylenically unsaturated double bond, and a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. Chosen from. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. The photopolymerizable compound has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.

  Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (a) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

General formula (a)
_{CH 2 = C (R) COOCH} 2 CH (R ') OH
(However, R and R ′ each represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these addition polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set in accordance with the performance design of the final colored polymerizable composition.
For example, it is selected from the following viewpoints. From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). It is also effective to adjust both sensitivity and intensity by using both of these.

In addition, other components (for example, binder polymers such as alkali-soluble resins, photopolymerization initiators, compatibility with colorants (pigments), and dispersibility are also included in the color polymerizable composition. The selection / use method is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination.
In addition, a specific structure may be selected for the purpose of improving the adhesion with a substrate or the like. The addition polymerizable compound is preferably used in the range of 5 to 70% by mass, more preferably 10 to 60% by mass with respect to the nonvolatile component in the colored polymerizable composition. These may be used alone or in combination of two or more. In addition, as the method of using the addition polymerizable compound, an appropriate structure, blending, and addition amount can be arbitrarily selected from the viewpoints of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface tackiness, and the like.

(Photopolymerization initiator)
Examples of the photopolymerization initiator constituting the colored polymerizable composition of the present invention include halomethyloxadiazole described in JP-A-57-6096, JP-B-59-1281, JP-A-53-133428. Active halogen compounds such as halomethyl-s-triazine described in US Pat. Nos. 4,677, and aromatic carbonyls such as ketals, acetals, or benzoin alkyl ethers described in US Pat. Compounds, aromatic ketone compounds such as benzophenones described in U.S. Pat. No. 4,199,420, (thio) xanthones or acridine compounds described in French Patent No. 2456741, JP-A-10-62986 Compounds such as coumarins or lophine dimers described in JP-A-8-0155; Sulfonium organic boron complexes such as 1 JP, and the like.

  As the photopolymerization initiator in the present invention, acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, active halogen compounds (triazine, oxadiazole, coumarin), acridine, biimidazole An oxime ester type is preferable.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Suitable examples include 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1. be able to.

  Preferred examples of the ketal photopolymerization initiator include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.

  Preferred examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, and 4,4′-dichlorobenzophenone. it can.

  Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the active halogen compound (triazine-based, oxadiazole-based, coumarin-based) include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl). ) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (Trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) ) -S-triazine, methoxystyryl-2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxystyryl -2,6-di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (di) Ethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -S-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2-trichloromethyl -5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, 3-methyl-5 -A No-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl- Preferable examples include 5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin.

  Preferable examples of the acridine photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the biimidazole photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, Preferred examples include 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer.

  In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl Examples thereof include carbonyl-diphenyl phosphonyl oxide and hexafluorophospho-trialkylphenyl phosphonium salt.

In this invention, it is not limited to the above photoinitiator, Other well-known things can also be used. For example, vicinal polykettle aldonyl compounds described in US Pat. No. 2,367,660, and α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, the triarylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, Benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516; C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Examples include Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and oxime ester compounds described in JP-A No. 2000-66385.
Moreover, these photoinitiators can also be used together.

  As content in the coloring polymeric composition of a photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of this composition, More preferably, it is 0.5-5.0. % By mass. When the content of the photopolymerization initiator is within this range, the polymerization reaction can proceed well to form a film with good strength.

[Alkali-soluble resin]
The colored polymerizable composition of the present invention preferably contains an alkali-soluble resin. By containing the alkali-soluble resin in the colored polymerizable composition, the pattern forming property can be further improved when the colored polymerizable composition is applied to pattern formation by a photolithography method.

  The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As the linear organic polymer, a polymer having a carboxylic acid in the side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Preferred examples also include acidic cellulose derivatives having a carboxylic acid, and polymers having a hydroxyl group and an acid anhydride added to the polymer, and a polymer having a (meth) acryloyl group in the side chain.

Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Etc.

  As a suitable thing of alkali-soluble resin in this invention, the copolymer of (meth) acrylic acid and the other monomer copolymerizable with this is mentioned especially. Here, (meth) acrylic acid is a general term that combines acrylic acid and methacrylic acid, and (meth) acrylate is also a general term for acrylate and methacrylate.

Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. it can.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH _2. = CR ¹ R ² , CH ₂ = C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² is an aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon ring, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. And the like.

These other copolymerizable monomers can be used singly or in combination of two or more.
Preferred other copolymerizable monomers are selected from CH ₂ ═CR ¹ R ² , CH ₂ ═C (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate, and styrene. At least one selected from the group consisting of CH ₂ ═CR ¹ R ² and / or CH ₂ ═C (R ¹ ) (COOR ³ ).

  The content of the alkali-soluble resin in the colored polymerizable composition is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and particularly preferably the total solid content of the composition. 2 to 15% by mass.

〔solvent〕
In general, the colored polymerizable composition of the present invention can be suitably prepared by using a solvent together with the aforementioned components.
Examples of the solvent used include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and lactic acid. Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate; methyl 3-oxypropionate, ethyl 3-oxypropionate Alkyl 3-esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxy Ethyl propionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvate Propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol No ethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone , Cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene and xylene; and the like.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using it independently.

[Other ingredients]
In the colored polymerizable composition of the present invention, if necessary, other than a sensitizing dye, an epoxy resin, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, a filler, and the above alkali-soluble resin. Various additives such as a polymer compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor.

[Sensitizing dye]
A sensitizing dye may be added to the colored polymerizable composition of the present invention as necessary. The sensitizing dye can promote the radical generation reaction of the photopolymerization initiator and the polymerization reaction of the photopolymerizable compound by the exposure at a wavelength that can be absorbed by the sensitizing dye.
Examples of such a sensitizing dye include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

(Spectral sensitizing dye or dye)
Spectral sensitizing dyes or dyes preferred as sensitizing dyes used in the present invention are polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal). ), Cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), thiazines (eg thionine, methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin) , Acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyll) Chlorophyllin, center metal-substituted chlorophyll), metal complexes (for example, the following compound), anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), and the like.

