JP2012212054A - Colored composition for color filter, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a colored composition for color filter which has excellent dispersibility, is superior in flowability and stable, and also has excellent developability; and a high-quality color filter that has a filter segment with a high contrast ratio or a black matrix with high optical density, using the colored composition for color filter.SOLUTION: A colored composition for color filter contains a colorant, a resin type dispersant, and a solvent, in which the colorant contains a pigment with an average primary particle diameter being 20-50 nm and an aspect ratio of pigment particles being 1:1-1:3.5, and the resin type dispersant contains an acrylic block copolymer which is A-B block copolymer or B-A-B block copolymer comprising A block having solvent affinity and B block having a nitrogen atom-containing functional group and of which amine value is 10 mgKOH/g or more and 99 mgKOH/g or less in terms of effective solid content.

Description

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. Other typical liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and electrolysis is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) method for vertically aligning nematic liquid crystal with optical properties, and Optical Convencence Bend (OCB) method in which the optical axes of uniaxial retardation films are orthogonal to each other to perform optical compensation Etc., and each has been put to practical use.

  A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. Increasing demands are being made.

  A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

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

  However, in general, a color filter in which a pigment is dispersed has a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by the pigment. That is, since light leaks when light must be blocked (OFF state) or transmitted light attenuates when light must be transmitted (ON state), display devices in the ON state and the OFF state There is a problem that the upper luminance ratio (contrast ratio) is low.

  In order to achieve high brightness and high contrast of the color filter, the pigment contained in the filter segment is often used after being refined. However, various pigments (similarly called crudes having a particle size of 10 to 100 μm produced by chemical reaction, which are made into a mixture of primary particles and aggregated secondary particles by pigmentation treatment) Even if the particles are refined by the refinement treatment method, the pigments whose primary particles or secondary particles have been refined generally tend to agglomerate. When the refinement is too advanced, a huge lump of pigment solid is formed. End up. Furthermore, even if the pigment that has been refined further is dispersed in a pigment carrier containing a resin or the like, and the secondary particles of the pigment are stabilized as close as possible to the primary particles, a stable coloring composition is obtained. It is very difficult.

  In addition, it is difficult to disperse pigments that have been refined into a pigment carrier containing a resin or the like, and it is difficult to disperse pigments stably at high concentrations. It is known to cause various problems.

  For example, pigment compositions containing pigments composed of fine particles often exhibit high viscosity, making it difficult to remove and transport the product from a disperser, and in the worst case, cause gelation during storage, It may even be difficult to use. Furthermore, regarding the surface of the color-developed product of the pigment composition, a poor state such as a decrease in gloss and poor leveling occurs. When different types of pigments are used in combination, color unevenness due to aggregation or phenomena such as sedimentation may cause uneven color and a marked reduction in coloring power.

  Therefore, in general, a resin-type dispersant is used in order to keep the dispersion state good. The resin-type dispersant has a structure of a part that is adsorbed to the pigment and a part that has a high affinity for the solvent as the dispersion medium, and the performance is determined by the balance of these two functional parts. Various types of resin-type dispersants are used according to the surface state of the pigment to be dispersed.

  As the resin-type dispersant, a structure-controlled one having a block type structure (Patent Document 1) or a comb structure (Patent Document 2) is known as having excellent pigment dispersibility. In either case, since the pigment has been made finer in recent years and the surface area has increased, it tends to be added in a large amount to ensure dispersion stability. Non-image area after development due to decrease in solubility in developer due to increase in amount of dispersant, poor solubility of developer in developer, development failure within specified time, or development possible In some cases, the undissolved product of the colored resin composition tends to remain. Furthermore, when the undissolved material of the colored resin composition remains on the non-pixel portion on the substrate, the obtained color filter causes a decrease in transmittance and contrast, and when it remains on the pattern edge portion, Such a situation may affect the subsequent process such as peeling or deterioration of the sealing property in the liquid crystal cell forming process.

  In the case of a comb-shaped structure, a comb tooth portion having a functional group such as a carboxyl group or an acryloyl group is grafted to a polyamine compound having a primary or secondary amino group, and the remaining primary or secondary amine is present on the pigment surface. However, primary or secondary amines are not preferred because they have active hydrogen with high reactivity.

  As described above, the color filter is required to have not only high contrast but also high brightness. In general, in order to obtain high brightness, when dispersing the pigment in the pigment carrier, the transparency of the dispersion is increased to close to the primary particles, and the spectral spectrum of the dispersion has high transmittance, thereby increasing the brightness. It has gained.

  In order to solve these problems, attempts have been made to improve the pigment dispersibility by adding a small amount by improving the structure and acid value of the acrylic block copolymer (see Patent Documents 3, 4 and 5).

Also, in the gaps between the red, green and blue filter segments of the color filter, a grid-like black pattern called a black matrix having a light shielding property (hereinafter sometimes simply referred to as BM) is provided for the purpose of improving contrast. It is common to form.
The black matrix is required to have excellent light shielding properties in order to improve the image quality of the liquid crystal display.

In recent years, in order to cope with higher definition and higher brightness, a black matrix is formed on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device from a conventional method of forming a black matrix on a color filter substrate. A BOA (Black Matrix on Array) method is being studied. This BOA method eliminates the need for a pasting process for alignment with the element, can greatly increase the pixel aperture ratio (aperture ratio), and can shorten the manufacturing process. Since the quality can be improved and the cost can be reduced, there are many advantages over the BM formed on the color filter substrate.

  Since these BMs are also required to have high light-shielding properties, dispersion stabilization at a high pigment concentration is required, and high resolution needs to be imparted simultaneously. As with color resists, in black matrix coloring compositions, the amount of dispersant added tends to increase in order to obtain dispersion stability. If the solubility in the developer is poor, development can be accomplished within a predetermined time. There is a problem in that the undissolved product of the colored resin composition tends to remain in the non-image area after development even if it is not developed or can be developed.

JP 2002-31713 A Japanese Patent Laid-Open No. 11-1515 JP 2006-265528 A JP 2006-321979 A JP 2009-25813 A

  The present invention is a color filter coloring composition having excellent dispersibility, good fluidity and stability, and excellent developability, and a high contrast ratio filter segment using the color filter coloring composition, Another object is to provide a high-quality color filter having a black matrix with a high optical density.

  As a result of intensive studies to solve the above problems, the present inventors have found that a pigment having an average primary particle diameter of 20 to 50 nm and a pigment particle aspect ratio of 1: 1 to 1: 3.5. An AB block copolymer or a B-A-B block copolymer comprising an A block having a solvophilic property, a B block having a functional group containing a nitrogen atom, and an amine It has been found that the above-mentioned problems can be solved by using an acrylic block copolymer having a value of 10 mgKOH / g or more and 99 mgKOH / g or less in terms of effective solid content as a resin-type dispersant.

That is, the present invention provides a color filter coloring composition containing a colorant, a resin-type dispersant, and a solvent.
The colorant contains a pigment having an average primary particle diameter of 20 to 50 nm and an aspect ratio of the pigment particles of 1: 1 to 1: 3.5;
The resin-type dispersant is an AB block copolymer or a B-A-B block copolymer composed of an A block having solvophilicity and a B block having a functional group containing a nitrogen atom, and The present invention relates to a color filter coloring composition comprising an acrylic block copolymer having an amine value of 10 mgKOH / g or more and 99 mgKOH / g or less in terms of effective solid content.

In the present invention, the acrylic block copolymer contains 5 to 40 mol% of a repeating unit represented by the following general formula (I) in a solvophilic A block and contains a nitrogen atom. In the B block which has this, it contains the repeating unit represented by the following general formula (II), It is related with the said coloring composition for color filters characterized by the above-mentioned.

[In General Formula (I), n represents an integer of 1 to 5, and R1 represents a hydrogen atom or a methyl group. ]

[In General Formula (II), R ₄ and R ₅ are each independently a cyclic or chain-like alkyl group which may have a substituent, an aryl group which may have a substituent, or An aralkyl group which may have a substituent is represented, R ₃ represents an alkylene group having 1 or more carbon atoms, and R ₂ represents a hydrogen atom or a methyl group. ]

Further, in the present invention, the acrylic block copolymer has a methacrylic acid ester monomer other than the structural unit represented by the general formula (I) in the A block having solvophilicity as a precursor. It is related with the said coloring composition for color filters characterized by containing the structural unit to perform 50-90 mol%.
Further, in the present invention, the coloring composition for a color filter according to any one of claims 1 to 3, wherein the colorant is a perylene-based black pigment.
In addition, the present invention relates to the coloring composition for a color filter, which further contains an acidic derivative of an organic pigment or a pigment derivative that is a metal salt thereof.

