JP2018132554A - Coloring resin composition, color filter, and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring resin composition that has a low contact angle to water, and reduced unevenness of application; a color filter having a pixel formed using the coloring resin composition; and an image display device having the color filter.SOLUTION: A coloring resin composition contains (A) a colorant, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator. The (B) dispersant contains a dispersant (b) having a repeating unit represented by a specific formula. The coloring resin composition further contains (F) a surfactant of 0.01 mass% or more in the total solid content.SELECTED DRAWING: None

Description

  The present invention relates to a colored resin composition, a color filter, and an image display device.

  Conventionally, pigment dispersion methods, dyeing methods, electrodeposition methods, and printing methods are known as methods for producing color filters used in liquid crystal display devices and the like. Among these, from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, etc., a pigment dispersion method having excellent characteristics on average is most widely adopted.

For color filters, improvements in color purity, saturation, and light transmission are required, and for the purpose of improving light transmission, the particle size of pigment particles is finely dispersed to ½ or less of its color wavelength. Although the method to do is known (nonpatent literature 1), when the particle size of a pigment is made small, a pigment will aggregate easily. For this reason, there has been a problem of yield reduction in the manufacturing process due to thickening of the composition.
As a study for suppressing pigment aggregation, various dispersants have been developed. For example, Patent Document 1 discloses a specific dispersant that disperses a large amount of pigment finely and uniformly and is excellent in dispersion stability. Patent Document 2 discloses a specific dispersant that exhibits excellent dispersibility and is excellent in alkali developability and dry redissolvability.

JP 2004-287366 A JP 2013-119568 A

Kiyoshi Hashizume “Journal of Color Material Association” (December 1967, p608)

In recent years, in order to broaden the color reproducibility of color filters, there is an increasing need to increase the content ratio of colorants such as pigments and dyes in the colored resin composition for forming color filters. In general, since the colorant has high hydrophobicity, the developability is poor, and there is a concern that the developability deteriorates due to the high content of the dispersion.
One parameter that serves as an index of developability of the colored resin composition is a contact angle of water with a cured product obtained by curing the composition. If the contact angle of water is small, water permeability is strong. In other words, the developability of the composition tends to be improved. On the other hand, when the contact angle of water is large, the water permeability is weak, and the developability of the composition tends to deteriorate.

  When the present inventors examined the colored resin compositions described in Patent Documents 1 and 2, it was found that it was difficult to achieve both a contact angle with water and coating unevenness.

  The present invention has been made in view of the above-described problems, and its object is to provide a colored resin composition having a low contact angle with water and good coating unevenness, and a color filter having pixels formed using the colored resin composition. An image display device having the color filter is provided.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific dispersant and a predetermined amount or more of a surfactant, thereby completing the present invention. It came to do. That is, the gist of the present invention is as follows.

[1] A colored resin composition comprising (A) a colorant, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator,
The (B) dispersant contains a dispersant (b) having a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II):
Furthermore, the colored resin composition contains 0.01% by mass or more of (F) surfactant in the total solid content.

(In formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² and R ³ each independently represents an alkylene group which may have a substituent. N represents an integer of 1 to 10. Represents.)

(In formula (II), R ⁴ represents a hydrogen atom or a methyl group. R ⁵ represents an alkylene group which may have a substituent. R ⁶ and R ⁷ each independently represents a hydrogen atom or a substituent. R ⁶ and R ⁷ may be bonded to each other to form a cyclic structure.

[2] The colored resin composition according to [1], wherein the dispersant (b) further has a repeating unit represented by the following general formula (III).

(In the formula (III), R ⁸ represents a hydrogen atom or a methyl group. R ⁹ represents an alkylene group which may have a substituent. R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom. Represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, any two of R ^{10 to} R ¹² being And may be bonded to each other to form a cyclic structure. X ⁻ represents a monovalent anion.)

[3] The colored resin composition according to [1] or [2], wherein the content ratio of the (F) surfactant is 1% by mass or less in the total solid content.
[4] The colored resin composition according to any one of [1] to [3], wherein the (F) surfactant contains a fluorine-based surfactant and / or a silicone-based surfactant.
[5] A color filter having pixels created using the colored resin composition according to any one of [1] to [4].
[6] An image display device having the color filter according to [5].

  According to the present invention, there are provided a colored resin composition having a low contact angle with water and good coating unevenness, a color filter having pixels formed using the colored resin composition, and an image display device having the color filter. be able to.

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL element having the color filter of the present invention.

The constituent requirements and the like of the present invention will be described in detail below, but these are examples of embodiments of the present invention and are not limited to these contents.
In addition, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) acrylic acid” is “ It means “acrylic acid and / or methacrylic acid”. Further, “total solid content” means all components other than the solvent components described later, which are contained in the colorant dispersion or the colored resin composition.

In the present invention, “weight average molecular weight” refers to polystyrene-reduced weight average molecular weight (Mw) by GPC (gel permeation chromatography).
In the present invention, the “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the mass of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. .

[1] Constituent Components of Colored Resin Composition Each constituent component of the colored resin composition of the present invention will be described below. The colored resin composition according to the present invention includes (A) a colorant, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator as essential components, and if further required. Further, additives other than the above components may be blended.
Hereinafter, each component will be described.

[1-1] (A) Colorant The colored resin composition of the present invention contains (A) a colorant as an essential component. Examples of the colorant include pigments and dyes. As the pigment, for example, when forming a pixel of a color filter, pigments of various colors such as a red pigment, a blue pigment, a green pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment can be used. 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. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. 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 , 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 dispersion stability, C.I. I. Pigment red 177, 254, or 275, and more preferably C.I. I. Pigment Red 177 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 dispersion stability, C.I. I. Pigment Blue 15: 3 or 15: 6, 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, 58 or 59. . Among these, from the viewpoint of dispersion stability, C.I. I. Pigment green 36, 58 or 59, more preferably C.I. I. Pigment Green 58 or 59.

  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 dispersion stability, C.I. I. Pigment Yellow 129, 138, 139, 150 or 185, more preferably C.I. I. Pigment Yellow 138, 150 or 185.

  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 dispersion stability, C.I. I. Pigment violet 23 or 29, 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.

  In addition, examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, and chromium oxide.

  Among the above-mentioned various pigments, they are often used at a high pigment concentration in order to reproduce a wide color gamut of a color filter, and have a large tendency to deteriorate developability. I. Pigment red 254, C.I. I. Pigment red 177, C.I. I. Pigment blue 15: 6, C.I. I. Pigment green 58, C.I. I. Pigment green 59, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 185 or C.I. I. Pigment Violet 23 is preferred, and C.I. I. Pigment red 254, C.I. I. Pigment red 177 or C.I. I. Pigment Blue 15: 6 is more preferable.

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.
These pigments are preferably used after being subjected to a dispersion treatment so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.3 μm or less.

  The average primary particle size of these pigments is usually 100 nm or less, preferably 50 nm or less, more preferably 40 nm or less, and particularly preferably 10 nm or more and 30 nm or less. Since the present invention is particularly effective in the case of a composition containing a highly atomized pigment, the case of containing a pigment having an average primary particle size of 10 nm to 30 nm is particularly preferable.

When forming a light shielding material such as a black matrix of a color filter using the colored resin composition of the present invention, a black pigment can be used. The black pigment may be used alone, or may be used by mixing the above-mentioned pigments such as red, green and blue. Examples of black pigments that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black. Among these, carbon black and titanium black are preferable from the viewpoints of light shielding rate and image characteristics.
Examples of carbon black include, for example, MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32 as products manufactured by Mitsubishi Chemical Corporation. , # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B Etc. are products made by Degussa, such as Printex3, Printex3OP, Printex30, P intex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Print ex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack 350, SpecialBlack250, SpecialBlack100, SpecialBlack6, Special Black5, Special Black4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170, etc. are products manufactured by Cabot Corporation: Monarch 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 900, Monarch 900, Monarch , REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, BLACK PEARLS 480, PEARLS 130, VULCAN XC72R, ELFTEX 8 etc. are the products made by Colombian Carbon Co., Ltd. as Raven11, Raven14, Raven15, Raven16, Raven22Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven10R, Raven10R, Raven10H, Raven80H, Raven80H , RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000 and the like.

  For the production of a resin black matrix having a high optical density and a high surface resistivity, it is particularly preferable to use resin-coated carbon black. The resin-coated carbon black is disclosed in, for example, JP-A-9-26571, JP-A-9-71733, JP-A-9-95625, JP-A-9-238863, or JP-A-11-60989. It can be obtained by treating the known carbon black by the method.

  Further, titanium black was prepared by heating a mixture of titanium dioxide and titanium metal in a reducing atmosphere for reduction (Japanese Patent Laid-Open No. 49-5432), and by high-temperature hydrolysis of titanium tetrachloride. A method of reducing ultrafine titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069). And a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610). It is not limited. Examples of commercially available titanium black include Titanium Black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.

  As an example of another black pigment, a plurality of pigments such as red, green, and blue can be mixed and used as a black pigment. Color materials that can be mixed for preparing a black pigment include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. In addition, other pigments that can be used for mixing are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26. The numbers in parentheses above indicate the color index (CI).

The particle size of these black pigments is preferably in the same range as described above for the pigments other than black.
In addition, the average primary particle diameter of a pigment can be calculated | required with the following method. First, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). Thereafter, the particle diameter of each pigment particle is determined for a plurality of (usually about 200 to 300) pigment particles, with the diameter corresponding to the area circle converted to the diameter of a circle having the same area.
Using the obtained primary particle size value, the number average value is calculated according to the following formula to obtain the average particle size.
Particle size of individual pigment particles: X1, X2, X3, X4,..., Xi,.
Average particle size = ΣXi / m

On the other hand, when carbon black is used as the black pigment, the average primary particle size is preferably 0.01 to 0.08 μm, and more preferably 0.02 to 0.05 μm from the viewpoint of developability. The DBP absorption is preferably 40 to 100 cc / 100 g, more preferably 50 to 80 cc / 100 g from the viewpoint of dispersibility and developability. Nitrogen adsorption specific surface area is preferably 50~120m ² / g, more preferably from the viewpoint of dispersion stability is 60~95m ² / g.

  In the case of carbon black, the particle shape is different from organic pigments, etc., where primary particles exist in a so-called fused structure like skewers, and fine pores are formed on the particle surface by post-processing. There is. Therefore, in order to represent the particle shape of the carbon black pigment, generally, in addition to the average particle diameter of primary particles obtained by the same method as that of the organic pigment, DBP absorption (JIS K6221) and nitrogen adsorption specific surface area (JIS) K6217) is measured and used as an index of structure and pore volume.

  On the other hand, as the dye, for example, a dye having xanthene, anthraquinone, or phthalocyanine as a basic skeleton and having a sulfonic acid group and / or a sulfonate group can be used. Specifically, xanthene dyes include Acid Red 52, Acid Red 87, Acid Red 91, Acid Red 92, Acid Red 94, Acid Red 289, and anthraquinone dyes include Acid Red 80, Acid Green 25, and Acid. Examples of the green 27, acid blue 25, acid blue 78, acid blue 112, acid blue 182, acid violet 34, acid violet 43, and phthalocyanine dyes include direct blue 86, direct blue 87, and acid blue 249.

  The dye used in the present invention is preferably insoluble in propylene glycol monomethyl ether acetate (PGMEA), which is an ester solvent. PGMEA is a solvent that is normally used in blue colored resin compositions for color filters using pigments because it is excellent in safety, coating properties, drying properties, and pigment dispersion stability. If the dye used in the present invention is insoluble in PGMEA, the dye can be stably present in the particle state in PGMEA without impairing the above characteristics, and it is easy to achieve both high contrast and high transmittance.

  PGMEA insolubility can be determined, for example, by the following method. 5 g of dye and 95 g of PGMEA are mixed and stirred to prepare a 5 mass% dye PGMEA mixed solution. In the mixed solution, the PGMEA-insoluble matter settles to the bottom, and the PGMEA-soluble matter remains in the mixed solution. Therefore, the bottom PGMEA-insoluble matter is removed by filtration. 1 g of the dye PGMEA solution after filtration is sampled, and the mass of the dye after drying PGMEA is measured, and the dye content ratio is measured. If the dye content ratio of the dye PGMEA solution is 0.5% by mass or less, it can be determined that PGMEA is insoluble.

  In the colored resin composition of the present invention, the content ratio of these (A) colorants is not particularly limited, but is generally 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, in the total solid content. More preferably 15% by mass or more, particularly preferably 20% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, particularly preferably. It is 40 mass% or less. There is a tendency that a sufficient color gamut can be ensured by setting it to the lower limit value or more, and there is a tendency that developability and electrical reliability can be ensured by setting the upper limit value or less.

  Further, when the colorant contains a pigment (A), the content ratio of the pigment is not particularly limited, but is generally 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, based on the total solid content. Preferably it is 15% by weight or more, particularly preferably 20% by weight or more, and usually 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 50% by weight or less, particularly preferably 40% by weight. It is below mass%. There is a tendency that a sufficient color gamut can be ensured by setting it to the lower limit value or more, and there is a tendency that developability and electrical reliability can be ensured by setting the upper limit value or less.

  In addition, when the colorant contains a dye (A), the content ratio of the dye is not particularly limited, but is generally 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, based on the total solid content. Preferably it is 15% by weight or more, particularly preferably 20% by weight or more, and usually 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 50% by weight or less, particularly preferably 40% by weight. It is below mass%. There is a tendency that a sufficient color gamut can be ensured by setting it to the lower limit value or more, and there is a tendency that developability and electrical reliability can be ensured by setting the upper limit value or less.

[1-2] (B) Dispersant The colored resin composition of the present invention contains (B) a dispersant for the purpose of stably dispersing (A) the colorant. In particular, the (B) dispersant contains a repeating unit represented by the following general formula (I) and a dispersing agent (b) having a repeating unit represented by the following general formula (II). . The colored resin composition of the present invention contains the dispersant (b) containing the repeating unit (I) containing a highly hydrophilic ester bond, whereby the hydrophilicity of the entire colored resin composition is increased and the contact angle with water. It is thought that it can be lowered.