The example of a more preferable spectral sensitizing dye or dye is illustrated below.
A styryl dye described in JP-B-37-13034; a cationic dye described in JP-A-62-143044; a quinoxalinium salt described in JP-B-59-24147; described in JP-A-64-33104 A new methylene blue compound; anthraquinones described in JP-A No. 64-56767; benzoxanthene dyes described in JP-A No. 2-1714; acridines described in JP-A Nos. 2-226148 and 2-226149 Pyryllium salts described in JP-B-40-28499; Cyanines described in JP-B-46-42363; Benzofuran dyes described in JP-A-2-63053; JP-A-2-85858, JP-A-2-216154 Conjugated ketone dyes disclosed in Japanese Patent Publication No. 57-10605; Azocinnamylidene derivatives described in Japanese Patent No. 0321; cyanine dyes described in Japanese Patent Laid-Open No. 1-287105; Japanese Patent Laid-Open Nos. 62-31844, 62-31848, 62-1443043 Xanthene dyes described above; aminostyryl ketone described in JP-B-59-28325; dye described in JP-A-2-17943; merocyanine dye described in JP-A-2-244050; described in JP-B-59-28326 Merocyanine dyes described in JP-A-59-89303; merocyanine dyes described in JP-A-8-129257; benzopyran dyes described in JP-A-8-334897.

(Dye having a maximum absorption wavelength at 350 to 450 nm)
Other preferred embodiments of the sensitizing dye include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 to 450 nm.
For example, polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, , Squalium).

  More preferable examples of the sensitizing dye include compounds represented by the following general formulas (XIV) to (XVIII).

(In General Formula (XIV), A ¹ represents a sulfur atom or —NR ⁶⁰ —, R ⁶⁰ represents an alkyl group or an aryl group, and L ⁰¹ represents the basicity of the dye in combination with the adjacent A ¹ and carbon atom. Represents a non-metallic atomic group forming a nucleus, R ⁶¹ and R ⁶² each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and R ⁶¹ and R ⁶² are bonded to each other to form an acidic nucleus of a dye. W may represent an oxygen atom or a sulfur atom.)
Preferred specific examples [(F-1) to (F-5)] of the compound represented by the general formula (XIV) are shown below.

(In the general formula (XV), Ar ¹ and Ar ² each independently represent an aryl group, ^{-L 02} - are connected via a bond by wherein ^{-L 02} -. Is -O- or -S- W is as defined in the general formula (XIV).)
Preferable examples of the compound represented by the general formula (XV) include the following [(F-6) to (F-8)].

(In the general formula (XVI), A ² represents a sulfur atom or —NR ⁶⁹ —, L ⁰³ represents a nonmetallic atomic group that forms a basic nucleus of the dye in combination with adjacent A ² and a carbon atom, represents ^{R 63, R 64, R 65} , R 66, 1 monovalent non-metallic atomic group ^{R 67} and ^{R 68} are each ^{independently, R 69} represents an alkyl group or an aryl group.)
Preferable examples of the compound represented by the general formula (XVI) include the following [(F-9) to (F-11)].

(In general formula (XVII), A ³ and A ⁴ each independently represent —S— or —NR ⁷³ —, and R ⁷³ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. , L ⁰⁴ and L ⁰⁵ each independently represents a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ³ , A ⁴ and a carbon atom, and R ⁷¹ and R ⁷² each independently represents 1 A non-metallic atomic group which can be bonded to each other to form an aliphatic or aromatic ring.)
Preferable examples of the compound represented by the general formula (XVII) include the following [(F-12) to (F-15)].

  In addition, examples of suitable sensitizing dyes used in the present invention include those represented by the following formula (XVIII).

(In General Formula (XVIII), A ⁵ represents an aromatic ring or a hetero ring which may have a substituent, X represents an oxygen atom, a sulfur atom, or —N (R ⁷⁴ ) —, and Y represents An oxygen atom, a sulfur atom, or ═N (R ⁷⁴ ), each of R ⁷⁴ , R ⁷⁵ , and R ⁷⁶ independently represents a hydrogen atom or a monovalent non-metallic atomic group, and A ⁵ and R ⁷⁴ , R ⁷⁵ and R ⁷⁶ can be bonded to each other to form an aliphatic or aromatic ring.)

Here, when R ⁷⁴ , R ⁷⁵ , and R ⁷⁶ represent a monovalent non-metallic atomic group, they preferably represent a substituted or unsubstituted alkyl group or aryl group.
Next, preferred examples of R ⁷⁴ , R ⁷⁵ and R ⁷⁶ will be specifically described. Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy , Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N-alkylureido group, N, N-dialkylureido group, N-arylureido Group, N, N-diarylureido group, N-alkyl-N-arylureido group, N-alkylureido group, N-arylureido group, N-alkyl-N-alkylureido group, N-alkyl-N-arylureido Group, N, N-dialkyl-N-alkylureido group, N, N-dialkyl-N-arylureido group, N-aryl-N-alkylureido group, N-aryl-N-arylureido group, N, N- Diaryl-N-alkylureido group, N, N-diaryl-N-arylureido group, N- Alkyl-N-aryl-N-alkylureido group, N-alkyl-N-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N- Alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group , Carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group Nyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfina Moyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfato group Famoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), a dialkyl phosphonate Group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate group). ), A phosphonooxy group (—OPO ₃ H ₂ ) and its conjugated base group (hereinafter referred to as phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), a diarylphosphonooxy group (—OPO ₃ (—OPO ₃ ( _{aryl) 2),} alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), Monoarukiruho Honookishi group _(-OPO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugated base group (hereinafter And cyano group, nitro group, aryl group, heteroaryl group, alkenyl group, alkynyl group, and silyl group.
Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.

  Specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group. , Ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl Group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonopheny Group, and a phosphate Hona preparative phenyl group.

  As the heteroaryl group, a group derived from a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and examples of the heteroaryl ring in the particularly preferred heteroaryl group include Is, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indolizine, indazole, indazole, Purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalazine, phenoxazine, flaza , Include phenoxazine and the like, it may be further benzo-fused or may have a substituent.

Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfide Moyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonato group, monoaryl phosphono group, aryl phospho Examples thereof include a nato group, a phosphonooxy group, a phosphonatoxy group, an aryl group, an alkenyl group, and an alkylidene group (such as a methylene group).