  In addition, the present invention relates to the colored composition for a color filter, further comprising a photopolymerizable monomer and a photopolymerization initiator.

  The present invention also relates to a color filter comprising a filter segment and / or a black matrix formed on the substrate from the colored composition for color filter.

The coloring composition for a color filter of the present invention is a stable coloring composition for a color filter excellent in fluidity and developability, and each color filter having a high contrast ratio by using the coloring composition for a color filter. Segments and high optical density black matrix patterns can be formed.
Therefore, a high quality color filter can be obtained by using the coloring composition for a color filter of the present invention.

First, various components of the coloring composition for a color filter of the present invention will be described.
<Colorant>
[Filter segment colorants]
The colorant of the present invention contains a pigment having an average primary particle diameter of 20 to 50 nm and an aspect ratio of pigment particles of 1: 1 to 1: 3.5. When the average primary particle size is less than 20 nm, pigment dispersion becomes difficult. Moreover, since an average primary particle diameter exceeds 50 nm, since a contrast ratio and a brightness fall, it is unpreferable. That is, when the average primary particle size is increased, the light of the backlight is scattered and leakage light is generated when the polarizing plate is crossed, leading to a reduction in contrast ratio. Further, since the transmittance decreases, it also affects the decrease in brightness. Further, when the aspect ratio of the pigment particles exceeds the range of 1: 1 to 1: 3.5, for example, when the shape is a needle shape, it is not preferable because the light scattering of the backlight and the transmittance are reduced. Preferably, when the aspect ratio of the pigment particles exhibits a spherical shape in the range of 1: 1 to 1: 3.5, the distance between the primary particles of each pigment is made more uniform, so light scattering is less likely to occur. Thus, the contrast ratio and brightness are increased.

  As the colorant of the present invention, for example, when forming each color filter segment, it is possible to use pigments of various colors such as red pigment, blue pigment, green pigment, yellow pigment, purple pigment, orange pigment, brown pigment. it can. Examples of the chemical structure include organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. In addition, various inorganic pigments can be used.

Specific examples of pigments that can be used are shown below. The following “CI” means a color index (CI).
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 9, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254, more preferably C.I. I. Pigment Red 177, 209, 224, 242, or 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment Blue 15: 6.

  Examples of the green pigment include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36 or 58.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, or 180.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Orange 38 or 71.

  A plurality of the above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

[Colorant for black matrix]
In the case of forming a black matrix, as a colorant, as a pigment having an average primary particle diameter of 20 to 50 nm and an aspect ratio of pigment particles of 1: 1 to 1: 3.5, a black pigment or the above-described pigment Mixed pigments of red, purple, yellow, green and blue pigments can be used. When the average primary particle size is less than 20 nm, pigment dispersion becomes difficult. Moreover, since an average primary particle diameter exceeds 50 nm, since light-shielding property falls, it is unpreferable. That is, when the average primary particle diameter is increased, the packing of the particles is sparse, and the concealability is reduced due to the formation of gaps. On the other hand, by suppressing the average primary particle diameter to 50 nm or less, the packing of the particles becomes dense and the light shielding property is improved. Further, even when the aspect ratio exceeds the range of 1: 1 to 1: 3.5, for example, the shape is needle-like, the packing of the particles becomes sparse, and the concealability is reduced due to gaps, which is not preferable. . Preferably, the pigment particles exhibit a spherical shape with an aspect ratio in the range of 1: 1 to 1: 3.5, more preferably in the range of 1: 1 to 1: 2.0. Since the distance is made more uniform, gaps are less likely to occur and the concealment is enhanced.

  Usable black pigments include perylene black pigments, carbon black, acetylene black, lamp black, bone black, graphite, iron black, titanium black, and pigments such as the above red, purple, yellow, green, and blue pigments. A mixed color system is mentioned. Among these, pigment mixed systems such as perylene black pigments, carbon black, red, purple, yellow, green, and blue pigments are preferable. More preferably, a perylene black pigment is used alone or a combination of a perylene black pigment and carbon black is used from the viewpoint of concealability and electrical characteristics.

When the perylene black pigment and carbon black are used in combination, the content of the perylene black pigment in 100% by weight of the black pigment is preferably 80 to 95% by weight. When the ratio of the perylene-based black pigment is 95% by weight or more, sufficient light shielding properties cannot be obtained around 1.0 μm. If it is less than 80% by weight, the transmittance at a wavelength of 1000 nm is lowered, and the infrared sensor for alignment may not be recognized. In addition, the increase in carbon black may increase the relative dielectric constant.

  In addition, the black matrix formed using the above-described perylene-based black pigment or a mixed color-based black coloring composition has excellent light-shielding properties, so that it has excellent display contrast of a color liquid crystal display device and low dielectric constant characteristics. Therefore, it is difficult to cause defects due to the electrical characteristics of the black matrix such as liquid crystal alignment disorder and conduction between electrodes formed on the TFT substrate, and it has excellent transmittance in the near infrared region. This is possible and is suitable for a driving substrate of a thin film transistor (TFT) type color liquid crystal display device.

Carbon black in the present invention is commercially available, for example, # 260, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 45L, # 47, # 47 manufactured by Mitsubishi Chemical Corporation. 50, # 52, MA7, MA8, MA11, MA100, MA100R, MA100S, MA230, manufactured by DEGUSSA PrIntex L, PrIntex P, PrIntex 30, PrIntex 35, PrIntex 40,
Examples include PrIntex 45, PrIntex 55, PrIntex 60, PrIntex 300, PrIntex 350, SpecIal Black 4, SpecIal Black 350, and SpecIal Black 550. Among these, # 45 is preferable from the viewpoint of obtaining a high OD. Carbon black may be used individually by 1 type, or 2 or more types may be mixed and used for it.

  In the colorant of the present invention, the content of the pigment having an average primary particle diameter of 20 to 50 nm and an aspect ratio of 1: 1 to 1: 3.5 is 30 to 30% in 100% by weight of the total colorant. It is preferably 100% by weight, and more preferably 50 to 100% by weight.

  In the colored composition of the present invention, the content of the pigment having an average primary particle diameter of 20 to 50 nm and an aspect ratio of 1: 1 to 1: 3.5 is usually 1% by weight in the total solid content. Above, preferably 5% by weight or more, and usually 95% by weight or less, preferably 85% by weight or less. If the ratio of the pigment is too small, the film thickness with respect to the color density becomes too large, which may adversely affect the gap control or the like when forming a liquid crystal cell. On the other hand, when the proportion of the colorant is too large, it is difficult to obtain dispersion stability.

[Miniaturization of pigment]
The pigment used in the present invention can have a primary particle diameter of 20 to 50 nm and an aspect ratio of 1: 1 to 1: 3.5 by salt milling or the like. By using such a pigment, it is possible to form a filter segment having a higher contrast ratio and to form a black matrix having a high light shielding property.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

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

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

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

<Resin type dispersant>
The resin-type dispersant in the present invention is an AB block copolymer or a B-A-B block copolymer comprising an A block having a solvophilic property and a B block having a functional group containing a nitrogen atom. And an acrylic block copolymer having an amine value of 10 mgKOH / g or more and 99 mgKOH / g or less in terms of effective solid content.

  The resin-type dispersant has a colorant-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. However, since the pigment adsorbing groups are randomly arranged in the random type dispersant, the viscosity tends to increase by crosslinking. On the other hand, in the block copolymer, the pigment adsorbing groups are arranged at high density, so that the adsorption to the pigment is strong and there is no crosslinking. For this reason, the block copolymer can ensure higher dispersion stability. Further, when the amine value is 10 mgKOH / g or more and 99 mgKOH / g or less, the solubility in the developer is improved, the development process can be performed within a predetermined time, and the non-pixel portion on the substrate is colored. The undissolved material of the resin composition does not remain.

The monomer that is a precursor of the A block having solvophilicity is not particularly limited as long as it does not have a functional group containing a nitrogen atom such as an amino group and can be copolymerized with the monomer constituting the B-block. No.
For example, styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth ) Octyl acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) (Meth) acrylic acid ester monomers such as acrylates; (meth) acrylic acid salt monomers such as (meth) acrylic acid chlorides; vinyl acetate monomers; allyl glycidyl ether, crotonic acid glycidyl ether Any polymer structure obtained by copolymerizing comonomers including glycidyl ether monomers.

  Among them, the A block includes a polyalkylene glycol (meth) acrylate such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate as a copolymerization component (that is, a partial structure derived from polyalkylene glycol (meth) acrylate). In particular, and preferably has a partial structure represented by the following general formula (I).