In the formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² and R ³ each independently represents an alkylene group which may have a substituent. n represents an integer of 1 to 10.

In the formula (II), R ⁴ represents a hydrogen atom or a methyl group. R ⁵ represents an alkylene group. R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group. R ⁶ and R ⁷ may be bonded to each other to form a cyclic structure.

  The repeating unit represented by the general formula (I) contained in the dispersant (b) may be one type or two or more types. Similarly, the repeating unit represented by the general formula (II) contained in the dispersant (b) may be one type or two or more types.

(R ² )
In the formula (I), R ² represents an alkylene group which may have a substituent. Examples of the alkylene group include linear, branched, cyclic, or combinations thereof. Although carbon number of an alkylene group is not specifically limited, Usually, 1 or more, Preferably it is 2 or more, More preferably, it is 3 or more, Preferably it is 10 or less, More preferably, it is 7 or less, More preferably, it is 5 or less. When the amount is not less than the lower limit, the dispersion stability tends to be improved, and when the amount is not more than the upper limit, the aggregation of the dispersant chain tends to be suppressed.

  Specific examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group. Among these, from the viewpoint of dispersion stability, a methylene group, An ethylene group or trimethylene group is preferred, and an ethylene group is more preferred.

  Examples of the substituent that the alkylene group may have include a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group, a carboxyl group, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, Anthracenyl group etc. are mentioned.

(R ³ )
In the formula (I), R ³ represents an alkylene group which may have a substituent. Examples of the alkylene group include linear, branched, cyclic, or combinations thereof. The number of carbon atoms of the alkylene group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, further preferably 4 or more, particularly preferably 5 or more, and preferably 10 or less, more preferably 9 or less. More preferably, it is 8 or less, more preferably 7 or less, and particularly preferably 6 or less. When the amount is not less than the lower limit, the dispersion stability tends to be improved, and when the amount is not more than the upper limit, the aggregation of the dispersant chain tends to be suppressed.

  Specific examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group. Among these, from the viewpoint of dispersion stability, a pentamethylene group , A hexamethylene group or a heptamethylene group is preferable, and a pentamethylene group is more preferable.

  Examples of the substituent that the alkylene group may have include a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group, a carboxyl group, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, Anthracenyl group etc. are mentioned.

(N)
In the formula (I), n represents an integer of 1 to 10, preferably 1 or more, more preferably 3 or more, further preferably 4 or more, particularly preferably 5 or more, and preferably 10 or less, 7 or less. Is more preferable, and 6 or less is more preferable. When the amount is not less than the lower limit, the dispersion stability tends to be improved, and when the amount is not more than the upper limit, the aggregation of the dispersant chain tends to be suppressed.

(R ⁵ )
In the formula (II), R ⁵ represents an alkylene group which may have a substituent. Examples of the alkylene group include linear, branched, cyclic, or combinations thereof. The number of carbon atoms of the alkylene group is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 7 or less, still more preferably 5 or less, and particularly preferably 3 or less. There exists a tendency for a synthesis | combination to become easy by setting it as the said lower limit or more, and there exists a tendency which suppresses aggregation of the chain | strand of a dispersing agent by setting it as the said upper limit or less.

  Specific examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group. Among these, from the viewpoint of dispersion stability, an ethylene group, A hexamethylene group or a heptamethylene group is preferable, and an ethylene group is more preferable.

  Examples of the substituent that the alkylene group may have include a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group, a carboxyl group, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, Anthracenyl group etc. are mentioned.

(R ⁶ and R ⁷⁾
In the formula (II), R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group which may have a substituent. Examples of the alkyl group include linear, branched, cyclic, or combinations thereof. Although carbon number of an alkyl group is not specifically limited, Usually, 1 or more, Preferably it is 10 or less, More preferably, it is 7 or less, More preferably, it is 5 or less, Most preferably, it is 3 or less. When the amount is not less than the lower limit, the dispersion stability tends to be improved, and when the amount is not more than the upper limit, the aggregation of the dispersant chain tends to be suppressed.

  Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Among these, from the viewpoint of dispersion stability, a methyl group, an ethyl group, and a propyl group are exemplified. Group, butyl group, pentyl group or hexyl group, preferably methyl group, ethyl group, propyl group or butyl group, more preferably methyl group or ethyl group, It is particularly preferred.

Examples of the substituent that the alkyl group may have include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group.
In the above formula (II), examples of the cyclic structure formed by combining R ⁶ and R ⁷ with each other include, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of these. Is mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following (II-i). These cyclic structures may further have a substituent.

Among these, from the viewpoint of dispersion stability, R ⁶ and R ⁷ are each independently preferably an alkyl group which may have a substituent, and are a methyl group, an ethyl group, a propyl group, or a butyl group. Are more preferable, a methyl group or an ethyl group is more preferable, and a methyl group is particularly preferable.

  On the other hand, the dispersant (b) may have a repeating unit other than the general formulas (I) and (II). For example, it is preferable to have a repeating unit represented by the following general formula (III) from the viewpoint of dispersion stability.

In the formula (III), R ⁸ represents a hydrogen atom or a methyl group. R ⁹ represents an alkylene group which may have a substituent. R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent or an aralkyl which may have a substituent. Represents a group. Any two of R ^{10 to} R ¹² may be bonded to each other to form a cyclic structure. X ⁻ represents a monovalent anion.
The repeating unit represented by the formula (III) contained in the dispersant (b) may be one type or two or more types.

(R ⁹ )
In the formula (III), R ⁹ represents an alkylene group which may have a substituent. Examples of the alkylene group include linear, branched, cyclic, or combinations thereof. The number of carbon atoms of the alkylene group is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 7 or less, still more preferably 5 or less, and particularly preferably 3 or less. There exists a tendency for a synthesis | combination to become easy by setting it as the said lower limit or more, and there exists a tendency which suppresses aggregation of the chain | strand of a dispersing agent by setting it as the said upper limit or less.

  Specific examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group. Among these, from the viewpoint of dispersion stability, an ethylene group, A hexamethylene group or a heptamethylene group is preferable, and an ethylene group is more preferable.

  Examples of the substituent that the alkylene group may have include a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group, a carboxyl group, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, Anthracenyl group etc. are mentioned.

(R ¹⁰ , R ¹¹ and R ¹² )
In the formula (III), R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group or a substituent which may have a substituent. An aralkyl group which may be present.
Examples of the alkyl group include linear, branched, cyclic, or combinations thereof. The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 7 or less, still more preferably 5 or less, and particularly preferably 3 or less. When the amount is not less than the lower limit, the dispersion stability tends to be improved, and when the amount is not more than the upper limit, the aggregation of the dispersant chain tends to be suppressed.

  Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Among these, from the viewpoint of dispersion stability, a methyl group, an ethyl group, and a propyl group are exemplified. Group, butyl group, pentyl group or hexyl group, preferably methyl group, ethyl group, propyl group or butyl group, more preferably methyl group or ethyl group, It is particularly preferred.

  Examples of the substituent that the alkyl group may have include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group.

  Although carbon number of an aryl group is not specifically limited, Usually, 4 or more, Preferably it is 5 or more, More preferably, it is 6 or more, Preferably it is 16 or less, More preferably, it is 12 or less, More preferably, it is 9 or less. When the amount is not less than the lower limit, the dispersion stability tends to be improved, and when the amount is not more than the upper limit, the aggregation of the dispersant chain tends to be suppressed.

  Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Among these, from the viewpoint of dispersion stability, a phenyl group, A methylphenyl group, an ethylphenyl group, a dimethylphenyl group or a diethylphenyl group is preferable, and a phenyl group, a methylphenyl group or an ethylphenyl group is more preferable.

  Examples of the substituent that the aryl group may have include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group.

  The number of carbon atoms of the aralkyl group is not particularly limited, but is usually 5 or more, preferably 6 or more, preferably 16 or less, more preferably 12 or less, and still more preferably 9 or less. When the amount is not less than the lower limit, the dispersion stability tends to be improved, and when the amount is not more than the upper limit, the aggregation of the dispersant chain tends to be suppressed.

  Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group. Among these, from the viewpoint of dispersion stability, a phenylmethylene group and a phenylethylene group , A phenylpropylene group or a phenylbutylene group, more preferably a phenylmethylene group or a phenylethylene group.

  Examples of the substituent that the aralkyl group may have include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group.

In the above formula (III), examples of the cyclic structure formed by combining any two of R ^{10 to} R ¹² with each other include, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocyclic ring or two of these condensed The condensed ring formed is mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples in which R ¹⁰ and R ¹¹ are bonded to each other to form a cyclic structure are listed in (III-i) below. These cyclic structures may further have a substituent.

Among these, from the viewpoint of dispersion stability, any one of R ¹⁰ , R ¹¹ and R ¹² is an aralkyl group which may have a substituent, and the remaining two may have a substituent. An alkyl group is preferred.

  Moreover, it is preferable that a dispersing agent (b) has a repeating unit represented by the following general formula (IV) from a hydrophilic viewpoint as repeating units other than the said general formula (I) and (II).

In the formula (IV), R ¹³ represents a hydrogen atom or a methyl group. R ¹⁴ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
The repeating unit represented by the formula (IV) contained in the dispersant (b) may be one type or two or more types.

(R ¹⁴ )
In the formula (IV), R ¹⁴ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
Examples of the alkyl group include linear, branched, cyclic, or combinations thereof. The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 7 or more, and preferably 15 or less, more preferably 10 or less. More preferably, it is 8 or less. When the amount is not less than the lower limit, the dispersion stability tends to be improved, and when the amount is not more than the upper limit, the aggregation of the dispersant chain tends to be suppressed.

  Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Among these, from the viewpoint of dispersion stability, a methyl group, an ethyl group, and a propyl group are exemplified. It is preferably a group, a butyl group, a pentyl group or a hexyl group, more preferably a methyl group, an ethyl group, a propyl group or a butyl group.

  Examples of the substituent that the alkyl group may have include a halogen atom and an alkoxy group.

  Although carbon number of an aryl group is not specifically limited, Usually, 4 or more, Preferably it is 5 or more, More preferably, it is 6 or more, Preferably it is 16 or less, More preferably, it is 14 or less, More preferably, it is 12 or less. When the amount is not less than the lower limit, the dispersion stability tends to be improved, and when the amount is not more than the upper limit, the aggregation of the dispersant chain tends to be suppressed.

  Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Among these, from the viewpoint of dispersion stability, a phenyl group, A methylphenyl group, an ethylphenyl group, a dimethylphenyl group, or a diethylphenyl group is preferable, and a phenyl group, a methylphenyl group, or an ethylphenyl group is more preferable.

  Examples of the substituent that the aryl group may have include a chain alkyl group, a halogen atom, and an alkoxy group.

  The number of carbon atoms of the aralkyl group is not particularly limited, but is usually 5 or more, preferably 6 or more, more preferably 7 or more, and preferably 16 or less, more preferably 14 or less, and still more preferably 12 or less. When the amount is not less than the lower limit, the dispersion stability tends to be improved, and when the amount is not more than the upper limit, the aggregation of the dispersant chain tends to be suppressed.

  Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group. Among these, from the viewpoint of dispersion stability, a phenylmethylene group and a phenylethylene group , A phenylpropylene group or a phenylbutylene group, more preferably a phenylmethylene group or a phenylethylene group.

  Examples of the substituent that the aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group.

Among these, from the viewpoint of dispersion stability, R ¹⁴ is preferably an alkyl group which may have a substituent or an aralkyl group which may have a substituent.

  The dispersant (b) is a repeating unit represented by the following general formula (V) from the viewpoint of developability of the entire colored resin composition as a repeating unit other than the general formulas (I) and (II). It is preferable to have.

In the formula (V), R ¹⁵ represents a hydrogen atom or a methyl group.

  Although the content rate of the repeating unit represented by the said general formula (I) in a dispersing agent (b) is not specifically limited, 1 mol% or more is preferable in all the repeating units, 2 mol% or more is more preferable, 3 mol% The above is more preferable, 30 mol% or less is preferable, 10 mol% or less is more preferable, and 5 mol% or less is more preferable. When it is at least the lower limit, the hydrophilicity tends to be improved, and when it is at most the upper limit, the dispersion stability tends to be improved.

  Although the content rate of the repeating unit represented by the said general formula (II) in a dispersing agent (b) is not specifically limited, 1 mol% or more is preferable in all the repeating units, 5 mol% or more is more preferable, 8 mol% The above is more preferable, 50 mol% or less is preferable, 30 mol% or less is more preferable, 20 mol% or less is further preferable, and 15 mol% or less is particularly preferable. When it is at least the lower limit, the dispersion stability tends to be improved, and when it is at most the upper limit, the hydrophilicity tends to be improved.

  When the dispersant (b) contains the repeating unit represented by the general formula (III), the content ratio is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more in all repeating units. Preferably, 10 mol% or more is more preferable, 15 mol% or more is particularly preferable, 50 mol% or less is preferable, 40 mol% or less is more preferable, 30 mol% or less is further preferable, and 20 mol% or less is particularly preferable. . When it is at least the lower limit, the dispersion stability tends to be improved, and when it is at most the upper limit, the hydrophilicity tends to be improved.

  When the dispersant (b) contains the repeating unit represented by the general formula (IV), the content ratio is not particularly limited, but is preferably 30 mol% or more, more preferably 40 mol% or more in all repeating units. Preferably, 50 mol% or more is more preferable, 99 mol% or less is preferable, 90 mol% or less is more preferable, 80 mol% or less is more preferable, and 70 mol% or less is especially preferable. When it is at least the lower limit, the hydrophilicity tends to be improved, and when it is at most the upper limit, the dispersion stability tends to be improved.

  When the dispersant (b) contains the repeating unit represented by the general formula (V), the content ratio is not particularly limited, but is preferably 1 mol% or more, more preferably 3 mol% or more in all repeating units. Preferably, 5 mol% or more is more preferable, 30 mol% or less is preferable, 20 mol% or less is more preferable, and 10 mol% or less is more preferable. There exists a tendency for developability to improve by making it into the said lower limit or more, and there exists a tendency for a dispersibility to improve or to improve hydrophilicity by making it into the said upper limit or less.