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of preferred substituted alkyl groups as R ⁷⁴ , R ⁷⁵ , or R ⁷⁶ obtained by combining the above substituents with an alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxy Methyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N -Cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, Xoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N- Methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatopropyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N -Tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group , Methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl Group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl Group, etc. can be mentioned.

Specific examples of preferred aryl groups as R ⁷⁴ , R ⁷⁵ , or R ⁷⁶ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable. preferable.

Specific examples of the preferable substituted aryl group as R ⁷⁴ , R ⁷⁵ , or R ⁷⁶ include a monovalent nonmetallic atomic group (other than a hydrogen atom) as a substituent on the ring-forming carbon atom of the aryl group. What has is used. Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, cal Xiphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl Methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, Examples include 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

In addition, more preferable examples of R ⁷⁵ and R ⁷⁶ include a substituted or unsubstituted alkyl group. A more preferred example of R ⁷⁴ includes a substituted or unsubstituted aryl group. The reason is not clear, but by having such a substituent, the interaction between the electronically excited state caused by light absorption and the initiator compound becomes particularly large, and the radical, acid or base of the initiator compound is generated. It is estimated that the efficiency is improved.

Next, A ⁵ in the general formula (XVIII) will be described. A ⁵ represents an aromatic ring or a heterocyclic ring which may have a substituent. Specific examples of the aromatic ring or heterocyclic ring which may have a substituent include R ⁷⁴ in formula (XVIII). , R ⁷⁵ , or R ⁷⁶ may be the same as those exemplified in the above description.
Among them, preferable A ⁵ includes an alkoxy group, a thioalkyl group, and an aryl group having an amino group, and particularly preferable A ⁵ includes an aryl group having an amino group.

Next, Y in the general formula (XVIII) will be described. Y is a nonmetallic atom or a nonmetallic atomic group directly connected to the nitrogen-containing heterocyclic ring in the general formula (XVIII) via a double bond, and more specifically, an oxygen atom, a sulfur atom, or ═N ( ^R74 ). Here, R ⁷⁴ represents a hydrogen atom or a monovalent nonmetallic atomic group. In the general formula (XVIII), X represents an oxygen atom, a sulfur atom, or —N (R ⁷⁴ ) —. R ⁷⁴ has the same meaning as in Y.

  Next, the compound represented by the general formula (XVIII-1), which is a preferred embodiment of the compound represented by the general formula (XVIII) used in the present invention, will be described.

In General Formula (XVIII-1), A ⁵ represents an aromatic ring or a hetero ring that may have a substituent, and X represents an oxygen atom, a sulfur atom, or —N (R ⁷⁴ ) —. R ⁷⁴ , R ⁷⁷ , and R ⁷⁸ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, and A ⁵ and R ⁷⁴ , R ⁷⁷ , and R ⁷⁸ are each aliphatic or aromatic. Can be linked to form a sex ring. Ar represents an aromatic ring or a heterocyclic ring having a substituent. However, the substituent on the Ar skeleton needs to have a sum of Hammett values greater than zero. Here, the sum of the Hammett values is greater than 0 means that the substituent has one substituent, and the Hammett value of the substituent may be greater than 0, and has a plurality of substituents. The sum of Hammett values at may be greater than zero.

In general formula (XVIII-1), A ⁵ and R ⁷⁴ have the same meanings as in general formula (XVIII), R ⁷⁷ is R ⁷⁵ in general formula (XVIII), and R ⁷⁸ is R in general formula (XVIII). ^It is synonymous with ⁷⁶ . Ar represents an aromatic ring or a hetero ring having a substituent, and is synonymous with A ⁵ in the general formula (XVIII).
However, as a substituent that can be introduced into Ar in the general formula (XVIII-1), it is essential that the sum of Hammett values is 0 or more. Examples of such a substituent include a trifluoromethyl group, Examples thereof include a carbonyl group, an ester group, a halogen atom, a nitro group, a cyano group, a sulfoxide group, an amide group, and a carboxyl group. The Hammett values of these substituents are shown below. Trifluoromethyl group (—CF ₃ , m: 0.43, p: 0.54), carbonyl group (eg, —COHm: 0.36, p: 0.43), ester group (—COOCH ₃ , m: 0 .37, p: 0.45), halogen atom (eg, Cl, m: 0.37, p: 0.23), cyano group (—CN, m: 0.56, p: 0.66), sulfoxide group (e.g. _{-SOCH 3, m: 0.52, p} : 0.45), amide groups (e.g. _{-NHCOCH 3, m: 0.21, p} : 0.00), carboxyl group (-COOH, m: 0. 37, p: 0.45). The parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value, and (m: 0.50) is the Hammett value of 0.50 when the substituent is introduced at the meta position. Indicates that there is. Among these, preferable examples of Ar include a phenyl group having a substituent, and preferable substituents on the Ar skeleton include an ester group and a cyano group. The substitution position is particularly preferably located at the ortho position on the Ar skeleton.

  Preferred specific examples of the sensitizing dye represented by the general formula (XVIII) according to the present invention [Exemplary compound (F1) to Illustrative compound (F56)] are shown below, but the present invention is not limited thereto. Absent.

  Among the sensitizing dyes applicable to the present invention, the compound represented by the general formula (XVIII) is preferable from the viewpoint of deep curability.

  The above sensitizing dye can be subjected to various chemical modifications as described below for the purpose of improving the characteristics of the colored polymerizable composition of the present invention. For example, by combining a sensitizing dye and an addition polymerizable compound structure (for example, an acryloyl group or a methacryloyl group) by a method such as a covalent bond, an ionic bond, or a hydrogen bond, It is possible to improve the effect of suppressing the unnecessary precipitation of the dye from the crosslinked cured film.

The content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and still more preferably 0.1% with respect to the total solid content of the colored polymerizable composition. ˜5 mass%.
When the content of the sensitizing dye is within this range, it is highly sensitive to the exposure wavelength of the ultra-high pressure mercury lamp, and it is preferable in terms of development margin and pattern formability as well as deep film curability.

(Epoxy resin)
The colored polymerizable composition of the present invention can use an epoxy resin as a thermal polymerization component in order to increase the strength of the formed coating film.
The epoxy resin is a compound having two or more epoxy rings in the molecule such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound.
For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( In addition to Tonasei Chemical Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103 and the like (manufactured by Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (manufactured by Daicel Chemical) Similar bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UC) can also be used.