[In General Formula (I), n represents an integer of 1 to 5, and R ₁ represents a hydrogen atom or a methyl group. ]

  As for the partial structure represented by general formula (I), it is especially preferable that 5-40 mol% is contained in A block.

  Further, from the viewpoint of improving dispersion stability, 50 to 90 mol% of a structural unit having a (meth) acrylic acid ester monomer other than the partial structure represented by the general formula (I) as a precursor in the A block. It is preferable to contain, More preferably, it is 60-80 mol%. Among them, (meth) acrylic acid ester monomers include (meth) methyl acrylate, (meth) ethyl acrylate (propyl meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth) It is preferable to use octyl acrylate because the dispersibility and stability of the coloring composition are excellent.

  By including the partial structure represented by the general formula (I) in the A block, hydrophilicity is imparted and the solubility in the developer is improved. On the other hand, the compatibility with the binder resin is increased and the dispersion stability is improved by further including a structural unit having a (meth) acrylate monomer other than the partial structure represented by the general formula (I) as a precursor. .

  The B block having a functional group containing a nitrogen atom preferably has a primary to tertiary amino group as the functional group. The content ratio of the primary to tertiary amino groups is preferably 10 mol% or more, more preferably 40 mol% or more of the entire nitrogen atom-containing functional group.

The amino group is preferably —NR ₄ R ₅ (wherein R ₄ and R ₅ each independently have a cyclic or chain-like alkyl group which may have a substituent, or a substituent. A preferable aryl group or an aralkyl group which may have a substituent may be represented by the following formula.

[In General Formula (II), R ₄ and R ₅ are each independently a cyclic or chain-like alkyl group which may have a substituent, an aryl group which may have a substituent, or An aralkyl group which may have a substituent is represented, R ₃ represents an alkylene group having 1 or more carbon atoms, and R ₂ represents a hydrogen atom or a methyl group. ]

Among them, R ₄ and R ₅ are preferably a methyl group, R ₃ is preferably a methylene group or an ethylene group, and R ₂ is preferably a methyl group. A preferable example of such a partial structure is represented by the following formula.

Two or more kinds of partial structures containing an amino group as described above may be contained in one B-block. In that case, the partial structure containing two or more kinds of amino groups may be contained in the B-block in any form of random copolymerization or block copolymerization. In addition, a partial structure not containing an amino group may be included in the B-block as long as the effects of the present invention are not impaired. Examples of such a partial structure include (meth) acrylic acid. Examples thereof include partial structures derived from ester monomers. The content of such a partial structure not containing an amino group in the B-block is preferably 0 to 60 mol%, more preferably 0 to 20 mol%, but such an amino group-free partial structure is a B-block. Most preferably it is not included.

  In addition, when a quaternary ammonium base is used as the B block having a functional group containing a nitrogen atom, it has a strong polarity and interacts with other resins to increase viscosity or gel without adsorbing to the colorant. There is. Accordingly, the functional group containing a nitrogen atom is preferably a primary, secondary or tertiary amine. Among these, tertiary amines are more preferable because they have both adsorption power to the colorant and stability.

That is, the acrylic block copolymer of the present invention contains 5 to 40 repeating units represented by the general formula (I) in the solvophilic A block from the viewpoint of improving dispersibility and developer solubility. It is preferable that the repeating unit represented by the general formula (II) is contained in the B block containing a mol% and having a functional group containing a nitrogen atom.

  In addition, when the acrylic block copolymer contains an acid group such as carboxylic acid or phosphoric acid, it causes an acid-base interaction with the amine site in the B block of the resin-type dispersant, thereby reducing dispersion stability. Therefore, the acid value is preferably low, and more preferably 0 mgKOH / g.

  The content of the acrylic block copolymer is preferably 1 to 70 parts by weight, and more preferably 10 to 60 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the acrylic block copolymer is less than 1 part by weight, it is difficult to obtain the pigment dispersibility effect. Moreover, when it exceeds 70 weight part, when developing the pixel pattern of a color filter by this photolithographic method using this coloring composition, alkali developability may fall.

  Further, the coloring composition for a color filter of the present invention may further contain other resin-type dispersant. Examples of the resin-type dispersant that can be used in combination include polycarboxylic acid esters such as polyurethane and polyacrylate, and unsaturated compounds. Polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, and modifications thereof , Oil-based dispersants such as amides and salts thereof formed by the reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (Meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl Alcohol, water-soluble resin or water-soluble polymer compounds such as polyvinyl pyrrolidone, polyester, modified polyacrylate, ethylene oxide / propylene oxide adduct can be used phosphate ester-based or the like.

  Examples of commercially available resin-type dispersants that can be used in the present invention include DIsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, manufactured by Big Chemie. 165, 166, 167, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 9076, 9077, or BYK-LPN6919, 21324, 21407, or AntI-Terra-U, 203, 204, Or BYK-P104, P104S, 220S, or SOLPERSE-3000, 9000, 13240, 13650, 13940, 17000, 1800 manufactured by Nihon Lubrizol Corporation, such as LactImon, LactImon-WS, or Bykumen 20,000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, 76500, etc., EFKA-46, 47, 48, manufactured by Fuka Chemicals 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402, 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503, 4300, 4330, etc. Examples include Addispar PA111, PB711, PB821, PB822, and PB824 manufactured by the company.

<Pigment derivative>
The colored composition for a color filter of the present invention preferably further contains a pigment derivative that is an acidic derivative of a machine pigment or a metal salt thereof. An acidic derivative of an organic pigment or a metal salt thereof has a great effect of preventing reaggregation of the pigment after dispersion because it further promotes the pigment adsorption of the pigment and the resin-type dispersant and improves the dispersibility of the pigment. Therefore, when a colored composition obtained by dispersing a pigment in a pigment carrier using an acidic derivative of an organic pigment or a metal salt thereof, a color filter having excellent stability can be obtained. Furthermore, a resin-type dispersant which is an AB block copolymer or a B-A-B block copolymer, comprising an A block having solvophilicity and a B block having a functional group containing a nitrogen atom, Dispersibility improves more by using it simultaneously. This is considered to promote the pigment adsorption of the dispersant by the acid-base interaction between the acidic substituent of the derivative arranged near the pigment and the basic substituent of the dispersant.

The structure of an acidic derivative of an organic pigment or a metal salt thereof is a compound represented by the following general formula (1).
P-Lx General formula (1)
(However,
P: organic pigment residue,
L: acidic substituent,
x: A hydrogen atom or a metal ion. )

Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; copper phthalocyanine, halogenated copper phthalocyanine, zinc phthalocyanine, halogenated zinc phthalocyanine, Phthalocyanine pigments such as metal-free phthalocyanine; Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigment; dioxazine pigment; perinone pigment; Thioindigo pigments; isoindoline pigments; isoindolinone pigments; selenium pigments; quinophthalone pigments; dioxazine pigments; metal complex pigments.
Among them, quinophthalone pigments, particularly quinophthalone yellow pigments C.I. I. Pigment Yellow 138 is preferable because it is excellent in productivity, dispersion stability, heat resistance, light resistance, solvent resistance, and the like of the coloring composition.

  Examples of the substituent constituting the acidic substituent of L include sulfonic acid, carboxylic acid, phosphoric acid and the like.

Examples of the metal ion of x include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as magnesium, calcium and barium, amphoteric metal ions such as aluminum and zinc, and transition metal ions such as iron and nickel. .
Of these, alkaline earth metal ions such as calcium and barium, amphoteric metal ions such as aluminum and zinc, and transition metal ions such as iron and nickel are preferable. Of these, aluminum ions are particularly preferred because of their high heat resistance and dispersibility.

[Sulphonic acid derivative of quinophthalone and its aluminum salt]
Particularly preferred as an acidic derivative of an organic pigment or a metal salt thereof is a sulfonic acid derivative of quinophthalone or an aluminum salt thereof. The sulfonic acid derivative of quinophthalone or its aluminum salt is excellent in the dispersion of the colorant and has a great effect of preventing reaggregation of the colorant after dispersion. Therefore, a colored composition obtained by dispersing a colorant in a colorant carrier such as a resin or an organic solvent using a sulfonic acid derivative of quinophthalone or an aluminum salt thereof is excellent in stability.

For example, quinophthalone yellow pigment C.I. I. The sulfonic acid derivative of quinophthalone composed of CI Pigment Yellow 138 is a compound represented by the following formula (2), and its aluminum salt is a compound represented by the following formula (3).