  The dispersant (b) may be a random copolymer or a block copolymer, but is preferably a block copolymer from the viewpoint of dispersion stability, and an A block containing a repeating unit having a solvophilic group, An AB block copolymer or BAB block copolymer composed of a B block containing a repeating unit having a pigment adsorbing group (dye adsorbing group) is more preferred. Examples of the repeating unit having a parent solvent group include those represented by the general formulas (I), (IV) and (V), and the repeating unit having a pigment adsorbing group (dye adsorbing group) What is represented by Formula (II) or (III) is mentioned.

  When the dispersing agent (b) is an AB block copolymer or a BAB block copolymer, the content of the repeating unit represented by the general formula (I) contained in the A block is particularly limited. However, 1 mol% or more is preferable, 2 mol% or more is more preferable, 3 mol% or more is more preferable, 30 mol% or less is preferable, 20 mol% or less is more preferable, and 10 mol% or less is further Preferably, 5 mol% or less is particularly preferable. When it is at least the lower limit, the hydrophilicity tends to be improved, and when it is at most the upper limit, the dispersion stability tends to be improved.

  Moreover, when the dispersing agent (b) contains the repeating unit represented by the general formula (IV), the content ratio in the A block is not particularly limited, but is preferably 30 mol% or more, more preferably 40 mol% or more. More preferably, 50 mol% or more is further preferable, 70 mol% or more is more preferable, 80 mol% or more is particularly preferable, 99 mol% or less is preferable, 97 mol% or less is more preferable, and 95 mol% or less is preferable. More preferably, it is more preferably 93 mol% or less, particularly preferably 90 mol% or less. When it is at least the lower limit, the hydrophilicity tends to be improved, and when it is at most the upper limit, the dispersion stability tends to be improved.

  Moreover, when the dispersing agent (b) contains the repeating unit represented by the general formula (V), the content ratio in the A block is not particularly limited, but is preferably 1 mol% or more, preferably 3 mol% or more. More preferably, 5 mol% or more is more preferable, 8 mol% or more is particularly preferable, 50 mol% or less is preferable, 40 mol% or less is more preferable, 30 mol% or less is more preferable, and 20 mol% or less is more. More preferred is 15 mol% or less. There exists a tendency for developability to improve by making it into the said lower limit or more, and there exists a tendency for a dispersibility to improve or to improve hydrophilicity by making it into the said upper limit or less.

  When the dispersing agent (b) is an AB block copolymer or a BAB block copolymer, the content of the repeating unit represented by the general formula (II) contained in the B block is particularly limited. However, 5 mol% or more is preferable, 10 mol% or more is more preferable, 20 mol% or more is more preferable, 30 mol% or more is particularly preferable, 90 mol% or less is preferable, and 70 mol% or less is more preferable. 60 mol% or less is more preferable, and 50 mol% or less is particularly preferable. When it is at least the lower limit, the dispersion stability tends to be improved, and when it is at most the upper limit, the hydrophilicity tends to be improved.

When the dispersant (b) contains a repeating unit represented by the general formula (III),
The content ratio in the B block is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, still more preferably 40 mol% or more, and more preferably 50 mol% or more. Particularly preferably, it is preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 80 mol% or less, and particularly preferably 70 mol% or less. When it is at least the lower limit, the dispersion stability tends to be improved, and when it is at most the upper limit, the hydrophilicity tends to be improved.

  The acid value of the dispersant (b) is not particularly limited, but is preferably 1 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 20 mgKOH / g or more, and preferably 200 mgKOH / g or less, 100 mgKOH / g g or less is more preferable, 60 mgKOH / g or less is more preferable, and 40 mgKOH / g or less is particularly preferable. There exists a tendency for the developability of the whole colored resin composition to improve by setting it as the said lower limit or more, and there exists a tendency for a dispersion stability to improve by setting it as the said upper limit or less.

  The amine value of the dispersant (b) is not particularly limited, but is preferably 1 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 20 mgKOH / g or more, particularly preferably 30 mgKOH / g or more, and 200 mgKOH / G or less, more preferably 150 mgKOH / g or less, still more preferably 120 mgKOH / g or less, still more preferably 100 mgKOH / g or less, particularly preferably 70 mgKOH / g or less, and most preferably 50 mgKOH / g or less. When the amount is not less than the lower limit, the dispersion stability tends to be improved, and when the amount is not more than the upper limit, the developability of the entire colored resin composition tends to be improved.

  Further, the molecular weight of the dispersant (b) is not particularly limited, but is preferably 8000 or more, more preferably 10,000 or more, and further preferably 11,000 or more in terms of polystyrene-converted weight average molecular weight (hereinafter sometimes referred to as “Mw”). Moreover, 60000 or less is preferable, 50000 or less is more preferable, and 40000 or less is more preferable. When the amount is not less than the lower limit, the dispersion stability tends to be improved, and when the amount is not more than the upper limit, the developability of the entire colored resin composition tends to be improved.

  The dispersant (b) can be produced by a known method. For example, it can be produced by living polymerization of a monomer for introducing each of the above repeating units. Examples of the living polymerization method include JP-A-9-62002, JP-A-2002-31713, and P.I. Lutz, P.M. Masson et al, Polym. Bull. 12, 79 (1984), B.I. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K .; Ute, et al, Polym. J. et al. 17, 977 (1985), 18, 1037 (1986), Koichi right hand, Koichi Hatada, polymer processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Thesis, 46, 189 (1989), M.M. Kuroki, T .; Aida, J .; Am. Chem. Soc, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.C. Y. Sogoh, W .; R. Known methods described in Hertler et al, Macromolecules, 20, 1473 (1987) and the like can be employed. Also, the method described in JP2013-119568A can be adopted.

  The (B) dispersant in the colored resin composition of the present invention may contain a dispersant other than the dispersant (b) (hereinafter abbreviated as “other dispersant”). Examples include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants. it can. Specific examples of these dispersants are trade names of EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by Big Chemie), Disparon (registered trademark, manufactured by Enomoto Kasei), SOLPERSE (registered trademark, Louvre). Zol), KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), TERPLUS (Otsuka Chemical Co., Ltd.), and the like.

  In the colored resin composition of the present invention, the content ratio of these (B) dispersants is not particularly limited, but is generally 1% by mass or more, preferably 3% by mass or more, more preferably 4% by mass or more, in the total solid content. More preferably 5% by mass or more, and usually 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and particularly preferably 10% by mass or less. By making the lower limit value or more, the storage stability of the dispersion in the colored resin composition becomes good, the storage stability of the entire colored composition tends to be good, and by making the upper limit value or less Since the amount of other components in the colored resin composition can be increased, the developability and electrical reliability tend to be good.

  In the colored resin composition of the present invention, the content ratio of these dispersants (b) is not particularly limited, but is generally 1% by mass or more, preferably 3% by mass or more, more preferably 4% by mass or more in the total solid content. More preferably 5% by mass or more, and usually 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and particularly preferably 10% by mass or less. The storage stability of the dispersion in the colored resin composition is improved by setting it to the lower limit value or more, and the storage stability of the entire colored resin composition tends to be good, and the upper limit value or less. Since the amount of other components in the colored resin composition can be increased, the developability and electrical reliability tend to be good.

[1-3] Dispersion aid The colored resin composition according to the present invention may contain a pigment derivative or the like as a dispersion aid in order to improve the dispersibility of the colorant and improve the dispersion stability. As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolo Derivatives such as pyrrole and dioxazine pigments may be mentioned. Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, preferably a sulfonamide group and a quaternary salt thereof, and a sulfonic acid group, and more preferably a sulfonic acid group. In addition, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions. Specific examples of pigment derivatives include azo pigment sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, isoindoline pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, quinacridone pigment sulfonic acid derivatives, Examples thereof include sulfonic acid derivatives of diketopyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments.

  The amount of the dispersion aid used is usually 0.1 parts by weight or more, usually 30 parts by weight or less, preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the colorant (A). More preferably, it is 5 parts by mass or less.

[1-4] (C) Solvent (C) The solvent adjusts the viscosity by dissolving or dispersing the colorant, dispersant, binder resin, photopolymerization initiator and other components in the colored resin composition of the present invention. Has the function of
The solvent (C) may be any solvent that can dissolve or disperse each component.

  Examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, Propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl -3-Methoxybutanol Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;

Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Examples thereof include nitriles such as acetonitrile and benzonitrile.

  Commercially available solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like. These solvents may be used alone or in combination of two or more.

When forming pixels of a color filter by photolithography, a solvent having a boiling point in the range of 100 to 200 ° C. (under a pressure of 101.25 [hPa], hereinafter the same applies to the boiling point) is selected. Is preferred. More preferably, it has a boiling point of 120-170 ° C.
Glycol alkyl ether acetates are preferred from the viewpoints of good balance between the solvent, applicability, surface tension, etc., and relatively high solubility of the components in the composition.

  In addition, glycol alkyl ether acetates may be used alone or in combination with other solvents. As the solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the colorant tends to aggregate, and the storage stability such as the viscosity of the colored resin composition obtained later tends to decrease. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

It is also preferable to use a solvent having a boiling point of 150 ° C. or higher in combination. By using such a high-boiling solvent in combination, the colored resin composition is difficult to dry, and has the effect of making it difficult for the mutual relationship of the colorant dispersion to break down due to rapid drying. The content of the high boiling point solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass with respect to the solvent. There is a tendency that it is possible to reduce the possibility that a coloring material component or the like precipitates and solidifies at the tip of the slit nozzle and causes a foreign substance defect by setting it to the lower limit value or more. As a result, the drying temperature tends to be low, and the possibility of causing problems such as tact defects in the reduced pressure drying process and pin marks of prebaking in the color filter manufacturing process described later tends to be reduced.
The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be separately contained.

When forming a pixel of a color filter by the ink jet method, a solvent having a boiling point of usually 130 ° C. or higher and 300 ° C. or lower, preferably 150 ° C. or higher and 280 ° C. or lower is appropriate. By setting it as the said lower limit or more, there exists a tendency for the uniformity of the coating film obtained to become favorable. In addition, there are many residual solvents in the coating film even after heat baking by setting the above upper limit value or less, resulting in quality defects, drying time in vacuum drying or the like becomes longer, and takt time is increased. There is a tendency that it is possible to reduce the possibility of the occurrence of problems.
The solvent vapor pressure is usually 10 mmHg or less, preferably 5 mmHg or less, more preferably 1 mmHg or less, from the viewpoint of the uniformity of the resulting coating film.

  In addition, in the production of color filters by the ink jet method, the ink emitted from the nozzle is very fine, from several to several tens of pL, so the solvent evaporates and concentrates before landing on the periphery of the nozzle opening or in the pixel bank.・ Tends to dry. In order to avoid this, it is preferable that the solvent has a high boiling point. Specifically, it is preferable to include a solvent having a boiling point of 180 ° C. or higher. More preferably, it contains a solvent having a boiling point of 200 ° C. or higher, particularly preferably a boiling point of 220 ° C. or higher. The high boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total solvent contained in the colorant dispersion and / or the colored resin composition. The mass% or more is most preferable. There exists a tendency which can fully exhibit the evaporation prevention effect of the solvent from a droplet by setting it as the said lower limit or more.

Preferred examples of the high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.
Furthermore, it is also effective to partially contain a solvent having a boiling point lower than 180 ° C. in order to adjust the viscosity of the colorant dispersion or the colored resin composition and the solubility of the solid content. As such a solvent, a solvent having low viscosity, high solubility, and low surface tension is preferable, and ethers, esters, ketones, and the like are preferable. Of these, cyclohexanone, dipropylene glycol dimethyl ether, cyclohexanol acetate, and the like are particularly preferable.

  On the other hand, when the solvent contains alcohols, the ejection stability in the ink jet method may deteriorate. Therefore, it is preferable that alcohol is 20 mass% or less in all the solvents, 10 mass% or less is more preferable, and 5 mass% or less is especially preferable.

  The content of the solvent in the entire colored resin composition of the present invention is not particularly limited, but the upper limit is usually 99% by mass or less, preferably 90% by mass or less, and more preferably 88% by mass or less. By setting it to the upper limit value or less, there is a tendency that it is easy to avoid that it becomes difficult to form a coating film due to excessive decrease in colorants, dispersants, and the like. On the other hand, the lower limit of the content ratio of the solvent is usually 70% by mass or more, preferably 75% by mass or more, more preferably 80% by mass or more, and further preferably 82% by mass or more in consideration of viscosity suitable for application. is there.

[1-5] (D) Binder resin The colored resin composition of the present invention contains (D) a binder resin. (D) By containing a binder resin, film curability by photopolymerization and solubility by a developer can be compatible.
(D) As the binder resin, a preferable resin tends to be different depending on what means is used for the colored resin composition to be cured. In the case of the photopolymerizable resin composition, examples of the binder resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11. Known polymer compounds described in publications such as JP-A-174224, JP-A-2000-56118, and JP-A-2003-233179 can be used, but preferably [1-5-1 ]: An unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer. Alkali-soluble resin [1-5-2] obtained by adding a polybasic acid anhydride to at least a part of the resin or the hydroxyl group generated by the addition reaction. Linear alkali-soluble resin containing a boxyl group [1-5-3] Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the carboxyl group-containing resin [1-5-4] (meth) Acrylic resin [1-5-5] Epoxy (meth) acrylate resin having a carboxyl group, and the like. Hereinafter, each of these resins will be described.

[1-5-1] Unsaturated monobasic acid in at least part of the epoxy group of the copolymer with respect to the copolymer of the epoxy group-containing (meth) acrylate and other radical polymerizable monomer Or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. As one of particularly preferred resins, “epoxy group-containing (meth) acrylate” Unsaturated monobasic acid is added to 10 to 100 mol% of the epoxy group of the copolymer with respect to the copolymer of 5 to 90 mol% and other radical polymerizable monomer 10 to 95 mol%. Or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of the hydroxyl group generated by the addition reaction.

  Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

  The other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is preferably a mono (meth) acrylate having a structure represented by the following general formula (V).

In formula (V), R ^{91 to} R ⁹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ , or R ⁹⁵ and R ⁹⁷ may be connected to each other to form a ring.
In the formula (V), the ring formed by connecting R ⁹⁶ and R ⁹⁸ or R ⁹⁵ and R ⁹⁷ is preferably an aliphatic ring, which may be saturated or unsaturated, and carbon The number is preferably 5-6.

Especially, as a structure represented by general formula (V), the structure represented by following formula (Va), (Vb), or (Vc) is preferable.
By introducing these structures into the binder resin, when the colored resin composition of the present invention is used in a color filter or an image display device, the heat resistance of the colored resin composition is improved, or the colored resin composition is used. It is possible to increase the intensity of the pixel formed by using.

  In addition, the mono (meth) acrylate which has a structure represented by general formula (V) may be used individually by 1 type, and may use 2 or more types together.

  As the mono (meth) acrylate having the structure represented by the general formula (V), various known ones can be used as long as the structure has the structure, and those represented by the following general formula (VI) are particularly preferable. .

In the formula (VI), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents the structure of the general formula (V).
In the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer, the repeating unit derived from the mono (meth) acrylate having the structure represented by the general formula (VI) is: Among repeating units derived from “other radical polymerizable monomers”, those containing 5 to 90 mol% are preferable, those containing 10 to 70 mol% are more preferable, and those containing 15 to 50 mol% are particularly preferable. preferable.

  The “other radical polymerizable monomer” other than the mono (meth) acrylate having the structure represented by the general formula (VI) is not particularly limited. Specifically, for example, vinyl aromatics such as styrene, styrene α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives; butadiene, 2,3-dimethylbutadiene, isoprene, Dienes such as chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid-n-butyl, (Meth) acrylic acid-sec-butyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid pentyl, (meth) acrylic acid neopentyl, (meth) acrylic acid isoamyl, (meth) acrylic acid hexyl, (meta ) -2-ethylhexyl acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic Cyclopentyl acid, cyclohexyl (meth) acrylate, (meth) acrylate-2-methylcyclohexyl, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, propargyl (meth) acrylate, ( (Meth) acrylic acid phenyl, (meth) acrylic acid naphthyl, (meth) acrylic acid anthracenyl, (meth) acrylic acid anthraninonyl, (meth) acrylic acid piperonyl, (meth) acrylic acid salicylate, (meth) acrylic acid furyl, (Meth) acrylic acid furfuryl, (meth) acrylic acid tetrahydrofuryl, (meth) acrylic acid pyranyl, (meth) acrylic acid benzyl, (meth) acrylic acid phenethyl, (meth) acrylic acid cresyl, (meth) acrylic acid-1 , 1,1-trifluoroe Chill, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as cumyl, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate; (Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, (Meth) acrylic acid amides such as N-di-iso-propylamide and (meth) acrylic acid anthracenylamide; Vinyl compounds such as anilic rilates, (meth) acryloylnitriles, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate; diethyl citraconic acid, diethyl maleate, Unsaturated dicarboxylic acid diesters such as diethyl fumarate and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; N- (meta ) Acrylyl phthalimide and the like.

  Among these “other radically polymerizable monomers”, at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide is used to impart excellent heat resistance and strength to the colored resin composition. It is effective to use In particular, in the repeating unit derived from “another radical polymerizable monomer”, the content of the repeating unit derived from at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide is 1 to 70 mol. %, Preferably 3 to 50 mol%.

A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; Propylene glycol monoalkyl ether acetates; Acetic esters such as dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, butyl carbitol; Triethylene glycol dialkyl Ethers; propylene glycol dialkyl Ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane and decane Petroleum petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate; dimethylformamide, N-methylpyrrolidone and the like. These solvents may be used alone or in combination of two or more.

The amount of these solvents to be used is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, with respect to 100 parts by mass of the resulting copolymer. When the amount of the solvent used is outside this range, it becomes difficult to control the molecular weight of the copolymer.
The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound catalyst should be used. Can do. Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.

  Specific examples thereof include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, and t-butyl peroxy-2-ethyl. Hexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (T-butylperoxy) hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxide Oxydicarbonate, diisopropyl -Oxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1- Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane and the like can be mentioned.

Examples of the azo compound catalyst include azobisisobutyronitrile and azobiscarbonamide.
Among these, one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature. The usage-amount of a radical polymerization initiator is 0.5-20 mass parts with respect to a total of 100 mass parts of the monomer used for a copolymerization reaction, Preferably it is 1-10 mass parts.

  The copolymerization reaction may be carried out by dissolving the monomer and radical polymerization initiator used in the copolymerization reaction in a solvent and raising the temperature while stirring, or by adding the monomer to which the radical polymerization initiator has been added. Alternatively, the reaction may be performed dropwise in a solvent that has been heated and stirred. Further, the monomer may be added dropwise while the temperature is raised by adding a radical polymerization initiator to the solvent. The reaction conditions can be freely changed according to the target molecular weight.

  In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Is preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter. What consists of 70 mol% and the latter 70-30 mol% is especially preferable.

By setting the content ratio of the epoxy group-containing (meth) acrylate to be the above lower limit value or more, there is a tendency that the addition amount of the polymerizable component and the alkali-soluble component described later can be suppressed, while the epoxy group-containing content is included. By making the content ratio of (meth) acrylate not more than the upper limit value, there is a tendency that heat resistance and strength are easily made sufficient.
Subsequently, an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali) are added to the epoxy group portion of the copolymer of the epoxy resin-containing (meth) acrylate and another radical polymerizable monomer. A soluble component).

As the “unsaturated monobasic acid” to be added to the epoxy group, known ones can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.
Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These 1 type may be used independently and may use 2 or more types together.

By adding such components, polymerizability can be imparted to the binder resin used in the present invention.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. If the addition ratio of unsaturated monobasic acid is too small, there is a concern about the adverse effects of the remaining epoxy groups on the temporal stability of the colored resin composition. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, as the “polybasic acid anhydride” to be added to the hydroxyl group generated when an unsaturated monobasic acid is added to the epoxy group of the copolymer, known ones can be used.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferable. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

By adding such a component, alkali solubility can be imparted to the binder resin used in the present invention.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%. When the addition ratio is too large, the remaining film ratio at the time of development may decrease, and when it is too small, the solubility may be insufficient. In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.

Furthermore, in order to improve photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be.
Moreover, in order to improve developability, you may add the glycidyl ether compound which does not have a polymerizable unsaturated group to some produced | generated carboxyl groups.

Both of these may be added.
Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group. As commercial products, for example, trade names “Denacol (registered trademark, the same shall apply hereinafter) EX-111”, “Denacol EX-121”, “Denacol EX-141”, “Denacol EX-145”, “Nagase Kasei Kogyo Co., Ltd.” There are “Denacol EX-146”, “Denacol EX-171”, “Denacol EX-192”, and the like.

The structure of such a resin is described in, for example, JP-A-8-297366 and JP-A-2001-89533, and is already known.
The above-mentioned binder resin has a polystyrene equivalent weight average molecular weight (Mw) measured by GPC of preferably 3000 or more, more preferably 5000 or more, further preferably 8000 or more, more preferably 50000 or less, and more preferably 30000 or less. , 20000 or less is more preferable. When it is at least the lower limit, heat resistance and film strength tend to be sufficient, and when it is at most the upper limit, insufficient solubility in the developer tends to be suppressed. Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

[1-5-2] Linear alkali-soluble resin containing a carboxyl group in the main chain The linear alkali-soluble resin containing a carboxyl group in the main chain is not particularly limited as long as it has a carboxyl group. Usually, it is obtained by polymerizing a polymerizable monomer containing a carboxyl group.

  Examples of the carboxyl group-containing polymerizable monomer include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl. Adipic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2 -(Meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyl Oxybutyl succinic acid, 2- (meta Vinyl monomers such as acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid; Monomers obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone; hydroxyalkyl (meth) acrylate to succinic acid, maleic acid, phthalic acid, or Examples thereof include monomers added with acids or anhydrides such as anhydrides thereof. A plurality of these may be used.

Among these, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is more preferable.
The linear alkali-soluble resin containing a carboxyl group in the main chain may be copolymerized with the above-mentioned polymerizable monomer having no carboxyl group to the carboxyl group-containing polymerizable monomer. .

  Other polymerizable monomers include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate , Benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxy Ethyl (meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobonyl (meth) acrylate (Meth) acrylic esters such as adamantyl (meth) acrylate; vinyl aromatics such as styrene and its derivatives; vinyl compounds such as N-vinylpyrrolidone; N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide N-substituted maleimides such as polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly 2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone macromonomer, etc. And the like. These may be used in combination.

  Particularly preferred are styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, They are butyl (meth) acrylate, isobutyl (meth) acrylate, tricyclodecanyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, and N-phenylmaleimide.

  The linear alkali-soluble resin containing a carboxyl group in the main chain may further have a hydroxyl group. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and the like. Is mentioned. By copolymerizing these with the above-mentioned various monomers, a resin having a carboxyl group and a hydroxyl group can be obtained.

  Specifically, as a linear alkali-soluble resin containing a carboxyl group in the main chain, for example, (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl ( Polymeric monomers that do not contain hydroxyl groups such as meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. A copolymer with a hydroxyl group-containing monomer; such as (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl methacrylate, etc. (Meta) Acry Copolymer of acid ester; copolymer of (meth) acrylic acid and styrene; copolymer of (meth) acrylic acid, styrene and α-methylstyrene; copolymer of (meth) acrylic acid and cyclohexylmaleimide A polymer etc. are mentioned.

From the viewpoint of excellent dispersibility of the colorant, a copolymer resin containing benzyl (meth) acrylate is particularly preferable.
The acid value of the linear alkali-soluble resin containing a carboxyl group in the main chain in the present invention is usually 30 to 500 mgKOH / g, preferably 40 to 350 mgKOH / g, more preferably 50 to 300 mgKOH / g.

  Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-20000 normally, Preferably it is 3000-50000, More preferably, it is 4000-30000. By making the lower limit value or more, the stability of the colored resin composition tends to be good, and by making it the upper limit value or less, when used for a color filter or a liquid crystal display device described later, There is a tendency for the solubility to be good.

[1-5-3] Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the resin described in [1-5-2] The above-described linear alkali-soluble resin containing a carboxyl group in the main chain A resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the resin is also particularly preferable.

The epoxy group-containing unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule.
For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, 4- Acyclic epoxy group-containing unsaturated compounds such as hydroxybutyl (meth) acrylate glycidyl ether can also be mentioned, but from the viewpoint of heat resistance and dispersibility of the colorant described later, an alicyclic epoxy group-containing unsaturated compound Is preferred.

  Here, as the alicyclic epoxy group-containing unsaturated compound, as the alicyclic epoxy group, for example, 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 7,8-epoxy [tricyclo [5 .2.1.0] dec-2-yl] group and the like. In addition, the ethylenically unsaturated group is preferably derived from a (meth) acryloyl group. Suitable alicyclic epoxy group-containing unsaturated compounds include the following general formulas (5a) to (5m). The compound which is made is mentioned.

In formulas (5a) to (5m), R ²¹ represents a hydrogen atom or a methyl group, R ²² represents an alkylene group, R ²³ represents a divalent hydrocarbon group, and m is an integer of 1 to 10.
In the general formulas (5a) to (5m), the alkylene group represented by R ²² preferably has 1 to 10 carbon atoms. Specific examples include a methylene group, an ethylene group, a propylene group, and a butylene group, and a methylene group, an ethylene group, and a propylene group are preferable. As the hydrocarbon group R ^13, preferably has 1 to 10 carbon atoms, alkylene group, a phenylene group, and the like.

These alicyclic epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.
Among these, a compound represented by the general formula (5c) is preferable, and 3,4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable.
In order to add the epoxy group-containing unsaturated compound to the carboxyl group portion of the resin described in [1-5-2], a known method can be used. For example, a carboxyl group-containing resin and an epoxy group-containing unsaturated compound are converted into a tertiary amine such as triethylamine or benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride A quaternary ammonium salt such as pyridine, triphenylphosphine, etc. in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours. Saturated compounds can be introduced.

The acid value of the carboxyl group-containing resin into which the epoxy group-containing unsaturated compound is introduced is usually 10 to 200 mgKOH / g, preferably 20 to 150 mgKOH / g, more preferably 30 to 150 mgKOH / g.
Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-100000 normally, Preferably it is 4000-50000, More preferably, it is 5000-30000.

[1-5-4] (Meth) acrylic resin As a (meth) acrylic resin, a polymer obtained by polymerizing (meth) acrylic acid and / or (meth) acrylic acid ester as monomer components Say. Preferred (meth) acrylic resins include, for example, a polymer obtained by polymerizing monomer components including (meth) acrylic acid and benzyl (meth) acrylate, and the following general formulas (6) and / or (7). A polymer obtained by polymerizing a monomer component essentially comprising the compound represented, and a polymer obtained by polymerizing the monomer component essentially comprising the compound represented by the general formulas (5a) to (5l) Can be mentioned.

In formula (6), R ^1a and R ^2a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In formula (7), R ^1b represents a hydrogen atom or an alkyl group which may have a substituent, L ³ represents a divalent linking group or a direct bond, and X is represented by the following formula (8). Or an adamantyl group which may be substituted. L ³ may be bonded to R ^3b or R ^4b in the following formula (8) to form a ring.

In formula (8), R ^2b , R ^3b and R ^4b each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an amino group, or an organic group, and L ¹ and L ² are each independently a direct bond or 2 Represents a valent linking group, and L ¹ , L ² and two or more of L ³ in the formula (7) may be bonded to each other to form a ring.

[1-5-4a] A polymer obtained by polymerizing a monomer component containing (meth) acrylic acid and benzyl (meth) acrylate. A monomer component containing (meth) acrylic acid and benzyl (meth) acrylate is polymerized. The polymer is preferably used because it has a high affinity with the colorant.