Examples of the cresol novolak type include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (manufactured by Tohto Kasei), Denacol EM-125, etc. (manufactured by Nagase Kasei), and biphenyl type As alicyclic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′-diglycidylbiphenyl, Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100 and the like (manufactured by Toto Kasei), Epiclon 430, 673, 695, 850S, 4032 (Dainippon Ink) It can be mentioned.
1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid Diglycidyl ester, amine type epoxy resins such as Epototo YH-434 and YH-434L, and glycidyl ester obtained by modifying dimer acid in the skeleton of bisphenol A type epoxy resin can also be used.

Among these, “molecular weight / number of epoxy rings” is preferably 100 or more, and more preferably 130 to 500. If the “molecular weight / number of epoxy rings” is small, the curability is high, the shrinkage at the time of curing is large, and if it is too large, the curability is insufficient, the reliability is poor, and the flatness is poor.
Specific preferred compounds include Epototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, Plaxel GL-61, GL-62, 3,5,3 ', 5'-tetramethyl. -4,4 'diglycidyl biphenyl, celoxide 2021, 2081, epolide GT-302, GT-403, EHPE-3150, etc. are mentioned.

(Fluorine organic compounds)
The colored polymerizable composition of the present invention contains a fluorine-based organic compound, thereby improving liquid properties (particularly fluidity) when used as a coating solution, and improving coating thickness uniformity and liquid-saving properties. be able to.
That is, the colored polymerizable composition containing a fluorine-based organic compound reduces the interfacial tension between the surface to be coated and the coating liquid, improves the wettability to the surface to be coated, and improves the coating property to the surface to be coated. Therefore, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that a film having a uniform thickness with small thickness unevenness can be formed.

  3-40 mass% is suitable for the fluorine content rate in a fluorine-type organic compound, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. When the fluorine content is within this range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  Examples of the fluorinated organic compound include MegaFuck F171, F172, F173, F177, F141, F142, F143, F144, R30, and F437 (above, Dainippon Ink and Chemicals, Inc.) Manufactured), FLORARD FC430, FC431, FC171 (above, manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (manufactured by Asahi Glass Co., Ltd.).

In particular, the fluorinated organic compound is effective in preventing coating unevenness and thickness unevenness when forming a thin coating film using the colored polymerizable composition of the present invention. Furthermore, it is also effective when the colored polymerizable composition of the present invention is applied to slit coating that easily causes liquid breakage.
As for the addition amount of a fluorine-type organic compound, 0.001-2.0 mass% is preferable with respect to the total mass of a coloring polymeric composition, More preferably, it is 0.005-1.0 mass%.

(Thermal polymerization initiator)
It is also effective to contain a thermal polymerization initiator in the colored polymerizable composition of the present invention.
Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds.
Examples of the azo compounds include azobis compounds, and examples of the peroxide compounds include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, and peroxide. Examples thereof include oxydicarbonate.

(Surfactant)
Various surfactants may be added to the colored polymerizable composition of the present invention from the viewpoint of improving coatability. As the surfactant, various nonionic, cationic, and anionic surfactants can be used in addition to the above-mentioned fluorine-based surfactant.
Of these, fluorine-based surfactants having a perfluoroalkyl group and nonionic surfactants are preferred as the nonionic surfactant.
Specific examples of the fluorosurfactant include Megafac (registered trademark) series manufactured by Dainippon Ink and Chemicals, Inc., and Fluorard (registered trademark) series manufactured by 3M.

Specific examples of cationic surfactants include phthalocyanine derivatives (commercially available product EFKA-745 (manufactured by Morishita Sangyo)), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) Polymer Polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).
Specific examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol dilaurate. Stearate, sorbitan fatty acid ester (pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, manufactured by BASF, Tetronic 304, 701, 704, 901, 904, 150R1, etc. are mentioned.
Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

(Other additives)
In addition to the above, various additives can be added to the colored polymerizable composition of the present invention.
Specific examples of additives include fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, and hydroxyl group Alkali-soluble resins such as those obtained by adding acid anhydride to polymers, alcohol-soluble nylon, phenoxy resin formed from bisphenol A and epichlorohydrin; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, Polymer dispersing agents such as EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), disperse aid 6, disperse aid 8, disperse aid 15, disperse aid 9100 (manufactured by Sannopco); Solsparse 3000, 5000, 000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 and other Solsperse dispersants (manufactured by Geneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84 , F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka) and Isonet S-20 (Sanyo Kasei); 2- (3-t-butyl-5-methyl-2-hydroxy UV absorbers such as phenyl) -5-chlorobenzotriazole and alkoxybenzophenone; and anti-aggregation agents such as sodium polyacrylate.

Further, when the alkali solubility of the uncured part is promoted and the developability of the colored polymerizable composition is further improved, the colored polymerizable composition of the present invention is added with an organic carboxylic acid, preferably a molecular weight of 1000 or less. It is preferable to add a low molecular weight organic carboxylic acid.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

Furthermore, you may add a thermal-polymerization inhibitor to the coloring polymeric composition of this invention.
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

  The colored polymerizable composition of the present invention is a photopolymerizable compound, a photopolymerization initiator, and, if necessary, an alkali-soluble resin, a solvent, and a surface active agent, compared to the pigment dispersion composition of the present invention described above. It can be prepared by adding an additive such as an agent.

Since the colored polymerizable composition of the present invention includes the pigment dispersion composition of the present invention, it is excellent in the dispersion stability of the pigment contained as the colorant. In addition, the colored film produced using the colored polymerizable composition of the present invention has high contrast and excellent surface smoothness because the color material is uniformly and stably dispersed.
For this reason, the colored polymerizable composition of the present invention is preferably used for forming a colored region of a color filter.

<Color filter and manufacturing method thereof>
The color filter of the present invention is characterized by having a colored pattern formed on the substrate using the above-described colored polymerizable composition of the present invention. Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

The method for producing a color filter of the present invention is characterized in that a film of the colored polymerizable composition of the present invention is formed on a substrate by coating, and preferably pre-baked, then exposed and developed sequentially. .
By such a method, a color filter used for a liquid crystal display element or a solid-state imaging element can be manufactured with low process difficulty, high quality, and low cost.
Hereinafter, each step will be described in detail.