Formula (2):

Formula (3):

  The aluminum salt of the sulfonic acid derivative of quinophthalone is synthesized by a conventional method, but the following method is industrially advantageous. That is, a dye is added to concentrated sulfuric acid or fuming sulfuric acid, and the mixture is heated to perform sulfonation. Next, the reaction solution is poured into a large amount of ice water, and the sulfonic acid derivative precipitated is filtered off with a filter press or the like and washed with water. The resulting aqueous paste of sulfonic acid derivative was redispersed in a large amount of water, adjusted to a weak alkali with aqueous sodium hydroxide solution, and then gradually added with aqueous aluminum sulfate solution to form sulfonic acid, This is a method of forming a salt. Thereafter, the aluminum salt of the sulfonic acid derivative of quinophthalone in powder form can be obtained through steps of filtration, washing with water, drying and pulverization.

  In the present invention, the total amount of the organic pigment acidic derivative or the metal salt thereof is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight with respect to 100 parts by weight of the colorant. More than a part. When the amount is less than 0.5 part by weight, the contrast ratio may be reduced due to a process involving high heat during the production of the color filter, and the light shielding property may be reduced in the black matrix. Moreover, it is preferably 40 parts by weight or less, and most preferably 20 parts by weight or less. If it exceeds 40 parts by weight, the light resistance may be deteriorated, and the electrical characteristics and the like may be deteriorated with a black matrix.

  The acidic derivative of an organic pigment or a metal salt thereof may be used alone or may contain both an acidic derivative and a metal salt, and each of them may be used in combination of two or more or other pigment derivatives.

Examples of the pigment derivative that can be used in combination with an acidic derivative of the organic pigment or a metal salt thereof include, for example, JP-A 63-305173, JP-B 57-15620, JP-B 59-40172, Examples thereof include those described in JP-A 63-17102, JP-B-5-9469 and the like.
<Resin>
The colored composition for a color filter of the present invention can contain a resin. The resin contained in the coloring composition for color filter of the present invention is a dispersion of a colorant, and a thermoplastic resin, a thermosetting resin, or the like can be used. The above-described resin preferably has a spectral transmittance of 80% or more, more preferably 9 in the entire wavelength region of 400 to 700 nm in the visible light region.
A transparent resin of 5% or more is preferable. Moreover, when using with the form of an alkali image development type photosensitive coloring composition, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

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

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

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

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

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

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

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

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like.
More than one type may be used together. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

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

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

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

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

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

  The acid value of the resin is the affinity for the colorant adsorbing group and the carboxyl group that acts as an alkali-soluble group during development, the colorant carrier, and the solvent from the viewpoint of the dispersibility, stability, developability, and heat resistance of the colorant. The balance between the aliphatic group and aromatic group serving as a group is important for the dispersibility, penetrability, developability, and durability of the pigment, and an acid value of 20 to 300 mgKOH / g is preferable. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, a fine pattern may not remain.

The resin is preferably used in an amount of 30 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high, and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 500 parts by weight or less.

<Solvent>
The solvent sufficiently disperses the colorant in the resin, and the filter composition is formed by applying the colored composition of the present invention on a transparent substrate such as a glass substrate so that the dry film thickness is 0.1 to 10 μm. Used to make things easier.
As the solvent, 1,2,3-trichloropropane, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-
Trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-
Butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m- Dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, P-chlorotoluene, P-diethylbenzene, seC-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether Ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene Glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol Ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether , Dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol Monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, acetic acid n- Examples include amyl, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid ester.
These solvents can be used singly or in combination of two or more at any ratio as required.

  Among them, since the dispersibility of the colorant of the present invention is good, glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, benzyl alcohol, etc. It is preferable to use ketones such as aromatic alcohols and cyclohexanone.

  The solvent is preferably used in an amount of 800 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the solvent can adjust the coloring composition to an appropriate viscosity and form a filter segment having a desired uniform film thickness.

The coloring composition for a color filter of the present invention can be used as a photosensitive coloring composition (resist material) for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

<Photopolymerizable monomer>
The photopolymerizable monomer used in the present invention includes monomers or oligomers that are cured by ultraviolet rays or heat to form a resin, and these can be used alone or in combination of two or more. The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability. .

  Examples of the photopolymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and β-carboxy. Ethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A Glycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (Meth) acrylic esters of methylolated melamine, various acrylic esters and methacrylic esters such as epoxy (meth) acrylate, urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, Pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, Although acrylonitrile etc. are mentioned, it is not necessarily limited to these.

<Photopolymerization initiator>
In the coloring composition for a color filter of the present invention, when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithography method, a photopolymerization initiator or the like is added to add a solvent development type or an alkali development type photosensitive. Can be prepared in the form of an ionic coloring composition.

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

  The content of the photopolymerization initiator is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 150 parts by weight from the viewpoint of photocurability and developability.

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

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

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

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

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

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

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

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

<Amine compound>
Moreover, the coloring composition for color filters of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen. Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

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

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

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

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

<Method for producing colored composition>
The color composition for color filter of the present invention comprises a colorant containing a pigment having an average primary particle diameter of 20 to 50 nm and an aspect ratio of pigment particles of 1: 1 to 1: 3.5, and a resin-type dispersion. It can be manufactured by dispersing finely using a dispersing agent such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor together with an agent and, if necessary, a pigment derivative, a resin, a solvent, and the like. Yes (pigment dispersion).

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

<Removal of coarse particles>
The colored composition for a color filter of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that the coloring composition for color filters substantially does not contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter in the present invention will be described.
The color filter of the present invention comprises a filter segment and / or a black matrix formed on the substrate from the coloring composition for a color filter of the present invention. For example, a black matrix and red, green, and blue filters Segments. The filter segment is formed on the substrate by applying the coloring composition of the present invention by a spin coat method or a die coat method.

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

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. An antifoaming agent or a surfactant can also be added to the developer.

  As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

  In order to increase UV exposure sensitivity, after applying and drying the above color filter coloring composition, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. Ultraviolet exposure can also be performed after forming a film.

  If the black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast of the liquid crystal display panel can be further increased. Examples of the black matrix include, but are not limited to, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, and a resin film in which a light-shielding agent is dispersed. A thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment and / or the black matrix on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

  Here, a method for forming a colored layer on the TFT substrate will be described. First, on the surface of the TFT substrate or on the surface of the substrate on which a passivation film such as a silicon nitride film is formed on the surface of the driving substrate, a light shielding layer is formed so as to divide the pixel forming portion as necessary. After forming and applying a colored composition in which a pigment is dispersed on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Next, this coating film is exposed through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked, whereby the pixel pattern has a predetermined arrangement. An arranged pixel array is formed. The photomask used at that time is provided with a pattern for forming a through hole or a U-shaped depression in addition to a pattern for forming a pixel.

  As the TFT substrate used for forming the colored layer, the same substrate as that of the color filter described above can be used, and these substrates include chemical treatment with a silane coupling agent, plasma treatment, ion plate, and the like. Appropriate pretreatments such as coating, sputtering, gas phase reaction, and vacuum deposition can also be performed. When the coloring composition is applied to the substrate, the same type as that of the above-described color filter substrate can be used.

The coating application film thickness of the filter segment is preferably 0.1 to 1 as the film thickness after drying.
The thickness is 0 μm, more preferably 0.5 to 6.0 μm.

  The coating thickness of the black matrix is preferably in the range of 0.2 to 10.0 μm, more preferably 0.2 to 5.0 μm, as the thickness after drying. Furthermore, it is more preferable that the thickness is in the range of 0.5 to 2.5 μm, which makes it easy to balance coating properties and light shielding properties.

  When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

  An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed on the color filter as necessary.

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

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

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. Also, the polymerization average molecular weight (Mw) of the resin, the acid value of the resin or resin-type dispersant, the amine value of the resin-type dispersant, the specific surface area of the pigment, the average primary particle diameter and aspect ratio of the pigment, and the contrast of the coating film The method for measuring the ratio is as follows.

<Resin polymerization average molecular weight (Mw)>
Polymerization average molecular weight (Mw) of the acrylic resin was converted to polystyrene using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. The weight average molecular weight (Mw).
<Acid value of resin or resin type dispersant>
The acid value was determined by potentiometric titration using a 0.1N potassium hydroxide / ethanol solution. An acid value shows the acid value of solid content.

<Amine value of resin-type dispersant>
The amine value was determined by potentiometric titration using a 0.1N aqueous hydrochloric acid solution, and then converted to an equivalent of potassium hydroxide. An amine value shows the amine value of solid content.

<Specific surface area of pigment>
The specific surface area of the pigment was measured by an automatic vapor adsorption amount measuring apparatus (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) using the nitrogen adsorption BET method.