  The ratio of the (meth) acrylic acid and benzyl (meth) acrylate in the monomer component is not particularly limited, but (meth) acrylic acid in the total monomer component is usually 10 to 90% by mass, preferably 15%. It is -80 mass%, More preferably, it is 20-70 mass%. Moreover, benzyl (meth) acrylate is 5-90 mass% normally in all the monomer components, Preferably it is 15-80 mass%, More preferably, it is 20-70 mass%. By setting it to the upper limit value or less, there is a tendency that the surface of the coating film can be prevented from becoming rough during development, and by setting the value to the lower limit value or more, development tends to be easy.

[1-5-4b] A polymer obtained by polymerizing a monomer component essentially comprising the compound represented by the general formula (6) and / or (7). First, the compound of the general formula (6) will be described.
In the ether dimer represented by the general formula (6), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ^1a and R ^2a is not particularly limited. Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance. R ^1a and R ^2a may be the same type of substituent or different substituents.

  Specific examples of the ether dimer include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, and the like.

  Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be used alone or in combination of two or more.

  Although the ratio of the ether dimer in the monomer component when obtaining the acrylic resin is not particularly limited, it is generally 2 to 60% by mass, preferably 5 to 55% by mass in the total monomer component, Preferably it is 5-50 mass%. By making the upper limit value or less, it tends to be difficult to obtain a low molecular weight product during polymerization or to be easily gelled. On the other hand, by setting the upper limit value or more, The coating film performance such as transparency and heat resistance tends to be sufficient.

Then, the compound of General formula (7) is demonstrated.
In General Formula (7), R ^1b preferably represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.
In the general formula (8), the organic groups represented by R ^2b , R ^3b and R ^4b are each independently, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an acyl group. Group, carboxyl group, acyloxy group and the like, preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a cyclohexane having 3 to 18 carbon atoms. An alkenyl group, an alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon atom, or an acyloxy group having 1 to 15 carbon atoms, Preferably, it is a C1-C10 alkyl group or a C3-C15 cycloalkyl group.

Preferred substituents among R ^2b , R ^3b and R ^4b are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
L ¹ , L ² and L ³ are each independently a direct bond, alkylene having 1 to 15 carbons, —O—, —S—, —C (═O) —, alkenylene having 1 to 15 carbons, and phenylene. Or a combination thereof.

As a preferable combination of L ¹ , L ² and L ³ , L ³ is a direct bond, alkylene having 1 to 5 carbon atoms, or a ring formed by combining with R ^3b or R ^4b, and L ¹ and L ² are Each independently represents a direct bond or alkylene having 1 to 5 carbon atoms.
Moreover, as a preferable thing of General formula (8), the compound represented by following General formula (9) can be mentioned.

In the formula (9), R ^2b , R ^3b , R ^4b , L ¹ and L ² have the same meaning as in the formula (8), and R ^5b and R ^6b are each independently a hydrogen atom, a hydroxyl group or a halogen atom. Represents an amino group or an organic group.
In general formula (9), the organic groups represented by R ^5b and R ^6b are each independently, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an acyl group, a carboxyl group, Or an acyloxy group and the like, preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, and a carbon number An alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon atom, or an acyloxy group having 1 to 15 carbon atoms, and more preferably a carbon number. It is a 1-10 alkyl group or a C3-C15 cycloalkyl group.

Preferred substituents among R ^5b and R ^6b are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
In addition, the alkyl group of R ^1b , each organic group of R ^2b , R ^3b and R ^4b , the divalent linking group of L ¹ , L ² and L ³ , and the adamantyl group of X are each independently a substituent. Specific examples thereof may include the following substituents.

Halogen atom; hydroxyl group; nitro group; cyano group; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, amyl group, t-amyl group, n-hexyl group A linear or branched alkyl group having 1 to 18 carbon atoms such as n-heptyl group, n-octyl group and t-octyl group; carbon number such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and adamantyl group A cycloalkyl group having 3 to 18 carbon atoms; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group and a hexenyl group; a cycloalkenyl group having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, amyl A linear or branched alkoxy group having 1 to 18 carbon atoms such as a xyl group, t-amyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, t-octyloxy group; methylthio group, Ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, s-butylthio group, t-butylthio group, amylthio group, t-amylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, a linear or branched alkylthio group having 1 to 18 carbon atoms such as t-octylthio group; an aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group and mesityl group; carbon such as benzyl group and phenethyl group Aralkyl group having 7 to 18 carbon atoms; straight chain or branched chain having 2 to 18 carbon atoms such as vinyloxy group, propenyloxy group, hexenyloxy group Alkenyloxy group; represented by -OCOR ^18; carboxyl group; an acyl group represented by -COR ^17; vinylthio group, propenylthio group, alkenylthio group linear or branched 2 to 18 carbon atoms such as hexenyl thio group An acyloxy group represented by —NR ¹⁹ R ²⁰ ; an acylamino group represented by —NHCOR ²¹ ; a carbamate group represented by —NHCOOR ²² ; a carbamoyl group represented by —CONR ²³ R ²⁴ ; Carboxylic acid ester group represented by ²⁵ ; sulfamoyl group represented by —SO ₃ NR ²⁶ R ²⁷ ; sulfonic acid ester group represented by —SO ₃ R ²⁸ ; 2-thienyl group, 2-pyridyl group, furyl group , Oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group, tetrahydrothiophene dioxide A saturated or unsaturated heterocyclic group such as a side group; a trialkylsilyl group such as a trimethylsilyl group;

R ^{17 to} R ²⁸ are each a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or The aralkyl group which may have a substituent is shown.
Moreover, the positional relationship of the said substituent is not specifically limited, When it has a some substituent, it may be same or different.

  Specific examples of the compound represented by the general formula (7) include the following.

  In the monomer component constituting the [1-5-4b] polymer according to the present invention, the ratio of the general formula (7) is not particularly limited, but is usually 0.5 to 60 mass in the total monomer components. %, Preferably 1 to 55% by mass, more preferably 5 to 50% by mass. When used as a dispersant when the amount is not more than the above upper limit value, the dispersion stability of the dispersion tends to be easily suppressed. On the other hand, when the amount is not less than the above lower limit value, the deterioration of soil stain suitability is suppressed. It tends to be easy to do.

  The (meth) acrylic resin of [1-5-4] in the present invention preferably has an acid group, including the polymers described in [1-5-4a] and [1-5-4b]. . By having an acid group, the resulting colored resin composition can be cured by a crosslinking reaction in which an acid group and an epoxy group react to form an ester bond (hereinafter abbreviated as acid-epoxy curing). Or a composition in which an uncured part can be visualized with an alkali developer. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups may be used alone or in combination of two or more.

  In order to introduce an acid group into the (meth) acrylic resin, for example, a monomer having an acid group and / or a “monomer capable of imparting an acid group after polymerization” (hereinafter, “monomer for introducing an acid group”) May be used as a monomer component. In addition, when using "monomer which can provide an acid group after superposition | polymerization" as a monomer component, the process for providing an acid group as mentioned later is required after superposition | polymerization.

Examples of the monomer having an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; maleic anhydride and itaconic anhydride. Although the monomer etc. which have a carboxylic anhydride group are mentioned, Especially, (meth) acrylic acid is preferable among these.
Examples of the monomer capable of adding an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; monomers having an epoxy group such as glycidyl (meth) acrylate; 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate.

These monomers for introducing an acid group may be only one type or two or more types.
When the monomer component for obtaining the (meth) acrylic resin also includes the monomer for introducing the acid group, the content ratio is not particularly limited, but usually 5% of all the monomer components. -70 mass%, Preferably it is 10-60 mass%.

[1-5-4] (Meth) acrylic resin may have a radical polymerizable double bond.
In order to introduce a radical polymerizable double bond into the (meth) acrylic resin, for example, “a monomer capable of imparting a radical polymerizable double bond after polymerization” (hereinafter referred to as “for introducing a radical polymerizable double bond”). May be referred to as a “monomer”.) Is polymerized as a monomer component, and then a treatment for imparting a radical polymerizable double bond as described later may be performed.

  Examples of the monomer capable of imparting a radical polymerizable double bond after polymerization include, for example, a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid; a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride Monomers: Monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. The monomer for introducing these radical polymerizable double bonds may be only one kind or two or more kinds.

In the case where the monomer component for obtaining the (meth) acrylic resin of [1-5-4] also contains a monomer for introducing the radical polymerizable double bond, the content ratio is particularly limited. However, it is usually 5 to 70% by mass, preferably 10 to 60% by mass, based on all monomer components.
When the (meth) acrylic resin of the present invention is a polymer having the compound of the general formula (6) as an essential monomer component described in the section [1-5-4a], it has an epoxy group. It is preferable.

In order to introduce an epoxy group, for example, a monomer having an epoxy group (hereinafter also referred to as “monomer for introducing an epoxy group”) may be polymerized as a monomer component.
Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These monomers for introducing an epoxy group may be only one type or two or more types.

When the monomer component for obtaining the (meth) acrylic resin of [1-5-4] also includes a monomer for introducing the epoxy group, the content ratio is not particularly limited, but usually Is 5 to 70% by mass, preferably 10 to 60% by mass, based on all monomer components.
The monomer component for obtaining the (meth) acrylic resin of [1-5-4] contains, in addition to the essential monomer component, other copolymerizable monomers as necessary. May be.

  Examples of other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate (Meth) acrylic acid esters such as; aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadienes such as butadiene and isoprene; Substituted butadiene compounds; ethylene, propylene, vinyl chloride , Ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate and the like.

Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.
In particular, when a part or all of the (meth) acrylic resin is used as a dispersant as described later, it is preferable to use benzyl (meth) acrylate, and the content thereof is usually all monomer components. It is good that it is 1 to 70% by mass, preferably 5 to 60% by mass.

When the monomer component for obtaining the (meth) acrylic resin also includes the other copolymerizable monomer, the content ratio is not particularly limited, but is preferably 95% by mass or less, and 85% by mass or less. Is more preferable.
Next, the production method (polymerization method) of [1-5-4] (meth) acrylic resin will be described.

  There is no particular limitation on the method for polymerizing the monomer component, and various conventionally known methods can be adopted, but the solution polymerization method is particularly preferable. The polymerization temperature and polymerization concentration (polymerization concentration = [total mass of monomer components / (total mass of monomer components + solvent mass)] × 100) are the types and ratios of the monomer components used. , Depending on the molecular weight of the target polymer. The polymerization temperature is preferably 40 to 150 ° C, more preferably 60 to 130 ° C. The polymerization concentration is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.

  Moreover, what is necessary is just to use the solvent used by normal radical polymerization reaction when using a solvent at the time of superposition | polymerization. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; Chloroform; Dimethyl sulfoxide and the like Is mentioned. These solvents may be used alone or in combination of two or more.

  When the monomer component is polymerized, a polymerization initiator may be used as necessary. The polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-amyl. Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexane Carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) and the like. These polymerization initiators may be used alone or in combination of two or more.

The amount of initiator used may be appropriately set according to the combination of monomers used, reaction conditions, target polymer molecular weight, etc., and is not particularly limited, but the weight average molecular weight without gelation. It is usually 0.1 to 15% by mass, more preferably 0.5 to 10% by mass with respect to the total monomer components in that several thousand to several tens of thousands of polymers can be obtained.
Moreover, you may add a chain transfer agent for molecular weight adjustment. Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid and methyl mercaptoacetate, and α-methylstyrene dimer. Preferred are n-dodecyl mercaptan and mercaptoacetic acid, which can be reduced and easily obtained. When a chain transfer agent is used, the amount used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but without gelation In terms of being able to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, it is usually 0.1 to 15% by mass, more preferably 0.5 to 10% by mass with respect to all monomer components.

In addition, when the compound of the general formula (6) is used as an essential monomer component, it is considered that the cyclization reaction of the ether dimer proceeds simultaneously in the polymerization reaction. The conversion rate is not necessarily 100 mol%.
When the acrylic resin is obtained, when the acid group is introduced by using the monomer capable of imparting the acid group described above as the monomer component, it is necessary to perform a treatment for imparting the acid group after polymerization. . The treatment varies depending on the type of monomer used. For example, when a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is used, succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride An acid anhydride such as a product may be added. When a monomer having an epoxy group such as glycidyl (meth) acrylate is used, a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol is added, or first ( An acid such as meth) acrylic acid may be added, and an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride or the like may be added to the resulting hydroxyl group. When a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate is used, for example, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.

When the (meth) acrylic resin of [1-5-4] is obtained, a radical polymerizable double bond is formed by using the monomer capable of imparting the radical polymerizable double bond described above as a monomer component. When introducing, it is necessary to perform a treatment for imparting a radically polymerizable double bond after polymerization.
The treatment varies depending on the type of monomer used. For example, when a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl ( A compound having an epoxy group and a radically polymerizable double bond such as (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether may be added. When a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride is used, a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate is added. Just do it. When a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether is used, ) A compound having an acid group such as acrylic acid and a radical polymerizable double bond may be added.

  The weight average molecular weight of the [1-5-4] (meth) acrylic resin is not particularly limited, but the polystyrene equivalent weight average molecular weight measured by GPC is preferably 2,000 to 200,000, more preferably 4,000 to 100,000. It is. When the amount is not more than the above upper limit value, the viscosity tends to be too low to easily form a coating film, and when the amount is not less than the above lower limit value, sufficient heat resistance tends to be easily exhibited.

When the said (meth) acrylic-type resin has an acid group, a preferable acid value is 30-500 mgKOH / g, More preferably, it is 50-400 mgKOH / g. By setting it as the said lower limit or more, there exists a tendency which is easy to apply to alkali image development, and when it is set to the said upper limit or less, there exists a tendency which it becomes easy to suppress becoming high viscosity and becoming difficult to form a coating film.
Among the (meth) acrylic resin components, the polymer having the compound represented by the general formula (6) as an essential monomer component is a compound known per se, for example, JP-A-2004-300203. And the compounds described in JP-A-2004-300204.