[Application]
In the present invention, in producing a color filter, a film of a colored polymerizable composition is formed by coating. As a coating method, known methods such as spin, slit-and-spin, and slit can be used, but slit coating is preferably used from the viewpoint of productivity.
As a substrate used for the color filter of the present invention, for example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, And a photoelectric conversion element substrate used for a solid-state imaging device or the like, for example, a silicone substrate or a plastic substrate.
On these substrates, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

In addition, a driving substrate (hereinafter referred to as “TFT type liquid crystal driving substrate”) on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed is used. In addition, a color pattern using the colored polymerizable composition of the present invention can be formed to produce a color filter.
Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of the TFT liquid crystal driving substrate can be used.

In the present invention, it is preferable to use slit coating as a method for applying the colored polymerizable composition of the present invention to a substrate. The slit coating conditions vary depending on the size of the coated substrate. For example, when coating is applied to a fifth generation glass substrate (1100 mm × 1250 mm), the colored polymerizable composition from the slit nozzle The discharge amount is usually 500 to 3000 microliters / second, preferably 800 to 2000 microliters / second, and the coating speed is usually 50 to 300 mm / second, preferably 100 to 250 mm / second. .
Moreover, as solid content of the coloring polymeric composition used at this slit application | coating process, it is 10-23% normally, Preferably it is 13-20%.

When forming a coating film with the colored polymerizable composition of the present invention on a substrate, the thickness of the coating film (after pre-baking treatment) is generally 0.3 to 5.0 μm, preferably 0.5 to 4 0.0 μm, most preferably 0.5 to 3.0 μm.
In the case of a color filter for a solid-state image sensor, the thickness of the coating film (after pre-baking treatment) is preferably in the range of 0.5 to 5.0 μm.

[Pre-bake]
As described above, the film of the colored polymerizable composition of the present invention is preferably formed on the substrate by a coating method and then prebaked.
If necessary, a vacuum treatment can be performed before pre-baking.
The vacuum drying conditions are such that the degree of vacuum is usually about 0.1 to 1.0 torr (13 to 133 Pa), preferably about 0.2 to 0.5 torr (27 to 67 Pa).
Moreover, when performing a prebaking process as needed, it is 50-140 degreeC using a hotplate, oven, etc., Preferably it is about 70-110 degreeC, and it carries out on the conditions for 10 to 300 seconds. it can. Note that high-frequency treatment or the like may be used in combination with the pre-bake treatment. High frequency processing can be used alone.

〔exposure〕
After the formed film is dried or pre-baked as desired, the coating film is exposed through a predetermined mask pattern.
The radiation used for exposure is particularly preferably ultraviolet rays such as g-line, h-line, i-line, and j-line.
When manufacturing a color filter for a liquid crystal display device, exposure using mainly h-line and i-line is preferably used by a proximity exposure machine and a mirror projection exposure machine.
Further, when manufacturing a color filter for a solid-state image sensor, it is preferable to mainly use i-line in a stepper exposure machine.
When manufacturing a color filter using a TFT type liquid crystal driving substrate, the photomask used has a through hole or a U-shaped depression in addition to a pattern for forming a pixel (colored pattern). The thing in which the pattern for forming is provided is used.

〔developing〕
Development is performed after the exposure. By this development, the uncured portion of the coating film after exposure is eluted into the developer, and only the cured portion remains on the substrate.
The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
As the developer, the colored polymerizable composition of the present invention is exposed and the exposed portion is polymerized and cured, and then the coating of the colored polymerizable composition in the uncured portion is dissolved while the cured portion is not dissolved. Any of them can be used.
Specifically, a developing solution obtained by combining various organic solvents or an alkaline aqueous solution can be used.

Examples of the organic solvent used in the developer include those described above that can be used in preparing the colored polymerizable composition of the present invention.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide. , Tetraethylammonium hydroxide, choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.01 An alkaline aqueous solution dissolved so as to be ˜1 mass% can be mentioned.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

The development method may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. It is also possible to prevent uneven development by previously moistening the surface to be developed with water or the like before touching the developer. In addition, development can be performed with the substrate inclined.
Further, when manufacturing a color filter for a solid-state image sensor, paddle development is also used.

After the development process, after a rinsing process for washing and removing excess developer, drying is performed, and then heat treatment (post-baking) is performed as necessary to complete the curing.
The rinse treatment is usually performed with pure water, but to save liquid, pure water is used in the final cleaning, and used pure water is used in the initial stage of cleaning. You may use the method of using a sound wave irradiation together.

After the rinse treatment, draining and drying are performed, and then a heat treatment at 100 ° C. to 250 ° C. is usually performed. This post-baking is heating after development for complete curing, and is preferably performed by heating at 200 ° C. to 250 ° C. (hard baking).
In this heat treatment (post-bake), the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with a formula.
It is preferable to perform UV cleaning after post-baking and before applying the next color. The UV cleaning is capable of performing at the glass substrate cleaning machine or the like (e.g. LC4000, product of Hitachi Electronics Engineering Ltd. Co.), the UV irradiation dose is usually 100mJ ^/ cm ² ~1000mJ ^/ cm 2 approximately. By performing the UV cleaning, the development residue can be removed, and the pattern forming property of the next color can be improved.

The color filter of the present invention can be manufactured by sequentially performing the above steps.
In addition, a color filter in which a cured film (colored pattern) colored in a plurality of colors is formed by sequentially repeating the above process for each color (3 colors or 4 colors) according to the desired number of hues. can do.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” means “part by mass”.
First, components used in Examples and Comparative Examples will be described.

<Synthesis of Resin B>
7.5 parts of the exemplified monomer M-11, 31.25 parts of methyl methacrylate, 11.25 parts of methacrylic acid, and 167 parts by weight of methoxypropylene glycol were introduced into a nitrogen-substituted three-necked flask, and a stirrer ( The mixture is stirred with Shinto Kagaku Co., Ltd. (Three-One Motor) and heated to 78 ° C. while flowing nitrogen into the flask. To this, 0.1 part of dimethyl-2,2′-azobis (2-methylpropionate) (V-601 manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated and stirred at 78 ° C. for 2 hours. After 2 hours, 0.1 part of V-601 was further added, and the mixture was heated and stirred for 3 hours to obtain a 30% solution of Resin B. The obtained resin B is a resin used before the drying process of the pigment during salt milling.