<Average primary particle diameter and aspect ratio of pigment>
The average primary particle diameter of pigment and the aspect ratio of pigment particles were measured by a method of directly measuring the size of primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size. Further, as described above, when measuring the short axis diameter and the long axis diameter of the primary particles of each pigment, the ratio of the average value of the short axis diameter and the long axis diameter is vertical and horizontal when the short axis diameter is 1. The ratio was determined. The electron microscope was a transmission type (TEM).

<Contrast ratio of coating film>
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the dried coating film of the colored composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing planes of the polarizing plate and the polarizing plate are parallel, light is transmitted through the polarizing plate, but if the polarizing plane is perpendicular, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dried coating film of the colored composition, scattering by the pigment particles occurs, resulting in deviation in a part of the polarization plane. When the amount of light transmitted through the plate is reduced and the polarizing plate is perpendicular, a part of the light is transmitted through the polarizing plate. This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.
(Contrast ratio) = (Luminance when parallel) / (Luminance when direct)
A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

  Then, the manufacturing method of the resin-type dispersing agent, pigment derivative, refinement | purification pigment, and acrylic resin solution which were used by the Example and the comparative example is demonstrated.

<Method for producing resin-type dispersant>
(Resin Dispersant Solution A)
In a four-necked separable flask equipped with a thermometer, stirrer, distillation tube and condenser, 80 parts of methyl ethyl ketone, 86.7 parts of butyl acrylate, 11.8 parts of Bremer PME-200 (methoxypolyethylene glycol-methacrylate), sparteine 2.8 parts and 1.9 parts of ethyl bromoisobutyrate were charged and heated to 40 ° C. under a nitrogen stream. 1.1 parts of cuprous chloride was added and the temperature was raised to 75 ° C. to initiate polymerization. After polymerization for 3 hours, the polymerization solution was sampled, and it was confirmed that the polymerization yield was 95% or more from the solid content of the polymerization, and the weight average molecular weight (Mw) was 6860, 1.4 parts of dimethylaminoethyl methacrylate, Then, 20.0 parts of methyl ethyl ketone was added, and polymerization was further performed. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling to room temperature. 100 parts of the resulting resin solution was diluted with 100 parts of methyl ethyl ketone, 60 parts of cation exchange resin “Diaion PK228LH (Mitsubishi Chemical Corporation)” was added and stirred at room temperature for 1 hour. 6 parts of 500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 30 minutes. The polymerization catalyst residue was removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin-type dispersant solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a resin-type dispersant solution A (dispersant A) having a solid content of 50% by weight (amine value 5 mgKOH / g, acid value). 0 mg KOH / g).

(Resin Dispersant Solution B)
In a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 80 parts of methyl ethyl ketone, 85.5 parts of butyl acrylate, 11.7 parts of Bremer PME-200 (methoxypolyethylene glycol-methacrylate), sparteine 2.8 parts and 1.9 parts of ethyl bromoisobutyrate were charged and heated to 40 ° C. under a nitrogen stream. 1.1 parts of cuprous chloride was added and the temperature was raised to 75 ° C. to initiate polymerization. After polymerization for 3 hours, the polymerization solution was sampled, and it was confirmed that the polymerization yield was 95% or more from the solid content of the polymerization, and the weight average molecular weight (Mw) was 6860, 2.9 parts of dimethylaminoethyl methacrylate, Then, 20.0 parts of methyl ethyl ketone was added, and polymerization was further performed. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling to room temperature. 100 parts of the resulting resin solution was diluted with 100 parts of methyl ethyl ketone, and the cation exchange resin “Diaion PK2” was diluted.
"28LH (Mitsubishi Chemical Co., Ltd.)" 60 parts was added and stirred at room temperature for 1 hour. Further, 6 parts of "KYOWARD 500SN (Kyowa Chemical Industry Co., Ltd.)" was added as a neutralizing agent and stirred for 30 minutes. The polymerization catalyst residue was removed by removing the cation exchange resin and the adsorbent by filtration. Furthermore, the resin-type dispersant solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a resin-type dispersant solution B (dispersant B) having a solid content of 50% by weight (amine value 10 mgKOH / g, acid value). 0 mg KOH / g).

(Resin type dispersant solution C)
In a four-necked separable flask equipped with a thermometer, stirrer, distillation tube, and condenser, 80 parts of methyl ethyl ketone, 71.0 parts of butyl acrylate, 9.0 parts of Bremer PME-200 (methoxypolyethylene glycol-methacrylate), sparteine 2.8 parts and 1.9 parts of ethyl bromoisobutyrate were charged and heated to 40 ° C. under a nitrogen stream. 1.1 parts of cuprous chloride was added and the temperature was raised to 75 ° C. to initiate polymerization. After polymerization for 3 hours, the polymerization solution was sampled, and it was confirmed that the polymerization yield was 95% or more from the solid content of the polymerization, and the weight average molecular weight (Mw) was 6860, 20.0 parts of dimethylaminoethyl methacrylate, Then, 20.0 parts of methyl ethyl ketone was added, and polymerization was further performed. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling to room temperature. 100 parts of the resulting resin solution was diluted with 100 parts of methyl ethyl ketone, 60 parts of cation exchange resin “Diaion PK228LH (Mitsubishi Chemical Corporation)” was added and stirred at room temperature for 1 hour. 6 parts of 500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 30 minutes. The polymerization catalyst residue was removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin-type dispersant solution was concentrated and substituted with ethylene glycol monomethyl ether acetate to obtain a resin-type dispersant solution C (dispersant C) having a solid content of 50% by weight (amine value 70 mgKOH / g, acid value). 0 mg KOH / g).

(Resin Dispersant Solution D)
In a four-necked separable flask equipped with a thermometer, stirrer, distillation tube, and condenser, 80 parts of methyl ethyl ketone, 64.1 parts of butyl acrylate, 8.7 parts of Blemmer PME-200 (methoxypolyethylene glycol-methacrylate), sparteine 2.8 parts and 1.9 parts of ethyl bromoisobutyrate were charged and heated to 40 ° C. under a nitrogen stream. 1.1 parts of cuprous chloride was added and the temperature was raised to 75 ° C. to initiate polymerization. After polymerization for 3 hours, the polymerization solution was sampled, and it was confirmed that the polymerization yield was 95% or more from the solid content of the polymerization, and the weight average molecular weight (Mw) was 6860, 27.1 parts of dimethylaminoethyl methacrylate, Then, 20.0 parts of methyl ethyl ketone was added, and polymerization was further performed. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling to room temperature. 100 parts of the resulting resin solution was diluted with 100 parts of methyl ethyl ketone, 60 parts of cation exchange resin “Diaion PK228LH (Mitsubishi Chemical Corporation)” was added and stirred at room temperature for 1 hour. 6 parts of 500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 30 minutes. The polymerization catalyst residue was removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin-type dispersant solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a resin-type dispersant solution D (dispersant D) having a solid content of 50% by weight (amine value 95 mgKOH / g, acid value). 0 mg KOH / g).

(Resin Dispersant Solution E)
In a four-necked separable flask equipped with a thermometer, stirrer, distillation tube, and condenser, 80 parts of methyl ethyl ketone, 57.8 parts of butyl acrylate, 7.9 parts of Bremer PME-200 (methoxypolyethylene glycol-methacrylate), sparteine 2.8 parts and 1.9 parts of ethyl bromoisobutyrate were charged and heated to 40 ° C. under a nitrogen stream. 1.1 parts of cuprous chloride was added and the temperature was raised to 75 ° C. to initiate polymerization. After polymerization for 3 hours, the polymerization solution was sampled, and it was confirmed that the polymerization yield was 95% or more from the solid content of the polymerization, and the weight average molecular weight (Mw) was 6860, 34.3 parts of dimethylaminoethyl methacrylate, Then, 20.0 parts of methyl ethyl ketone was added, and polymerization was further performed. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling to room temperature. 100 parts of the resulting resin solution was diluted with 100 parts of methyl ethyl ketone, 60 parts of cation exchange resin “Diaion PK228LH (Mitsubishi Chemical Corporation)” was added and stirred at room temperature for 1 hour. 6 parts of 500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 30 minutes. The polymerization catalyst residue was removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin-type dispersant solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a resin-type dispersant solution E (dispersant E) having a solid content of 50% by weight (amine value 120 mgKOH / g, acid value). 0 mg KOH / g).