[1-5-5] Epoxy acrylate resin having carboxyl group Epoxy acrylate resin is an α, β-unsaturated monocarboxylic acid in an epoxy resin or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group in an ester moiety. It is synthesized by addition and further reacting with a polybasic acid anhydride. Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to “acrylate”, but epoxy resin is a raw material, and “acrylate” is a representative example. It is named like this according to common usage.

  As an epoxy resin as a raw material, for example, a bisphenol A type epoxy resin (for example, “Epicoat (registered trademark, the same applies hereinafter) 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004”, etc., manufactured by Mitsubishi Chemical Corporation) , Epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol A type epoxy resin and epichlorohydrin (for example, “NER-1302” (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin ( For example, “Epicoat 807”, “EP-4001”, “EP-4002”, “EP-4004 etc.” manufactured by Mitsubishi Chemical Corporation), an epoxy resin obtained by the reaction of an alcoholic hydroxyl group of bisphenol F type epoxy resin with epichlorohydrin (For example, “NER- manufactured by Nippon Kayaku Co., Ltd. 406 "(epoxy equivalent 350, softening point 66 ° C)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example," YX-4000 "manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (for example, Nippon Kayaku Co., Ltd.) "EPPN-201" manufactured by Mitsubishi Chemical Corporation, "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Co., Ltd.), (o, m, p-) cresol novolac type epoxy resin (For example, “EOCN (registered trademark, the same shall apply hereinafter) -102S”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, “TEPIC manufactured by Nissan Chemical Co., Ltd.) (Registered trademark) "), trisphenol methane type epoxy resin (for example," EPPN (registered trademark)-"manufactured by Nippon Kayaku Co., Ltd.) 01 ”,“ EPN-502 ”,“ EPPN-503 ”), fluorene epoxy resin (for example, cardo epoxy resin“ ESF-300 ”manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin (manufactured by Daicel Chemical Industries, Ltd.) "Celoxide (registered trademark, the same shall apply hereinafter) 2021P", "Celoxide EHPE"), a dicyclopentadiene type epoxy resin obtained by glycidylation of a phenol resin by reaction of dicyclopentadiene and phenol (for example, "Nippon Kayaku" XD-1000 "," EXA-7200 "manufactured by Dainippon Ink," NC-3000 "," NC-7300 "manufactured by Nippon Kayaku Co., Ltd.), and an epoxy resin represented by the following structural formula 355450) and the like can be preferably used.

These may be used alone or in combination of two or more.
Another example of the epoxy resin is a copolymer type epoxy resin. Examples of the copolymerization type epoxy resin include glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, vinylcyclohexene oxide and the like (hereinafter referred to as “first component of copolymerization type epoxy resin”) and one other than these. Functional ethylenically unsaturated group-containing compound (hereinafter referred to as “second component of copolymerization type epoxy resin”), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxy Ethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α-methylstyrene, glycerin mono (meth) acrylate, the following general formula (10 Compound represented by Al one or more selected, reacting the city include a copolymer obtained by.

In formula (10), R ⁶¹ represents a hydrogen atom or a methyl group, R ⁶² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and r is an integer of 2 to 10. Examples of the compound of the general formula (10) include polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and tetraethylene glycol mono (meth) acrylate; methoxydiethylene glycol mono ( Examples thereof include alkoxy polyethylene glycol (meth) acrylates such as meth) acrylate, methoxytriethylene glycol mono (meth) acrylate, and methoxytetraethylene glycol mono (meth) acrylate.

As for the molecular weight of the said copolymerization type epoxy resin, about 1000-200000 is preferable. Further, the amount of the first component of the copolymerization type epoxy resin used is preferably 10% by mass or more, particularly preferably 20% by mass or more, preferably 70%, based on the second component of the copolymerization type epoxy resin. It is at most 50% by mass, particularly preferably at most 50% by mass.
As such a copolymerization type epoxy resin, specifically, “CP-15”, “CP-30”, “CP-50”, “CP-20SA”, “CP-510SA” manufactured by NOF Corporation, “CP-50S”, “CP-50M”, “CP-20MA” and the like are exemplified.

  The molecular weight of the raw material epoxy resin is usually in the range of 200 to 200,000, preferably 300 to 100,000, as the weight average molecular weight in terms of polystyrene measured by GPC. If the weight average molecular weight is less than the above range, there are many cases where a problem occurs in the film forming property. Conversely, if the resin exceeds the above range, gelation easily occurs during the addition reaction of α, β-unsaturated monocarboxylic acid. May be difficult.

Examples of the α, β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid and the like, preferably acrylic acid and methacrylic acid, and particularly acrylic acid is highly reactive. Therefore, it is preferable.
The α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion includes acrylic acid-2-succinoyloxyethyl, acrylic acid-2-malenoyloxyethyl, acrylic acid-2-phthaloyloxyethyl, Acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid-2-succinoyloxyethyl, methacrylic acid-2-malenoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexahydrophthalo Yloxyethyl, crotonic acid-2-succinoyloxyethyl, and the like. Preferred are acrylic acid-2-malenoyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate, and particularly acrylic acid-2-maleic acid. Noyloxyethyl is preferred. These may be used alone or in combination of two or more.

  The addition reaction of an α, β-unsaturated monocarboxylic acid or ester thereof with an epoxy resin can be carried out by using a known method, for example, by reacting at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. can do. As the esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine; quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.

  The amount of α, β-unsaturated monocarboxylic acid or ester thereof used is preferably in the range of 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1, relative to 1 equivalent of the epoxy group of the raw material epoxy resin. Equivalent range. If the amount of α, β-unsaturated monocarboxylic acid or ester thereof used is small, the amount of unsaturated groups introduced is insufficient, and the subsequent reaction with the polybasic acid anhydride becomes insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, if the amount used is large, α, β-unsaturated monocarboxylic acid or ester thereof remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.

  The polybasic acid anhydride to be further added to the epoxy resin to which the α, β-unsaturated carboxylic acid or ester thereof is added includes maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, biphenyltetra Carboxylic acid dianhydride and the like, preferably maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, Biphenyltetracarboxylic dianhydride Particularly preferred compounds are tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. These may be used alone or in combination of two or more.

A known method can also be used for the addition reaction of polybasic acid anhydride, and it can be carried out by continuing the reaction under the same conditions as the addition reaction of α, β-unsaturated carboxylic acid or ester thereof.
The addition amount of the polybasic acid anhydride is preferably such that the acid value of the resulting epoxy acrylate resin is in the range of 10 to 150 mg-KOH / g, more preferably in the range of 20 to 140 mg-KOH / g. If the acid value of the resin is too small, the alkali developability is poor, and if the acid value of the resin is too large, the curing performance tends to be inferior.

  In addition, as an epoxy acrylate resin having a carboxyl group, for example, a naphthalene-containing resin described in JP-A-6-49174; JP-A-2003-89716, JP-A-2003-165830, JP-A-2005-325331, Examples include fluorene-containing resins described in JP-A No. 2001-354735; resins described in JP-A Nos. 2005-126684, 2005-55814, and 2004-295084.

Moreover, the commercially available epoxy acrylate resin which has a carboxyl group can also be used, and "ACA-200M" by Daicel Corporation etc. can be mentioned as a commercial item, for example.
As the binder resin, for example, an acrylic binder described in JP-A-2005-154708 can also be used.
Of the various binder resins described above, particularly preferred is a copolymer of [1-5-1] “epoxy group-containing (meth) acrylate and other radical polymerizable monomer. A resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group of the coal, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction " It is.

As binder resin in this invention, 1 type may be used independently among the above-mentioned various binder resins, and 2 or more types may be used together.
The above-mentioned various binder resins contribute to the dispersion stability due to the synergistic effect particularly in combination with the above-mentioned dispersant and the like, and as a result, the amount of the dispersant added can be reduced, so that the developability is improved. Specifically, for example, it is preferable because an effect of being able to form a high-density color pixel having excellent adhesion to the substrate without remaining undissolved material in the non-image portion on the substrate is preferable.

  Specifically, a part of the binder resin is used in the dispersion treatment step described later together with the above-described dispersant and dispersion aid. At this time, the binder resin is preferably used in an amount of about 5 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of the colorant in the colorant dispersion.

  When used in the dispersion treatment step together with a dispersant, the acid value of the binder resin is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, further preferably 50 mgKOH / g or more, particularly preferably 80 mgKOH / g or more, 500 mgKOH / g or less is preferable, 300 mgKOH / g or less is more preferable, 200 mgKOH / g or less is more preferable, and 150 mgKOH / g or less is particularly preferable. When the amount is not more than the above upper limit value, the viscosity tends to be suppressed and the synthesis is difficult to be suppressed, and when the amount is not less than the above lower limit value, alkali development tends to be easy.

  When used in a dispersion treatment step together with a dispersant, the weight average molecular weight in terms of polystyrene measured by GPC of the binder resin is preferably 1000 or more, more preferably 3000 or more, most preferably 5000 or more, and 200000 or less. Is preferably 50,000 or less, more preferably 30,000 or less, and most preferably 10,000 or less. When the amount is not more than the upper limit, alkali development tends to be easy, and when the amount is not less than the lower limit, the dispersion stability tends to be good.

  In the colored resin composition of the present invention, the content ratio of the binder resin in the total solid content is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass. Or more, more preferably 30% by mass or more, particularly preferably 40% by mass or more, most preferably 45% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass. Hereinafter, it is more preferably 55% by mass or less. By setting it to the lower limit value or more, a strong film can be obtained and the adhesion to the substrate tends to be excellent. Moreover, by setting it as the said upper limit or less, there exists a tendency for the permeability of the developing solution to an exposure part to be low, and to suppress the deterioration of the surface smoothness and sensitivity of a pixel.

[1-6] (E) Photopolymerization initiator The colored resin composition of the present invention contains (E) a photopolymerization initiator. (E) By containing a photopolymerization initiator, film curability by photopolymerization can be obtained.
(E) The photopolymerization initiator can also be used as a mixture (photopolymerization initiation system) with an accelerator (chain transfer agent) and an additive such as a sensitizing dye added as necessary. The photopolymerization initiation system is a component that has a function of directly absorbing light or photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.

Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A Nos. 59-152396 and 61-151197, and hexaarylbiimidazoles described in JP-A-10-39503. Derivatives, halomethyl-s-triazine derivatives, radical activators such as N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α- Examples thereof include aminoalkylphenone compounds and oxime ester initiators described in JP-A No. 2000-80068.

Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;

2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxa Diazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5 monofuryl-1,3 Halomethylated oxadiazole derivatives such as 4-oxadiazole;
2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- ( 2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5- Imidazole derivatives such as diphenylimidazole dimer;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;

Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1,1,1 An acetophenone derivative such as trichloromethyl- (p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;

benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as benzanthrone;
Dicyclopentadienyl-Ti-dichloride, dicyclopentagenyl-Ti-bis-phenyl, dicyclopentaenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, Dicyclopentagenenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentaenyl-Ti-bis-2,4,6-trifluorophen-1-yl, Dicyclopentagenyl-Ti-2,6-diplorophen-1-yl, dicyclopentagenenyl-Ti-2,4-difluorophen-1-yl, dimethylcyclopentaenyl-Ti-bis-2,3 , 4,5,6-pentafluorophen-1-yl, dimethylcyclopentagenyl-Ti-bis-2,6-difluorophen-1-yl, dicyclopentaje Le -Ti-2,6-difluoro-3- (pyrr-1-yl) - titanocene derivatives such as 1-yl;

2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Α-aminoalkylphenone compounds such as
1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- Yl] -1- (O-acetyloxime).

Among these, an oxime ester compound is preferable from the viewpoint of sensitivity and surface properties.
Oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in the structure, so they are highly sensitive in small amounts and stable against thermal reactions. Therefore, it is possible to design a photosensitive resin composition with high sensitivity in a small amount. In particular, an oxime ester-based compound having a carbazole ring which may have a substituent is preferable from the viewpoint of light absorption with respect to i-line (365 nm) of an exposure light source.

  Examples of oxime ester compounds include compounds represented by the following formula (V).

(In formula (V), R ¹⁰¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroaryl group having 4 to 25 carbon atoms. An alkyl group, any of which may have a substituent, or R ¹⁰¹ may be bonded to X or Z to form a ring;
R ¹⁰² is an alkanoyl group having 2 to 20 carbon atoms, alkenoyl of 3 to 25 carbon atoms, cycloalkanoyl group having 4 to 8 carbon atoms, aryloyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms , An aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroaryloyl group having 3 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms, It may have a substituent.

X represents at least one of a divalent aromatic hydrocarbon ring group and an aromatic hetero group formed by condensation of two or more rings which may have a substituent.
Z represents an aromatic ring group which may have a substituent or a heterocyclic group which may have a substituent.
Of the compounds represented by the formula (V), compounds in which X is a carbazole ring which may have a substituent are preferred, and specifically, compounds represented by the following formula (VI), etc. Among them, the compound represented by the following formula (VII) is particularly preferable.

In formula (VI), R ¹⁰¹ , R ¹⁰² and Z have the same definitions as in formula (V). R ^{103 to} R ¹⁰⁹ each independently represent a hydrogen atom or an arbitrary substituent.

In formula (VII), R ^101a represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following formula (VIIa).

In formula (VIIa), R ¹¹⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroarylalkyl having 4 to 25 carbon atoms. Indicates a group. * Represents a binding site. )
R ^102a represents an alkanoyl group having 2 to 4 carbon atoms, and X ^a represents a 3,6-carbazolyl group in which the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms. Za represents ^a phenyl group which may be substituted with an alkyl group or a naphthyl group which may be substituted with a morpholino group.

  Commercial products may be used as the oxime initiator. Examples of commercially available products include OXE-01, OXE-02 (BASF), TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG-314 (Changzhou Powerful Electronic New Materials Co., Ltd.) Ltd. (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD).

  Examples of the accelerator constituting the photopolymerization initiation system component include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, and 2-mercaptobenzo. A mercapto compound having a heterocyclic ring such as oxazole or 2-mercaptobenzimidazole or an aliphatic polyfunctional mercapto compound is used.

  These photopolymerization initiators and accelerators may be used alone or in combination of two or more.