<Synthesis of Resin A>
Resin A was synthesized in the same manner except that the monomers used in the synthesis of Resin B and the amounts charged were replaced with the monomers and amounts listed in Table 1 below. The obtained resin A is a resin used before the drying process of the pigment during salt milling.
Table 1 below shows the monomers used when synthesizing Resins A and B, the amounts charged, the weight average molecular weights of the synthesized Resin A and Resin B, and the acid value. Here, as the weight average molecular weight, a value calculated by polystyrene conversion by GPC (gel permeation chromatography) measurement under the following conditions is used.
Column used: TSKgel MultiporeHXL-M
(Porous polydisperse type linear column) manufactured by Tosoh Eluent: THF
Flow rate: 1.0 ml / min
Temperature: 40 ° C
Detection condition: RI
System: High-speed GPC equipment set (Toso-HLC-8220)

The acid value is a value measured by the following method.
(Measurement method of acid value)
Titration with a 0.1 N · KOH ethanol solution was performed for calculation. The acid value of the solution was determined according to the acid value measurement method of JIS K 0070: 1992 “Testing method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”. A certain amount of resin was dissolved in methoxy-2-propyl acetate, and titration was performed with a KOH / ethanol solution using phenolphthalein as an indicator for measurement.

In Table 1 above, the monomer M-11 refers to the exemplified monomers listed as preferred specific examples of the monomer represented by the general formula (1), the maleimide, and the maleimide derivative. In Table 1, details of the monomers used for the synthesis of Resin A are as follows.
St: Styrene BzMA: Benzyl methacrylate MAA: Methacrylic acid MMA: Methyl methacrylate

Next, in the examples and comparative examples, various dispersants used in preparing the pigment dispersion composition will be described.
Resin (1): ^* AA-6 / monomer M-11 / styrene / methacrylic acid
= 55/10/20/15 (mass%) copolymer
(Weight average molecular weight 20,000)
^* AA-6: One-end methacryloylated polymethyl methacrylate oligomer
(Mn = 6000, manufactured by Toagosei Chemical Industry Co., Ltd.)
Resin (2): Maleimide / styrene / methacrylic acid = 20/65/15 (mass%)
Copolymer (weight average molecular weight 20,000)

  Moreover, the structure of the pigment derivative used in preparation of salt milling and a pigment dispersion composition is as follows.

[Example 1]
(Manufacturing method of treated pigment using salt milling)
(A) Irgafore Red BT-CF (manufactured by Ciba Japan Co., Ltd., Pigment Red 254) 50 g, sodium chloride 500 g (average particle size 10 μm) which is a water-soluble inorganic salt, and (A) diketopyrrolopyrrole pigment in the present invention; 150 g of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a water-soluble organic solvent, was charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 10 hours.
Next, 25 g of the resin A solution (solid content: 30% by mass) synthesized as described above was added to this mixture and mixed, and this mixture was poured into about 3 liters of warm water and heated to about 70 ° C. while being heated. The mixture was stirred with a speed mixer for about 1 hour to form a slurry. Thereafter, filtration and washing were carried out to remove sodium chloride and the solvent, followed by drying in a hot air oven at 60 ° C. for about 24 hours, and a surface-treated (A) diketopyrrolo in which resin A was adhered to at least a part of the surface. A pyrrole pigment was obtained.
When the particle diameter of the obtained treated pigment was measured with a transmission electron microscope, the average primary particle diameter was 30 nm. For the measurement of the particles, an average value obtained by measuring 500 average values of the major axis and the minor axis of the pigment at a magnification of 100,000 times is used.

[Example 1]
<Preparation of pigment dispersion composition>
The components of the following composition (1) are mixed, and using a homogenizer, the rotational speed is 3,000 r. p. m. And stirred for 1 hour to prepare a mixed solution containing the pigment.

[Composition (1)]
・ Surface treated diketopyrrolopyrrole pigment obtained by the above method [component (A)] 86 parts ・ Pigment derivative (1) (the above structure) 10 parts ・ Pigment derivative (3) [the above structure: component (B)] 10 copies
[13.4 parts per 100 parts of component (A)]
Pigment derivative (4) [the structure: component (C)] 5 parts
[6.69 parts per 100 parts of component (A)]
Dispersbyk-2001 (byk chemie) 33 parts 50% 30% 1-methoxy-2-propyl acetate solution of resin (1) 50 parts 30% 1-methoxy-2-propyl acetate solution of resin (2) 1-methoxy-2-propyl acetate 767 parts

  Subsequently, the mixed solution obtained above was pre-dispersed for 20 minutes with a bead disperser (Dispermat, GETZMANN) using 0.8 mmφ zirconia beads (Nikkato Co., Ltd.). Thereafter, this dispersion was performed for 2 hours in a bead disperser Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) using 0.10 mmφ zirconia beads (manufactured by Nikkato Co., Ltd.), and the red pigment dispersion composition of Example 1 Got.

(Evaluation of pigment dispersion composition)
The dispersibility and dispersion stability of the obtained pigment dispersion composition were evaluated.
With respect to the prepared pigment dispersion composition, the viscosity η1 (25 ° C.) immediately after the preparation and the viscosity η2 (25 ° C.) after one week after the preparation were measured using an E-type viscometer. Both η1 and η2 were 9 cp, and it was confirmed that good dispersibility and dispersion stability were exhibited.

[Example 2]
<Preparation of colored polymerizable composition>
Using the pigment dispersion composition obtained in Example 1 above, a colored polymerizable composition having the following composition (2) was prepared.
The red pigment dispersion composition A and the yellow pigment dispersion composition A were prepared as follows.