(Resin Dispersant Solution F)
In a four-necked separable flask equipped with a thermometer, stirrer, distillation tube, and condenser, 80 parts of methyl ethyl ketone, 70.4 parts of butyl acrylate, 9.6 parts of Bremer PME-200 (methoxypolyethylene glycol-methacrylate), sparteine 2.8 parts, 1.9 parts of ethyl bromoisobutyrate, and 20.0 parts of dimethylaminoethyl methacrylate were charged and heated to 40 ° C. under a nitrogen stream. 1.1 parts of cuprous chloride was added and the temperature was raised to 75 ° C. to initiate polymerization. After polymerization for 3 hours, the polymerization solution was sampled, and it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling to room temperature. 100 parts of the resulting resin solution was diluted with 100 parts of methyl ethyl ketone, 60 parts of cation exchange resin “Diaion PK228LH (Mitsubishi Chemical Corporation)” was added and stirred at room temperature for 1 hour. 6 parts of 500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 30 minutes. The polymerization catalyst residue was removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin-type dispersant solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a resin-type dispersant solution F (dispersant F) having a solid content of 50% by weight (amine value 70 mgKOH / g, acid value). 0 mg KOH / g).

Table 1 summarizes the resin structure of each resin-type dispersant and the amine value in terms of effective solid content.

<Method for producing pigment derivative>
(Pigment derivative 1 (metal salt of quinophthalone skeleton sulfonic acid))
30 parts of quinophthalone yellow pigment (CI Pigment Yellow 138) was dissolved in 300 parts of 98% sulfuric acid and stirred at 70 ° C. for 8 hours to carry out sulfonation reaction. The end point of the reaction was defined as the point at which no change in the spectrum was observed by measuring the spectrum of the sulfuric acid solution. Next, this reaction solution was poured into 3000 parts of ice water, and the precipitated sulfonated dye derivative was filtered off, washed with water and dried. I. A quinophthalone sulfonic acid having a structure represented by the formula (4), which is a sulfonated derivative of CI Pigment Yellow 138, was obtained. The yield after drying was 334 parts and the yield was 99%.

The paste of quinophthalone skeleton sulfonic acid was redispersed in 10,000 parts of water (pH 2.5). Next, the solution was adjusted to pH 11 with an aqueous sodium hydroxide solution and dissolved to give a red solution. To this solution, 278 parts of an aqueous aluminum sulfate solution (liquid sulfuric acid band) was gradually added. Precipitates appear one after another from the dropped portion, and the pH decreases with the addition, and the pH is 3.6 at the end of the addition. No bleed was seen. The slurry containing this precipitate was filtered off and washed with water. I. The pigment derivative 1 which is a metal salt of a quinophthalone skeleton sulfonic acid having a structure represented by the formula (5) which is an aluminum salt of a sulfonated derivative of Pigment Yellow 138 was obtained. The yield after drying was 334 parts, and the yield was 99%.
Formula (5)

<Production method of fine pigment>
(Green pigment PG-1)
Phthalocyanine green pigment C.I. I. 500 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 8 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a green pigment PG-1 was obtained.

(Green pigment PG-2)
Phthalocyanine green pigment C.I. I. 500 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 2 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a green pigment PG-2 was obtained.

(Green pigment PG-3)
Phthalocyanine green pigment C.I. I. 500 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 40 ° C. for 12 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a green pigment PG-3 was obtained.

(Green pigment PG-4)
Phthalocyanine green pigment C.I. I. 500 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 2 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a green pigment PG-4 was obtained.

(Green pigment PG-5)
Phthalocyanine green pigment C.I. I. 500 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 4 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a green pigment PG-5 was obtained.

(Yellow pigment PY-1)
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 8 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A yellow pigment PY-1 was obtained.

(Yellow pigment PY-2)
Quinophthalone yellow pigment C.I. I. Pigment Yellow 138 (BASF “K0961HD”) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 80 ° C. for 8 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A yellow pigment PY-2 was obtained.

(Yellow pigment PY-3)
Isoindoline yellow pigment C.I. I. 200 parts of Pigment Yellow 185 (“PalItol Yellow L1155” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 8 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A yellow pigment PY-3 was obtained.

(Black pigment PBLK-2)
Perylene black pigment C.I. I. Pigment Black 32 ("PalIogen Black L0086" manufactured by BASF) was charged in 500 parts, 2500 parts of sodium chloride, and 250 parts of diethylene glycol in a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 12 hours. . Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a black pigment PBLK-2 was obtained.

(Black pigment PBLK-3)
Perylene-based black pigment ("Lumogen Black FK4281" manufactured by BASF)), 500 parts, 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 40 ° C for 12 hours. Kneaded. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a black pigment PBLK-3 was obtained.

(Black pigment PBLK-4)
Perylene black pigment C.I. I. 500 parts of CI Pigment Black 31 ("PalIogen Black S0084" manufactured by BASF)), 250 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 5 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a black pigment PBLK-4 was obtained.

(Black pigment PBLK-5)
500 parts of perylene-based black pigment ("Lumogen Black FK4281" manufactured by BASF), 250 parts of sodium chloride, and 250 parts of diethylene glycol are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 5 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a black pigment PBLK-5 was obtained.
Table 2 shows the average primary particle diameter and aspect ratio of the pigment.

PY-4: nickel complex yellow pigment C.I. I. Pigment Yellow 150 ("E-4GN" manufactured by LANXESS)
PY-5: quinophthalone yellow pigment C.I. I. Pigment Yellow 138 (BASF “K0961HD”)
PY-6: Isoindoline-based yellow pigment C.I. I. Pigment Yellow 185 ("PalIto Yellow L1155" manufactured by BASF)
PBLK-1: “Lumogen Black FK4” manufactured by BASF
280 "
PBLK-6: Carbon black pigment “# 45” manufactured by Mitsubishi Chemical Corporation
PBLK-7: Carbon black pigment “MA220” manufactured by Mitsubishi Chemical Corporation

<Method for producing acrylic resin solution>
(Adjustment of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Ether resin was added to obtain an acrylic resin solution 1.

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

[Example 1]
(Pigment dispersion (D-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a pigment dispersion (DP-11) was produced.
Green pigment PG-1: 10.0 parts acrylic resin solution 1: 35.0 parts propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin-type dispersant solution C (dispersant C): 6.0 parts

[Examples 2-14, Comparative Examples 1-16]
Hereinafter, the pigment dispersion (D-2 to 34) was prepared in the same manner as the pigment dispersion (D-1) except that the pigments and pigment derivatives were changed to the compositions and blending amounts shown in Tables 3 and 4. .

<Evaluation of pigment dispersion>
The viscosity characteristics and contrast ratio (CR) or optical density (OD) of the obtained pigment dispersion were evaluated by the following methods. The results are shown in Tables 5 and 6.

(Viscosity characteristics)
As for the viscosity of the pigment dispersion, an initial viscosity at 25 ° C. was measured using an E type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.). Separately, 25 g of the pigment dispersion was allowed to stand at 40 ° C. for 7 days in a sealed state in a glass container, and then the viscosity was measured by the same method as described above to obtain the time-dependent viscosity. In addition, a three-level evaluation was performed according to the following criteria.
○: Viscosity less than 20 mPa · s Δ: Viscosity of 20 mPa · s or more, less than 40 mPa · s ×: Viscosity of 40 mPa · s or more

(Contrast ratio (CR))
Using the obtained pigment dispersion (D-1 to 17), a spin coater was used to produce a three-point coated substrate so that the dry film thickness was about 1 μm by changing the rotation speed. After coating, the film was dried in a hot air oven at 80 ° C. for 30 minutes, and the film thickness and the contrast ratio were measured. The contrast ratio (CR) at a film thickness of 1 μm was determined from the three points of data by the primary correlation method. In addition, a three-level evaluation was performed according to the following criteria.
○: CR 8000 or more Δ: CR less than 8000, 6000 or more X: Less than CR 6000

(Optical density (OD))
The obtained pigment dispersion (D-18 to 30) was applied to a 100 mm × 100 mm glass substrate by a spin coating method, and then a coating film having a dry film thickness of 1.0 μm was prepared and heated at 230 ° C. for 20 minutes. . The optical density (OD) of the pigment dispersion-coated substrate thus obtained was measured with a Macbeth densitometer (GRETAG D200-II), and the optical density (OD) at a film thickness of 1.0 μm was determined.
Moreover, OD was evaluated in three stages according to the following criteria.
○: OD 1.5 or more Δ: OD 1.3 or more and less than 1.5 ×: OD less than 1.3

  A colorant containing a pigment having an average primary particle diameter of 20 to 50 nm and an aspect ratio of pigment particles of 1: 1 to 1: 3.5, an A block having solvophilicity, and a functional group containing a nitrogen atom An acrylic block copolymer or an AB block copolymer comprising a B block having a group, and an amine value of 10 mgKOH / g or more and 99 mgKOH / g or less in terms of effective solid content The colored compositions for color filters of the present invention containing a block copolymer with a resin-type dispersant all had good results that the viscosity was low and stable, and the CR was high.