The blending ratio of the photopolymerization initiator is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably, in the total solid content of the colored resin composition of the present invention. Is 1.5% by mass or more, more preferably 2% by mass or more, particularly preferably 2.5% by mass or more, and usually 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less. More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less. There is a tendency that the sensitivity to the exposure light beam can be sufficiently secured by setting it to the lower limit value or more, and suppressing the decrease in solubility in the developing solution of the unexposed portion by preventing the development failure by setting the upper limit value or less. There is a tendency to be able to.
If necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source can be added to the photopolymerization initiation system component for the purpose of increasing the sensitivity. Examples of these sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, and coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335. 3-ketocoumarin compounds described in JP-A-3-239703 and 5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A 47-2528, 54- No. 155292, Japanese Patent Publication No. 45-37377, Japanese Patent Laid-Open No. 48-84183, Japanese Patent Publication No. 52-112682, Japanese Patent Publication No. 58-15503, Japanese Patent Publication No. 60-88005, Japanese Patent Publication No. 59-56403, Japanese Patent Publication No. Japanese Unexamined Patent Publication No. 2-69, Japanese Unexamined Patent Publication No. 57-168088, Japanese Unexamined Patent Publication No. 5-107761, Japanese Unexamined Patent Publication No. 5-210240. Distribution, may be mentioned dyes having a dialkyl aminobenzene skeleton described in JP-A-4-288818.

  Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-di Tilaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, ( p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. P-dialkylaminophenyl group-containing compounds. Of these, 4,4'-dialkylaminobenzophenone is most preferred.

A sensitizing dye may also be used individually by 1 type, and 2 or more types may be mixed and used for it.
The blending ratio of the sensitizing dye in the colored resin composition according to the present invention is usually 0% by mass or more, preferably 0.2% by mass or more, more preferably 0.5% in the total solid content of the colored resin composition. It is in the range of not less than mass%, usually not more than 20 mass%, preferably not more than 15 mass%, more preferably not more than 10 mass%.

[1-7] (F) Surfactant The colored resin composition of the present invention contains 0.01% by mass or more of (F) surfactant in the total solid content. (F) By containing surfactant in the said range, it is thought that the surface tension of a coloring composition falls, the uniformity at the time of application | coating becomes favorable, and an application | coating nonuniformity does not generate | occur | produce easily.
Various surfactants such as anionic, cationic, nonionic and amphoteric surfactants can be used as surfactants, but nonionic surfactants are less likely to adversely affect various properties. It is preferable to use an agent, and among these, a fluorine-based surfactant and / or a silicone-based surfactant are effective in terms of coatability.

  As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain is suitable. Specifically, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octaethylene glycol di ( 1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2- Tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8,9, Examples include 9,10,10-decafluorododecane and 1,1,2,2,3,3-hexafluorodecane. Examples of these commercially available products include “BM-1000” and “BM-1100” manufactured by BM Chemie, “Megafuck F142D”, “Megafuck F172”, “Megafuck F173”, and “Megafuck F183” manufactured by DIC. ”,“ Megafuck F470 ”,“ Megafuck F475 ”,“ Megafuck F554 ”,“ Megafuck F559 ”,“ FC430 ”manufactured by 3M Japan,“ DFX-18 ”manufactured by Neos, and the like.

  Examples of the silicone surfactant include “KF-6011”, “KF-6011P”, “KF-6012”, “KF-6013”, “KF-6015”, “KF-6016”, and “KF-6017” manufactured by Shin-Etsu Silicone Co., Ltd. "KF-6017P", "KF-6004", "KF-6043", "KF-6048", "KF-6028", "KF-6028P", "KF-6038", "BYK323", "BYK330" manufactured by BYK Chemie Product.

  Examples of nonionic surfactants other than fluorosurfactants and silicone surfactants include polyoxyethylene alkyl ethers and polyoxyethylene polyoxypropylene alkyl ethers as polyoxyethylene surfactants. , Polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid Esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbit fatty acid esters, polyoxyethylene sorbit fatty acid esters, etc. That. Examples of these commercially available products include polyoxyethylene surfactants such as “Emulgen 104P” and “Emulgen A60” manufactured by Kao Corporation.

  Examples of the anionic surfactant include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, and higher alcohol sulfates. Ester salts, aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special Examples thereof include polymer surfactants. Among these, special polymer surfactants are preferable, and special polycarboxylic acid type polymer surfactants are more preferable. Commercially available products can be used as such anionic surfactants, such as “Emar 10” manufactured by Kao Corporation for alkyl sulfate esters, and “Perex NB-L” manufactured by Kao Corporation for alkylnaphthalene sulfonates. Examples of special polymer surfactants include “Homogenol L-18” and “Homogenol L-100” manufactured by Kao Corporation.

Further, the cationic surfactants include quaternary ammonium salts, imidazoline derivatives, alkylamine salts and the like, and the amphoteric surfactants include betaine type compounds, imidazolium salts, imidazolines, amino acids. Etc. Of these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred. Examples of commercially available products include “Acetamine 24” manufactured by Kao Corporation for alkylamine salts, and “Cotamine 24P” and “Cotamine 86W” manufactured by Kao Corporation for quaternary ammonium salts.
Further, the surfactant may be used in combination of two or more kinds, for example, silicone surfactant / fluorine surfactant, silicone surfactant / special polymer surfactant, fluorine surfactant. / Special polymer surfactant combinations and the like. Of these, a combination of silicone surfactant / fluorine surfactant is preferable.

  (F) Although the content rate of surfactant is not specifically limited, It is 0.005 mass% or more normally in all solid content, 0.01 mass% or more is preferable, 0.015 mass% or more is more preferable, 0 0.02% by mass or more is more preferable, 3% by mass or less is preferable, 2% by mass or less is more preferable, 1% by mass or less is more preferable, 0.8% by mass or less is more preferable, and 0.6% by mass. The following are particularly preferred: When the amount is not less than the lower limit, the surface tension of the colored composition is reduced and the uniformity during coating tends to be good, and uneven coating tends to be difficult to occur. The repelling of the applied colored resin composition tends to be reduced.

[1-8] Other solid content The colored resin composition of the present invention may further contain a solid content other than the above components as necessary. Examples of such components include photopolymerizable monomers, organic carboxylic acids, organic carboxylic acid anhydrides, thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protective agents, adhesion improvers, development improvers, dyes, and the like. It is done.

[1-8-1] Photopolymerizable Monomer The photopolymerizable monomer is not particularly limited as long as it is a low molecular weight compound that can be polymerized. However, an addition-polymerizable compound having at least one ethylenic double bond (hereinafter, (Referred to as “ethylenic compound”). The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of the aforementioned photopolymerization initiation system when the colored resin composition of the present invention is irradiated with actinic rays. . In addition, the monomer in this invention means the concept which opposes what is called a polymeric substance, and means the concept also containing a dimer, a trimer, and an oligomer other than the monomer of a narrow sense.

  Examples of the ethylenic compound include an unsaturated carboxylic acid, an ester thereof with a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, An ester, a polyisocyanate compound and a (meth) acryloyl-containing hydroxy compound obtained by an esterification reaction with a saturated carboxylic acid and a polyvalent carboxylic acid and the polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound or aromatic polyhydroxy compound; And an ethylenic compound having a urethane skeleton obtained by reacting.

Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane triacrylate, trimethylol ethane triacrylate, pentaerythritol.















Examples include acrylic acid esters such as tall diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, the acrylic acid part of these acrylates is a methacrylic acid ester replaced with a methacrylic acid part, an itaconic acid ester replaced with an itaconic acid part, a crotonic acid ester replaced with a crotonic acid part, or a maleic acid replaced with a maleic acid part Examples include esters.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Typical examples include, for example, condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol. And condensates of glycerin and the like.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclohexane diisocyanate and isophorone diisocyanate. Alicyclic diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3- (Meth) acryloyl group-containing hydroxy compounds such as hydroxy (1,1,1-trimethacryloyloxymethyl) propane Reaction products thereof.

In addition, as the ethylenic compound used in the present invention, for example, acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are also useful.
The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. The polyfunctional monomer provided is preferred, and particularly preferably in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the amount is not less than the lower limit, the development and dissolution properties tend to be favorable, and when the amount is not more than the upper limit, the production and handling are favorable, and the curability such as the surface smoothness of the pixel tends to be favorable. is there. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

  In the present invention, more preferred polyfunctional monomers having an acid group are mainly dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate which are commercially available as TO1382 manufactured by Toagosei Co., Ltd. It is a mixture as a component. Other polyfunctional monomers can be used in combination with this polyfunctional monomer. Also, those described in paragraphs [0056] and [0057] of JP2013-140346A can be used.

  Moreover, in this invention, it is preferable to use the polymerizable monomer of Unexamined-Japanese-Patent No. 2013-195971 from a viewpoint of making the chemical resistance of a pixel and the linearity of the edge of a pixel favorable. From the viewpoint of achieving both sensitivity of the coating film and shortening of the development time, it is preferable to use a polymerizable monomer described in JP2013-195974A.

  The content of these photopolymerizable monomers is usually 0% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass in the total solid content of the colored resin composition of the present invention. %, Usually 80% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, and particularly preferably 25% by mass or less.

[1-8-2] Organic carboxylic acid, organic carboxylic acid anhydride The colored resin composition of the present invention may contain an organic carboxylic acid and / or an organic carboxylic acid anhydride having a molecular weight of 1000 or less.
Specific examples of the organic carboxylic acid compound include aliphatic carboxylic acids and aromatic carboxylic acids. Aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, methacrylic acid and other monocarboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid And dicarboxylic acids such as adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, and tricarboxylic acids such as tricarbaric acid and aconitic acid. Examples of the aromatic carboxylic acid include carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and carboxylic acids in which a carboxyl group is bonded to the phenyl group through a carbon bond. Among these, those having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500, specifically maleic acid, malonic acid, succinic acid, and itaconic acid are preferred.

  Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specifically, acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, Aliphatic carboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride Things. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, those having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500, specifically maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferred.

The addition amount of these organic carboxylic acids and / or organic carboxylic anhydrides is usually 0.01% by mass or more, preferably 0.03% by mass or more, more preferably 0.05% by mass or more in the total solid content. Yes, 10 mass% or less, preferably 5 mass% or less, more preferably 3 mass% or less.
By adding these organic carboxylic acids and / or organic carboxylic anhydrides having a molecular weight of 1000 or less, it is possible to further reduce the remaining undissolved matter of the colored resin composition while maintaining high pattern adhesion. .

[1-8-3] Thermal polymerization inhibitor As the thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like are used. . The blending amount of the thermal polymerization inhibitor is preferably in the range of 3% by mass or less based on the total solid content of the composition.

[1-8-4] Plasticizer Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. Is used. The blending amount of these plasticizers is preferably in the range of usually 10% by mass or less with respect to the total solid content of the composition.

[2] Preparation of Colored Resin Composition Next, a method for preparing the colored resin composition according to the present invention (hereinafter sometimes referred to as a resist) will be described.

  First, a predetermined amount of each of the colorant, the solvent, and the dispersant is weighed, and the colorant is dispersed in the dispersion treatment step to prepare a colorant dispersion. In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By performing this dispersion treatment, the coloring material is made fine particles, so that the coating characteristics of the colored resin composition are improved, and the transmittance of the pixels in the color filter substrate of the product is improved.

When dispersing the colorant, as described above, it is preferable to use a dispersion aid or a dispersion resin as appropriate.
When the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set to 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time varies depending on the composition of the colorant dispersion, the size of the sand grinder apparatus, and the like, and therefore needs to be adjusted as appropriate.

  The colorant dispersion obtained by the above dispersion treatment is mixed with a solvent, a binder resin, a photopolymerization initiator, and in some cases, a predetermined amount of a photopolymerizable monomer and components other than those described above to obtain a uniform dispersion solution ( Colored resin composition). In each of the dispersion treatment step and the mixing step, fine dust may be mixed. Therefore, it is preferable to filter the obtained colorant dispersion or dispersion solution with a filter or the like.

[3] Production of Color Filter Substrate Next, the color filter according to the present invention will be described.
The color filter which concerns on this invention has a pixel formed using the above-mentioned colored resin composition.
[3-1] Transparent substrate (support)
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of materials include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, polysulfone thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, and poly (meth) acrylic. Examples thereof include thermosetting resin sheets such as a resin, and various glasses. Among these, glass or heat resistant resin is preferable from the viewpoint of heat resistance.

  The transparent substrate may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resins, etc., as necessary, in order to improve surface properties such as adhesiveness. . The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less.

[3-2] Black Matrix A color filter according to the present invention can be manufactured by providing a black matrix on the above-described transparent substrate and further forming pixel images of red, green, and blue normally. The colored resin composition is used as the black matrix forming coating solution or the red, green, and blue pixel (resist pattern) forming coating solution. Using the resist, coating, heat drying, image exposure, development on a resin black matrix forming surface formed on a transparent substrate or a metal black matrix forming surface formed using a chromium compound or other light shielding metal material And a pixel image is formed by performing each process of thermosetting.

The black matrix is formed on a transparent substrate using a light shielding metal thin film or a colored resin composition for black matrix. As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide, and chromium nitride, nickel and tungsten alloys, and the like may be used, and these may be laminated in a plurality of layers.
These metal light shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape with a positive photoresist, ceric ammonium nitrate, perchloric acid and / or nitric acid are added to chromium. Other materials are etched using an etchant according to the material, and finally a positive photoresist is stripped with a dedicated stripper to form a black matrix. be able to.

  In this case, first, a thin film of the metal or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, after forming a coating film of the colored resin composition on the thin film, the coating film is exposed and developed using a photomask having a repeated pattern such as stripes, mosaics, and triangles to form a resist image. Thereafter, this coating film can be etched to form a black matrix.

  When using the photosensitive coloring resin composition for black matrix, a black matrix is formed using the coloring resin composition containing a black coloring material. For example, black color material such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black or the like, or red, green, blue or the like appropriately selected from inorganic or organic pigments and dyes A black matrix can be formed in the same manner as described below for forming a red, green, and blue pixel image using a colored resin composition containing a black color material by mixing.