(Red pigment dispersion composition A)
In the production method of the treated pigment, the same procedure as in Example 1 was performed except that “red pigment (“ chromophthaled red A2B ”: PR177” manufactured by BASF) was used instead of “Irgaphore Red BT-CF”. Salt milling was performed to obtain a treated pigment having a primary average particle size of 28 nm. Thereafter, a red pigment dispersion composition A was obtained in the same manner as in Example 1 except that the obtained treated pigment was used and “pigment derivative (5)” was used instead of “pigment derivative (1)”. .
Moreover, the yellow pigment dispersion composition A was prepared as follows.
(Yellow pigment dispersion composition A)
Example 1 and Example 1 except that, in the method for producing the treated pigment, “yellow pigment (“ E4GN-GT: PY150 ”manufactured by LANXESS)” was used instead of “Irgafore Red BT-CF”. Similarly, salt milling was performed to obtain a treated pigment having a primary average particle size of 30 nm. Thereafter, a yellow pigment dispersion composition A was obtained in the same manner as in Example 1 except that the obtained treated pigment was used and “pigment derivative (6)” was used instead of “pigment derivative (1)”.

[Composition (2)]
-800 parts of the red pigment dispersion composition obtained in Example 1-800 parts of the red pigment dispersion composition A-400 parts of the yellow pigment dispersion composition A-80 parts of dipentaerythritol pentahexaacrylate (photopolymerizable compound) 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl]-
2,6-di (trichloromethyl) -S-triazine (photopolymerization initiator) 30 parts benzyl methacrylate / methacrylic acid (= 70/30 [mass ratio]) copolymer (weight average molecular weight: 10,000) Propylene glycol monomethyl ether acetate solution (solid content 30%) (alkali-soluble resin) 300 parts, 1-methoxy-2-propyl acetate (solvent) 590 parts, ethyl 3-ethoxypropionate (solvent) 400 parts

<Preparation of color filter using colored polymerizable composition>
The obtained colored polymerizable composition (color resist solution) was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the x value serving as an index of color density was 0.650. It was dried in an oven at 90 ° C. for 60 seconds (pre-baking). Then, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). Covered with aqueous solution and allowed to stand for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been subjected to the photo-curing treatment and the development treatment as described above is heat-treated in an oven at 220 ° C. for 30 minutes (post-baking) to form a colored film for constituting a color filter on the glass substrate. A colored filter substrate (color filter) having a colored region was prepared.
Further with respect to the prepared substrate, a glass substrate washer UV washed with (LC4000, Hitachi Electronics Engineering Co., Ltd.) (20 mW / cm ² at 500 mJ / cm ^2), after which the pre-baking, the development, the post The bake was performed again. Thereafter, the UV cleaning, the pre-baking, the development, and the post-baking were further performed to obtain an evaluation colored filter substrate (color filter).

  The colored polymerizable composition (color resist solution) prepared as described above and the evaluation colored filter substrate (color filter) prepared from the colored polymerizable composition were evaluated as follows. The results are shown in Table 2.

-1. Viscosity measurement
About the prepared colored polymerizable composition (color resist solution), the viscosity η1 (25 ° C.) immediately after the preparation and the viscosity η2 (25 ° C.) after one week after the preparation were measured using an E-type viscometer. did.

-2. Measurement and evaluation of contrast
The contrast of the produced colored filter substrate for evaluation (color filter) was measured as follows.
That is, a colored filter substrate for evaluation is placed between two polarizing plates, and the luminance when the polarization axis is parallel and the luminance when the polarization axis is orthogonal are measured using BM-5 manufactured by Topcon Corporation. A value obtained by dividing by the luminance at the time of orthogonality (= luminance at the time of parallel / luminance at the time of orthogonality) was used as an index for evaluating contrast. (This evaluation method was referred to “1990 7th Color Optical Conference, 512-color display 10.4“ size TFT-LCD color filter, Ueki, Koseki, Fukunaga, Yamanaka ”).

-3. Surface roughness measurement
About the produced colored filter substrate for evaluation (color filter), the surface roughness of the colored film surface was measured using an atomic force microscope (NanoScope IIIa, manufactured by Nanoworld).

[Example 3]
In Example 1, salt milling was performed in the same manner as in Example 1 except that 0.8 g of the pigment derivative (1) was further added during salt milling to obtain a treated pigment. The average primary particle size was 26 nm. Thereafter, using the obtained treated pigment, a red pigment dispersion composition was obtained in the same manner as in Example 1. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, the same evaluation as in Example 2 was performed. The results are shown in Table 2.

[Example 4]
In Example 1, salt milling was performed in the same manner as in Example 1 except that 0.9 g of the pigment derivative (2) was further added at the time of salt milling to obtain a treated pigment. The average primary particle size was 23 nm. Thereafter, using the obtained treated pigment, a red pigment dispersion composition was obtained in the same manner as in Example 1. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, the same evaluation as in Example 2 was performed. The results are shown in Table 2.

[Example 5]
In Example 1, salt milling was performed in the same manner as in Example 1 except that 0.9 g of the pigment derivative (2) was further added, and after kneading, “resin A solution (solid content) A treated pigment was obtained in the same manner as in Example 1 except that the “resin B solution (solid content: 30% by mass)” obtained in the above synthesis example was used instead of “30% by mass)”. The average primary particle size was 23 nm. Thereafter, using the obtained treated pigment, a red pigment dispersion composition was obtained in the same manner as in Example 1. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, the same evaluation as in Example 2 was performed. The results are shown in Table 2.

[Example 6]
In Example 1, salt milling was performed in the same manner as in Example 1 except that 0.9 g of the pigment derivative (2) was further added, and after kneading, “resin A solution (solid content) A treated pigment was obtained in the same manner as in Example 1 except that “Resin B solution (solid content 30% by mass)” was used instead of “30% by mass)”. The average primary particle size was 23 nm. Thereafter, using the obtained treated pigment, a red pigment dispersion composition was prepared in the same manner as in Example 2 except that “10 parts of pigment derivative (2)” was used instead of “10 parts of pigment derivative (1)”. Obtained. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 1, the same evaluation as in Example 2 was performed. The results are shown in Table 2.

[Example 7]
In Example 1, salt milling was performed in the same manner as in Example 1 except that 0.9 g of the pigment derivative (2) was further added, and after kneading, “resin A solution (solid content) A treated pigment was obtained in the same manner as in Example 1 except that “Resin B solution (solid content 30% by mass)” was used instead of “30% by mass)”. The average primary particle size was 23 nm. Then, using the obtained treated pigment, instead of “pigment derivative (1) 10 parts, pigment derivative (3) 10 parts, pigment derivative (4) 5 parts”, “pigment derivative (2) 11 parts, pigment derivative ( A red pigment dispersion composition was obtained in the same manner as in Example 1 except that 3) 7 parts and pigment derivative (4) 7 parts were used. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, the same evaluation as in Example 2 was performed. The results are shown in Table 2.