  In particular, the pigment dispersion (D-3) of Example 3 using a metal salt of a quinophthalone skeleton sulfonic acid has a better CR and viscosity than the pigment dispersion (D-1) of Example 1. This is a more preferable result.

  On the other hand, Comparative Example 1 containing pigment particles having an average primary particle diameter of 15 nm greatly increases the viscosity, Comparative Example 2 including pigment particles having an average primary particle diameter of 100 nm, and a pigment having an aspect ratio of 1: 4.5. Comparative Example 3 containing particles is greatly inferior in CR.

Further, the pigment dispersion (D-13) of Comparative Example 5 in which the amine value of the resin-type dispersant is less than 10 mgKOH / g and the pigment dispersion (D-12) of Comparative Example 4 in which the amine value of 99 mgKOH / g or more is high. The pigment dispersion (D-13) of Comparative Example 5 having a viscosity, particularly less than 10 mg KOH / g, also has a low CR, and the pigment dispersion (D-14) of Comparative Example 6 using a random type dispersant was used. )
Resulted in a high viscosity.

  A colorant containing a pigment having an average primary particle diameter of 20 to 50 nm and an aspect ratio of pigment particles of 1: 1 to 1: 3.5, an A block having solvophilicity, and a functional group containing a nitrogen atom An acrylic block copolymer or an AB block copolymer comprising a B block having a group, and an amine value of 10 mgKOH / g or more and 99 mgKOH / g or less in terms of effective solid content The colored compositions for color filters of the present invention containing a block copolymer and a resin-type dispersant all had good results of low viscosity and stability, and high OD.

  On the other hand, the pigment dispersion (D-20) of Example 11 using a metal salt of quinophthalone skeleton sulfonic acid with respect to the pigment dispersion (D-18) of Example 9 is more preferable because the viscosity is still better. It was a result.

  On the other hand, the pigment dispersion (D-24) of Comparative Example 10 containing pigment particles having an average primary particle diameter of 15 nm significantly thickened, and the pigment of Comparative Example 11 containing pigment particles having an average primary particle diameter of 100 nm. The dispersion (D-25) has a large OD. Further, the pigment dispersion (D-26) of Comparative Example 12 containing pigment particles having an aspect ratio of 1: 4.0 is greatly inferior in OD.

  In addition, the pigment dispersion (D-28) of Comparative Example 14 in which the amine value of the resin-type dispersant is less than 10 mgKOH / g, and the pigment dispersion (D-27) of Comparative Example 13 in which the amine value is 99 mgKOH / g or more, The viscosity increased. In particular, the pigment dispersion (D-28) of Comparative Example 14 that is less than 10 mg KOH / g has a low CR, and the viscosity of the pigment dispersion (D-29) of Comparative Example 15 using a random type dispersant is low. The result was high.

[Example 19]
(Photosensitive coloring composition (R-1))
After stirring and mixing the following mixture uniformly, it is filtered through a 1.0 μm filter,
The photosensitive coloring composition (R-1) was obtained.
(Pigment dispersion) (Total 50 parts)
Pigment dispersion 1; Pigment dispersion (D-1): 30.0 parts Pigment dispersion 2; Pigment dispersion (D-10): 20.0 parts Acrylic resin solution 2: 10.6 parts Trimethylolpropane triacrylate : 4.2 parts (“NK ESTER ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan): 1.2 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.) "KBM-803"): 0.4 part ethylene glycol monomethyl ether acetate: 23.2 parts

[Examples 20 to 35, Comparative Examples 17 to 31]
(Photosensitive coloring composition (R-2 to 32))
The photosensitive colored composition (R-2 to 32) was the same as the photosensitive colored composition (R-1) except that the pigment dispersion was changed to the type and blending amount of the pigment dispersion shown in Tables 7 and 8. Got. In the photosensitive coloring composition, the pigment dispersions 1 and 2 are used in combination, but the total amount as the pigment dispersion is 50 parts in all the photosensitive coloring compositions.

<Evaluation of photosensitive coloring composition>
The viscosity characteristics, contrast ratio (CR) or optical density (OD), and development speed of the obtained photosensitive coloring composition were evaluated by the following methods. The results are shown in Table 5.

(Viscosity characteristics)
The viscosity of the photosensitive coloring composition was determined by measuring the initial viscosity at 25 ° C. using an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.). Separately, 25 g of the pigment dispersion was allowed to stand at 40 ° C. for 7 days in a sealed state in a glass container, and then the viscosity was measured by the same method as described above to obtain the time-dependent viscosity.
○: Viscosity less than 4.0 mPa · s Δ: Viscosity of 4.0 mPa · s or more, less than 7.0 mPa · s ×: Viscosity of 7.0 mPa · s or more

(Contrast ratio (CR))
Using the obtained photosensitive coloring composition (R-1 to 18), a spin coater was used to produce a three-point coated substrate so that the dry film thickness was about 2 μm by changing the rotation speed. After coating, the film was dried in a hot air oven at 80 ° C. for 30 minutes, and the film thickness and the contrast ratio were measured. The contrast ratio (CR) at a film thickness of 1 μm was determined from the three points of data by the primary correlation method. In addition, a three-level evaluation was performed according to the following criteria.
○: CR 8000 or more Δ: CR less than 8000, 6000 or more X: Less than CR 6000

(Optical density (OD))
After coating the obtained photosensitive coloring composition (R-19 to 32) on a 100 mm × 100 mm glass substrate by a spin coating method, a coating film having a dry film thickness of 1.0 μm was prepared, and the coating was performed at 230 ° C. for 20 minutes. Heated. The optical density (OD) of the pigment dispersion-coated substrate thus obtained was measured with a Macbeth densitometer (GRETAG D200-II), and the optical density (OD) at a film thickness of 1.0 μm was determined.
Moreover, OD was evaluated in three stages according to the following criteria.
○: OD 1.5 or more Δ: OD 1.3 or more and less than 1.5 ×: OD less than 1.3

(Development speed)
After coating the photosensitive coloring composition on a 10 cm × 10 cm glass substrate by spin coating, the solvent was removed by heating at 70 ° C. for 15 minutes in a clean oven to obtain a coating film of about 2 μm. Next, this substrate was exposed at 60 mJ / cm ² through a mask pattern with a high-pressure mercury lamp, and then subjected to spray development at a pressure of 0.25 MPa using a 0.04 wt% aqueous potassium hydroxide solution (developer temperature 26 ° C.), The time until the colored coating film was dissolved and the substrate surface was exposed (development dissolution time) was measured. The development dissolution time for each photosensitive coloring composition was measured and evaluated in three stages according to the following criteria.
○: Less than 20 seconds
Δ: 20 seconds or more, less than 30 ×: 30 seconds or more

  A colorant containing a pigment having an average primary particle diameter of 20 to 50 nm and an aspect ratio of pigment particles of 1: 1 to 1: 3.5, an A block having solvophilicity, and a functional group containing a nitrogen atom An acrylic block copolymer or an AB block copolymer comprising a B block having a group, and an amine value of 10 mgKOH / g or more and 99 mgKOH / g or less in terms of effective solid content The colored compositions for color filters of the present invention containing a block copolymer and a resin-type dispersant all had good results that the viscosity was low and stable, the CR was high, and the development speed was fast.

  Among them, the photosensitive coloring composition (R-3) of Example 21 using a metal salt of quinophthalone skeleton sulfonic acid with respect to the photosensitive coloring composition (R-1) of Example 19 further has CR and viscosity. Was more preferable because

  On the other hand, the photosensitive coloring composition (R-11) of Comparative Example 17 containing pigment particles having an average primary particle size of 15 nm had a high initial viscosity and increased significantly over time. On the other hand, the photosensitive colored composition (R-12) of Comparative Example 18 containing pigment particles having an average primary particle diameter of 100 nm has a large CR. Furthermore, the photosensitive coloring composition (R-13) of Comparative Example 19 containing pigment particles having an aspect ratio of 1: 4.5 has a large CR.

Moreover, the photosensitive coloring composition (R-15) of Comparative Example 21 in which the amine value of the resin-type dispersant is less than 10 mgKOH / g has a high viscosity and a low CR. Moreover, the photosensitive coloring composition (R-14) of Comparative Example 20, which is 99 mgKOH / g or more, similarly has a high viscosity. In addition, the photosensitive coloring composition (R-14) of Comparative Example 20 had a low development speed due to a high amine value. Moreover, the photosensitive coloring composition (R-16) of Comparative Example 22 using a random type dispersant resulted in a high viscosity.
Thus, none of the comparative examples was able to satisfy all of CR, viscosity, and development speed.