[3-3] Formation of Pixels A colored resin composition of one of red, green, and blue is applied on a transparent substrate provided with a black matrix, dried, and a photomask is overlaid on the coating film. A pixel image is formed by image exposure through a photomask, development, and if necessary, heat curing or photocuring to create a colored layer. A color filter image can be formed by performing this operation for each of the three colored resin compositions of red, green, and blue.

  The color resin composition for color filters can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, there is no influence of mist adhering when using the spin coating method, and the generation of foreign matter is further suppressed. It is preferable from a viewpoint.

  If the thickness of the coating film is too large, pattern development becomes difficult and it may be difficult to adjust the gap in the liquid crystal cell forming step. On the other hand, if it is too small, it is difficult to increase the colorant concentration. May not be possible. The thickness of the coating film is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm as the film thickness after drying. The range is as follows.

[3-4] Drying of Coating Film The coating film after the colored resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, IR oven, or convection oven. Alternatively, a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature may be used.

  The drying temperature condition is usually 50 ° C. or higher, preferably 70 ° C. or higher, and usually 200 ° C. or lower, preferably 160 ° C. or lower, particularly preferably 130 ° C. or lower. Moreover, although it depends on the heating temperature, the drying time is preferably 30 seconds or longer, particularly 60 seconds or longer, and usually 10 minutes or shorter, especially 5 minutes. The higher the drying temperature, the better the adhesion to the transparent substrate. However, when the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure.

[3-5] Exposure Step Image exposure is performed by superimposing a negative matrix pattern on the coating film of the colored resin composition and irradiating an ultraviolet light source or a visible light source through this mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

[3-6] Development Step The color filter according to the present invention is an organic solvent or surfactant after image exposure with the above-mentioned light source to the coating film using the colored resin composition according to the present invention. By carrying out development using an aqueous solution containing an alkaline compound and an alkaline compound, an image can be formed on a substrate for production. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.
There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, further 40 ° C. or lower. Is preferred. The development method can be any method such as immersion development, spray development, brush development, and ultrasonic development.

[3-7] Thermosetting treatment The color filter after development is subjected to thermosetting treatment. In this case, the thermosetting treatment conditions are such that the temperature is usually 100 ° C. or more, preferably 150 ° C. or more, and usually 280 ° C. or less, preferably 250 ° C. or less, and the time is 5 minutes or more and 60 minutes or less. Selected by range. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.

[3-8] Formation of Transparent Electrode The color filter according to the present invention forms a transparent electrode such as ITO on an image as it is, and is used as a part of a component such as a color display or a liquid crystal display device. However, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

[4] Image display device (panel)
Next, the image display apparatus of the present invention will be described. The image display device of the present invention has the color filter described above. Hereinafter, a liquid crystal display device and an organic EL display device will be described in detail as the image display device.

[4-1] Liquid Crystal Display Device A method for manufacturing a liquid crystal display device according to the present invention will be described. The liquid crystal display device according to the present invention is generally formed by forming an alignment film on the color filter according to the present invention, spraying spacers on the alignment film, and then bonding to a counter substrate to form a liquid crystal cell. The liquid crystal is injected into the liquid crystal cell and connected to the counter electrode to complete. The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to form a surface state in which the tilt of the liquid crystal can be adjusted.

  As the spacer, a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by a photolithography method, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of vacuum in the liquid crystal cell is usually in the range of 1 × 10 ⁻² Pa or more, preferably 1 × 10 ⁻³ Pa or more, and usually 1 × 10 ⁻⁷ Pa or less, preferably 1 × 10 ⁻⁶ Pa or less. . The liquid crystal cell is preferably heated during decompression, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower.

The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. In the liquid crystal cell into which liquid crystal is injected, a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.
The type of liquid crystal is not particularly limited, and may be any of conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, and may be any of lyotropic liquid crystals, thermotropic liquid crystals, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

[4-2] Organic EL Display Device When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, a pixel 20 is formed on a transparent support substrate 10 by the colored resin composition of the present invention. A multicolor organic EL element is produced by laminating the organic light-emitting body 500 on the blue color filter formed with the organic protective layer 30 and the inorganic oxide film 40 therebetween.

  As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the following examples, “part” represents “part by mass”.

<Blue pigment>
As a blue pigment, C.I. which is a copper phthalocyanine complex. I. Pigment Blue 15: 6 (Chromofine Blue 6311EC, manufactured by Dainichi Seika) was used.

<Dispersant A>
A methacrylic AB block copolymer comprising an A block containing a repeating unit having a philic solvent group and a B block containing a repeating unit having a pigment adsorbing group. It has a repeating unit of the following formulas (g) to (n). The amine value is 36 mgKOH / g, and the acid value is 25 mgKOH / g.
The content ratio of the following repeating units (g) to (n) in all repeating units is (g) 36.1 mol%, (h) 12.3 mol%, (i) 8.27 mol%, (j) 6.83 mol%, (k) 2.15 mol%, (l) 7.34 mol%, (m) 10.8 mol%, and (n) 16.2%.

<Dispersant B: Dispersant “BYK-LPN21116” manufactured by Big Chemie Corporation>
A methacrylic AB block copolymer comprising an A block containing a repeating unit having a philic solvent group and a B block containing a repeating unit having a pigment adsorbing group. It has a repeating unit of the following formulas (1a), (2a) and (3a). The amine value is 70 mgKOH / g, and the acid value is 1 mgKOH / g or less.

  The content ratios of the following formulas (1a), (2a), and (3a) in all repeating units are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively.

<Dispersant C: Dispersant “Disperbyk-2000” manufactured by Big Chemie Corporation>
A methacrylic AB block copolymer comprising an A block containing a repeating unit having a philic solvent group and a B block containing a repeating unit having a pigment adsorbing group. It has a repeating unit of the following formulas (1c), (2c) and (3c). The amine value is 10 mgKOH / g, and the acid value is 1 mgKOH / g or less.

  The content ratios of the following formulas (1c), (2c), and (3c) in all repeating units are 30.1 mol%, 3.3 mol%, and 6.7 mol%, respectively.

<Dispersion resin A>
Dispersion resin A was synthesized by the following procedure.
First, a separable flask equipped with a cooling tube as a reaction vessel was prepared, charged with 400 parts by mass of propylene glycol monomethyl ether acetate, purged with nitrogen, and then heated in an oil bath with stirring until the temperature of the reaction vessel reached 90 ° C. The temperature rose.

  Meanwhile, 30 parts by mass of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, t-butylperoxy-2-ethyl in the monomer tank Charge 5.2 parts by weight of hexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate, and 5.2 parts by weight of n-dodecyl mercaptan and 27 parts by weight of propylene glycol monomethyl ether acetate in a chain transfer agent tank After stabilizing at 90 ° C., dropping was started from the monomer tank and the chain transfer agent tank to initiate polymerization. While maintaining the temperature at 90 ° C., dropping was carried out over 135 minutes each, and 60 minutes after the dropping was finished, the temperature was raised and the reaction vessel was brought to 110 ° C.

After maintaining at 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 parts by mass of triethylamine were charged into the reaction vessel and left at 110 ° C. For 9 hours.
It cooled to room temperature and obtained the polymer solution of weight average molecular weight Mw8000 of polystyrene conversion measured by GPC, and the acid value of 101 mgKOH / g as the dispersion resin A.

<Binder resin A>
Binder resin A was synthesized by the following procedure.
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. 20 parts by mass of styrene, 57 parts by mass of glycidyl methacrylate, and 82 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and the mixture was further stirred at 120 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 27 parts by mass of acrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Then, 52 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 120 ° C. for 3.5 hours. The weight average molecular weight Mw in terms of polystyrene measured by GPC of the binder resin A thus obtained was about 8,000.

<Photopolymerizable monomer A>
A-9550 [mixture of dipentaerythritol hexa and pentaacrylate] (double bond equivalent: 100, manufactured by Shin-Nakamura Chemical Co., Ltd.)
<Photopolymerization initiator A>
Oxime ester compounds having the following chemical structure

<Surfactant A>
DIC Mega Fuck F-559
<Surfactant B>
BYK-330 manufactured by Big Chemie

<Preparation of pigment dispersion>
13.58 parts by mass of the blue pigment, 3.88 parts by mass (solid content) of the dispersant described in Table 1, 4.54 parts by mass (solid content) of the dispersion resin A, and a solvent (propylene glycol monomethyl ether) Acetate / propylene glycol monomethyl ether = 7/3 (mass ratio)) is used in such an amount that the solid content of the entire pigment dispersion is 20% by mass, and 225 parts by mass of zirconia beads having a diameter of 0.5 mm are filled in a stainless steel container. Then, it was dispersed for 6 hours with a paint shaker to prepare blue pigment dispersions A to C.

<Preparation of colored resin composition>
(Examples 1-3, Comparative Examples 1 and 2)
Other components shown in Table 2 were mixed with each of the blue pigment dispersions to prepare a colored resin composition so that the total solid content was 15% by mass. The combinations of the blue pigment dispersion liquid type and the surfactant amount were as shown in Table 3.
In addition, the compounding quantity of the coloring material in Table 2, binder resin, and a photopolymerizable monomer is a solid content conversion value, and PGMEA was added so that the total solid content of a colored resin composition might be 15 mass%. Moreover, the sum of the solid content conversion value of the blending amount of the binder resin and the blending amount of the surfactant was set to 42 parts by mass.

<Evaluation of contact angle with water>
Each colored resin composition was applied on a 50 mm square, 0.6 mm thick glass substrate (Asahi Glass Co., Ltd., AN100) with a spin coater, and then dried at 80 ° C. for 3 minutes. Subsequently, the whole surface exposure process was performed with the exposure amount of 40 mJ / cm < ² > with the 2kW high pressure mercury lamp. Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes.

One microliter of water was dropped onto the coated substrate thus obtained using a microsyringe, and the contact angle θ 30 seconds after dropping was measured with LCD-400S manufactured by Kyowa Interface Science Co., Ltd. The contact angle was evaluated according to the following criteria.
○: Contact angle is 80 ° or less △: Contact angle is larger than 80 ° and smaller than 82 ° ×: Contact angle is 82 ° or more

<Evaluation of coating unevenness>
On a 50 mm square, 0.6 mm thick glass substrate (Asahi Glass Co., Ltd. AN100), each colored resin composition was applied with a spin coater at a rotational speed such that the film thickness after application was 2.0 μm. When the surface of the coated substrate was uneven, “×” was evaluated as “◯”.
The results measured as described above are shown in Table 3 below.

  From Table 3, when the dispersing agent A which has a repeating unit of Formula (I) and Formula (II) is used like Examples 1-3, surfactant amount (solid content ratio) is 0.01 mass. In the case of% or more, the contact angle with respect to water was low, and coating unevenness did not occur and was good. This is because, even if a certain amount or more of a highly hydrophobic surfactant is used in order to reduce the surface tension so that coating unevenness does not occur, the dispersant A contains the repeating unit of the formula (I) containing a highly hydrophilic ester bond. It is considered that the contact angle to water was sufficiently low

  On the other hand, when Dispersant B or Dispersant C is used as in Comparative Examples 1 to 7, if the amount of the surfactant is decreased, the contact angle to water can be lowered, but coating unevenness occurs, conversely. When the amount of the surfactant is increased, coating unevenness does not occur, but the contact angle with water increases. This is because, when a certain amount or more of a highly hydrophobic surfactant is used in order to reduce the surface tension so that coating unevenness does not occur, the dispersant B or C is a dispersion having low hydrophilicity that does not contain the repeating unit of formula (I). Since it is an agent, the contact angle becomes high. Further, if the amount of the surfactant having high hydrophobicity is set to a certain amount or less in order to reduce the contact angle, it is considered that the surface tension of the coating film is increased and coating unevenness has occurred.

  In addition, even when Dispersant A was used as in Comparative Example 7, when the surfactant was not included, the contact angle with water was low, but coating unevenness occurred. This is considered to be because when the amount of the surfactant is not more than a certain amount, the surface tension of the coating film is increased and coating unevenness occurs.

  As described above, by using the dispersant having the repeating units of the formulas (I) and (II) and using a surfactant in a certain amount or more, the contact angle with water is low and coating unevenness is also generated. It can be said that it is good without. Since the contact angle with water is low, the developer easily penetrates during development, and the resist is also easily dissolved in the developer, preventing reattachment of the dissolved resist to the color filter and blocking of the drain filter of the developing machine. In addition, since coating unevenness does not occur, it can be considered that the inspection hindrance in the color filter manufacturing process can be suppressed and the yield can be improved.

DESCRIPTION OF SYMBOLS 100 Organic EL element 10 Transparent support substrate 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode

Claims (6)

A colored resin composition comprising (A) a colorant, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator,
The (B) dispersant contains a dispersant (b) having a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II):
Furthermore, the colored resin composition contains 0.01% by mass or more of (F) surfactant in the total solid content.

(In formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² and R ³ each independently represents an alkylene group which may have a substituent. N represents an integer of 1 to 10. Represents.)

(In formula (II), R ⁴ represents a hydrogen atom or a methyl group. R ⁵ represents an alkylene group which may have a substituent. R ⁶ and R ⁷ each independently represents a hydrogen atom or a substituent. R ⁶ and R ⁷ may be bonded to each other to form a cyclic structure. The colored resin composition according to claim 1, wherein the dispersant (b) further has a repeating unit represented by the following general formula (III).

(In the formula (III), R ⁸ represents a hydrogen atom or a methyl group. R ⁹ represents an alkylene group which may have a substituent. R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom. Represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, any two of R ^{10 to} R ¹² being And may be bonded to each other to form a cyclic structure. X ⁻ represents a monovalent anion.)   The colored resin composition according to claim 1 or 2, wherein a content ratio of the (F) surfactant is 1% by mass or less in the total solid content.   The colored resin composition according to any one of claims 1 to 3, wherein the (F) surfactant contains a fluorine-based surfactant and / or a silicone-based surfactant.   The color filter which has a pixel created using the colored resin composition of any one of Claims 1-4.   An image display device comprising the color filter according to claim 5.

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