[Comparative Example 1]
Salt milling was performed in the same manner as in Example 1 to obtain a treated pigment. The average primary particle size was 30 nm. Thereafter, using the obtained treated pigment, instead of “86 parts of the treated pigment obtained by the above method”, “103 parts of the treated pigment obtained by the above method” were used, and “pigment derivative (3)”. In addition, a red pigment dispersion composition was obtained in the same manner as in Example 1 except that the “pigment derivative (4)” was not used. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, the same evaluation as in Example 2 was performed. The results are shown in Table 2.

[Comparative Example 2]
In Example 1, salt milling was performed in the same manner as in Example 1 except that 0.8 g of the pigment derivative (1) was further added during salt milling to obtain a treated pigment. The average primary particle size was 26 nm. Thereafter, using the obtained treated pigment, instead of “86 parts of the treated pigment obtained by the above method”, “103 parts of the treated pigment obtained by the above method” were used, and “pigment derivative (3)”. In addition, a red pigment dispersion composition was obtained in the same manner as in Example 1 except that the “pigment derivative (4)” was not used. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, the same evaluation as in Example 2 was performed. The results are shown in Table 2.

[Comparative Example 3]
In Example 1, salt milling was performed in the same manner as in Example 1 except that 0.8 g of the pigment derivative (1) was further added during salt milling to obtain a treated pigment. The average primary particle size was 26 nm. Thereafter, the treated pigment thus obtained was used, and the same procedure as in Example 1 was conducted except that “15 parts of pigment derivative (3)” was used instead of “10 parts of pigment derivative (3) and 5 parts of pigment derivative (4)”. Thus, a red pigment dispersion composition was obtained. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, the same evaluation as in Example 2 was performed. The results are shown in Table 2.

[Comparative Example 4]
In Example 1, salt milling was performed in the same manner as in Example 1 except that 0.8 g of the pigment derivative (1) was further added during salt milling to obtain a treated pigment. The average primary particle size was 26 nm. Thereafter, the same treatment as in Example 1 was carried out except that the obtained treated pigment was used and “pigment derivative (4) 15 parts” was used instead of “pigment derivative (3) 10 parts, pigment derivative (4) 5 parts”. Thus, a red pigment dispersion composition was obtained. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, the same evaluation as in Example 2 was performed. The results are shown in Table 2.

[Comparative Example 5]
In Example 1, salt milling was performed in the same manner as in Example 1 except that 1 g of the pigment derivative (4) was further added during salt milling to obtain a treated pigment. The average primary particle size was 24 nm. Thereafter, using the obtained treated pigment, instead of “86 parts of the treated pigment obtained by the above method”, “103 parts of the treated pigment obtained by the above method” were used, and “pigment derivative (3)”. In addition, a red pigment dispersion composition was obtained in the same manner as in Example 1 except that the “pigment derivative (4)” was not used. Further, after obtaining a red colored polymerizable composition in the same manner as in Example 2, the same evaluation as in Example 2 was performed. The results are shown in Table 2.

As is apparent from Table 2, the colored polymerizable compositions of Examples 2 to 7 prepared using the pigment dispersion composition of the present invention of Example 1 do not show an increase in viscosity after storage. From this, it can be seen that the organic pigment contained is excellent in dispersion stability. Moreover, it turns out that the colored filter (color filter) formed using this colored polymeric composition is excellent in contrast, and can form a colored film with small surface roughness.
From these results, it is estimated that the colored polymerizable composition of the present invention provides a color filter having high contrast and reduced pixel defects due to surface roughness and the like.

Claims (9)

  Diketopyrrolopyrrole pigment, 0.1 to 30 parts by weight of phthalimidoalkylated diketopyrrolopyrrole to 100 parts by weight of the diketopyrrolopyrrole pigment, 0.1 to 100 parts by weight of the diketopyrrolopyrrole pigment A pigment dispersion composition containing -20 parts by mass of a phthalimidoalkylated quinacridone and at least one organic solvent.   The pigment dispersion composition according to claim 1, wherein the average primary particle diameter of the diketopyrrolopyrrole pigment is 10 nm to 30 nm. The diketopyrrolopyrrole pigment is,
Mechanically kneading a diketopyrrolopyrrole pigment, a water-soluble inorganic salt, and a water-soluble organic solvent that does not substantially dissolve the water-soluble inorganic salt;
Removing the water-soluble inorganic salt and the water-soluble organic solvent;
Drying the contacted diketopyrrolopyrrole pigment;
Contacting the resin with the diketopyrrolopyrrole pigment prior to the drying step;
The pigment dispersion composition according to claim 1, wherein the pigment dispersion composition is a diketopyrrolopyrrole pigment obtained by a method having the following.   The pigment dispersion composition according to claim 3, wherein the resin is a polymer compound having an acid value of 50 to 300 mgKOH / g. To a diketopyrrolopyrrole pigment having an average primary particle diameter of 10 nm to 30 nm, 0.1 to 30 parts by mass of a phthalimide alkylated diketopyrrolopyrrole and 100% by mass of the diketopyrrolopyrrole pigment and the diketopyrrolo Adding 0.1 to 20 parts by weight of phthalimide alkylated quinacridone to 100 parts by weight of a pyrrole pigment;
Diketopyrrolopyrrole pigment, 0.1 to 30 parts by weight of phthalimidoalkylated diketopyrrolopyrrole per 100 parts by weight of the diketopyrrolopyrrole pigment and 0.1 to 20 parts by weight per 100 parts by weight of the diketopyrrolopyrrole pigment And a step of dispersing a mass part of phthalimidoalkylated quinacridone together with an organic solvent.   The coloring polymeric composition containing the pigment dispersion composition of any one of Claim 1 to 4, a photopolymerizable compound, and a photoinitiator.   The colored polymerizable composition according to claim 6, further comprising an alkali-soluble resin.   A color filter using the colored polymerizable composition according to claim 6.   A method for producing a color filter, wherein the colored polymerizable composition according to claim 6 or 7 is applied onto a substrate to form a coating film, the formed film is exposed, and then developed.