  A colorant containing a pigment having an average primary particle diameter of 20 to 50 nm and an aspect ratio of pigment particles of 1: 1 to 1: 3.5, an A block having solvophilicity, and a functional group containing a nitrogen atom An acrylic block copolymer or an AB block copolymer comprising a B block having a group, and an amine value of 10 mgKOH / g or more and 99 mgKOH / g or less in terms of effective solid content The colored compositions for color filters of the present invention containing a block copolymer and a resin-type dispersant all had good results that the viscosity was low and stable, the OD was high, and the development speed was fast.

Among them, the photosensitive colored composition (R-21) of Example 27 using a metal salt of quinophthalone skeleton sulfonic acid with respect to the photosensitive colored composition (R-19) of Example 25 has a better viscosity. Therefore, more preferable results were obtained.

  On the other hand, the photosensitive coloring composition (R-26) of Comparative Example 25 containing pigment particles having an average primary particle diameter of 15 nm significantly thickened, and Comparative Example 26 containing pigment particles having an average primary particle diameter of 100 nm. The photosensitive coloring composition (R-27) has a large OD. Furthermore, the photosensitive coloring composition (R-28) of Comparative Example 27 containing pigment particles having an aspect ratio of 1: 4.0 has a large inferior OD.

  Moreover, the photosensitive coloring composition (R-30) of the comparative example 29 whose amine value of a resin type dispersing agent is less than 10 mgKOH / g, and the photosensitive coloring composition (R-29) of the comparative example 28 which is 99 mgKOH / g or more. ) Has a high viscosity. Moreover, the photosensitive coloring composition (R-29) of Comparative Example 28 was a result of a slow development speed due to a high amine value. Moreover, the photosensitive coloring composition (R-31) of Comparative Example 30 using a random type dispersant resulted in a high viscosity.

<Manufacture of color filters>
First, a total of 5.0 parts of the green pigment and the yellow pigment in the photosensitive coloring composition (R-1), 5.0 parts of the carbon black pigment (PBLK-7) in the black photosensitive coloring composition 1, red In the photosensitive coloring composition 1, C.I. I. Pigment Red 254 / C.I. I. Pigment Red 177 = 3.0 parts / 2.0 parts, C.I. I. Pigment Green 58 / C.I. I. Pigment Yellow 150 = 3.0 parts / 2.0 parts, the blue photosensitive coloring composition 1 has C.I. I. Except for replacing Pigment Blue 15: 3 with 5.0 parts, each color photosensitive coloring composition was prepared in the same manner as the photosensitive coloring composition (R-1), and the black photosensitive coloring composition 1 and the red photosensitive coloring matter were prepared. Photosensitive coloring composition 1, green photosensitive coloring composition 1, and blue photosensitive coloring composition 1 were obtained.

[Manufacture of color filter 1]
The black photosensitive coloring composition 1 was coated on a 100 mm × 100 mm glass substrate with a die coater to a thickness of about 1.0 μm, and the solvent was removed and dried in an oven at 70 ° C. for 20 minutes. Subsequently, stripe pattern exposure was performed with ultraviolet rays using an exposure apparatus. The exposure amount was 100 mJ / cm ² . Furthermore, after spray development with a developer composed of an aqueous sodium carbonate solution to remove unexposed portions, the substrate was washed with ion-exchanged water, and this substrate was heated at 230 ° C. for 20 minutes to form a black matrix having a line width of about 10 μm. .

Next, the red photosensitive coloring composition 1 was applied to a thickness of about 2 μm on the glass substrate on which the black matrix was formed, and the solvent was removed and dried in an oven at 70 ° C. for 20 minutes. Subsequently, stripe pattern exposure was performed with ultraviolet rays using an exposure apparatus. The exposure amount was 100 mJ / cm ² . Furthermore, after spray development with a developer composed of an aqueous sodium carbonate solution to remove unexposed portions, the substrate is washed with ion-exchanged water, and this substrate is heated at 230 ° C. for 30 minutes to form a red filter segment having a line width of about 50 μm. did. Next, by the same operation, a green filter segment is formed using the photosensitive coloring composition (R-1) next to the red filter segment, and then a blue filter segment is formed using the blue photosensitive coloring composition 1. A color filter 1 having three color filter segments on a glass substrate was obtained.

[Manufacture of color filter 2]
The photosensitive coloring composition (R-24) was coated on a 100 mm × 100 mm TFT substrate with a die coater to a thickness of about 1.0 μm, and the solvent was removed and dried in an oven at 70 ° C. for 20 minutes. Subsequently, stripe pattern exposure was performed with ultraviolet rays using an exposure apparatus. The exposure amount was 100 mJ / cm ² . Furthermore, after spray development with a developer composed of an aqueous sodium carbonate solution to remove unexposed portions, the substrate was washed with ion-exchanged water, and this substrate was heated at 230 ° C. for 20 minutes to form a black matrix having a line width of about 10 μm. .

Next, the red photosensitive coloring composition 1 was applied to a thickness of about 2 μm on the glass substrate on which the black matrix was formed, and the solvent was removed and dried in an oven at 70 ° C. for 20 minutes. Subsequently, stripe pattern exposure was performed with ultraviolet rays using an exposure apparatus. The exposure amount was 100 mJ / cm ² . Furthermore, after spray development with a developer composed of an aqueous sodium carbonate solution to remove unexposed portions, the substrate is washed with ion-exchanged water, and this substrate is heated at 230 ° C. for 30 minutes to form a red filter segment having a line width of about 50 μm. did. Next, by the same operation, a green filter segment is formed using the green photosensitive coloring composition 1 next to the red filter segment, and then a blue filter segment is formed using the blue photosensitive coloring composition 1, and on the same glass substrate. A color filter 2 having three color filter segments was obtained.

  Both color filters 1 and 2 have at least one of a filter segment and a black matrix formed from the color filter coloring composition of the present invention, so patterning is possible in a short time without leaving a residue in the development process. Since the contrast ratio is high and the color reproduction region is wide, a liquid crystal display device using the color filter can express a vivid and vivid color.

  The color filter 2 of the present invention has a BM formed on the TFT, but has excellent electrical characteristics and no image sticking. In addition, since the manufacturing process can be simplified, a liquid crystal display device using the color filter has a high response speed and can reproduce bright colors at low cost.

Claims (7)

In a color filter coloring composition comprising a colorant, a resin-type dispersant, and a solvent, the colorant has an average primary particle diameter of 20 to 50 nm and an aspect ratio of pigment particles of 1: 1 to 1. Containing a pigment which is 1: 3.5,
The resin-type dispersant is an AB block copolymer or a B-A-B block copolymer composed of an A block having solvophilicity and a B block having a functional group containing a nitrogen atom, and A coloring composition for a color filter comprising an acrylic block copolymer having an amine value of 10 mgKOH / g or more and 99 mgKOH / g or less in terms of effective solid content. The acrylic block copolymer contains 5 to 40 mol% of a repeating unit represented by the following general formula (I) in the A block having solvophilicity, and in the B block having a functional group containing a nitrogen atom The coloring composition for a color filter according to claim 1, comprising a repeating unit represented by the following general formula (II).

[In General Formula (I), n represents an integer of 1 to 5, and R1 represents a hydrogen atom or a methyl group. ]

[In General Formula (II), R ₄ and R ₅ are each independently a cyclic or chain-like alkyl group which may have a substituent, an aryl group which may have a substituent, or An aralkyl group which may have a substituent is represented, R ₃ represents an alkylene group having 1 or more carbon atoms, and R ₂ represents a hydrogen atom or a methyl group. ]   The acrylic block copolymer has 50 to 50 structural units having a (meth) acrylate monomer other than the structural unit represented by the general formula (I) as a precursor in the solvophilic A block. The coloring composition for color filters according to claim 2, comprising 90 mol%.   The coloring composition for a color filter according to any one of claims 1 to 3, wherein the colorant is a perylene-based black pigment.   The coloring composition for a color filter according to any one of claims 1 to 4, further comprising an acidic derivative of an organic pigment or a pigment derivative that is a metal salt thereof. Furthermore, the coloring composition for color filters of any one of Claim 1 thru | or 5 containing a photopolymerizable monomer and a photoinitiator.   A color filter comprising a filter segment and / or a black matrix formed from the coloring composition for a color filter according to any one of claims 1 to 6 on a substrate.