JP2006343648A - Color material dispersion liquid for color filter, curable resin composition for color filter, method for producing the same, color filter, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition for a color filter, whose viscosity is little raises of storage time and which has excellent stability with the lapse of time. <P>SOLUTION: In the curable resin composition containing a color material, a dispersant, a binder resin, and a solvent, the content of moisture is set to be ≤0.35 wt.% based on the weight of all components. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a colorant dispersion used for a color filter, a curable resin composition and a method for producing the same, and a color filter and a liquid crystal display device using the same.

  Conventionally, a pigment dispersion method, a dyeing method, an electrodeposition method, and a printing method are known as methods for producing a color filter used in a liquid crystal display device or 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.

  In the pigment dispersion method, a pixel pattern is formed on a substrate using a curable resin composition (hereinafter also referred to as “resist” as appropriate) containing a pigment (coloring material), a binder resin, and a solvent. Is the method. The resist is usually prepared by mixing a binder resin, a solvent, or the like with a color material dispersion (hereinafter sometimes referred to as “ink” as appropriate) obtained by dispersing a pigment (color material) in a solvent. .

  In addition, a technique of adding a phosphate acrylate or the like to a resist is mainly known for the purpose of improving adhesion at the time of forming a pixel pattern (see Patent Document 1 and Patent Document 2).

Japanese Patent No. 3577754 JP 2000-338322 A

  However, conventional resists have insufficient stability over time, and the viscosity tends to increase with storage and the plate-making property tends to decrease. In particular, in the resist containing phosphoric acid acrylate, such a problem regarding the stability over time is remarkable, and improvement thereof has been demanded.

  The present invention has been made in view of the above problems. That is, the object of the present invention is to provide a curable resin composition for a color filter that has little increase in viscosity accompanying storage and is excellent in stability over time, a method for producing the same, and a color material dispersion for a color filter used in the production thereof. The present invention also provides a color filter and a liquid crystal display device using the curable resin composition for a color filter.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention can suppress the increase in viscosity accompanying the preservation of the resist by reducing the water content of the resist compared to the conventional one, and improve the stability over time. I found that it is possible. Furthermore, paying attention to the fact that the water contained in the resist is mainly derived from the color material dispersion liquid, the water content of the color material dispersion liquid can be reduced more effectively than before to effectively reduce the water content of the resist. As a result, the inventors have obtained knowledge that the above problems can be effectively solved, and have completed the present invention.

  That is, the gist of the present invention is a color material dispersion for a color filter containing a color material, a dispersant, and a solvent, wherein the ratio of water content to the total amount of components is 0.6% by weight or less. The present invention resides in a color material dispersion for a color filter (claim 1).

  Another gist of the present invention is a curable resin composition for a color filter containing a color material, a dispersant, a binder resin, and a solvent, which is formed using the above-described color material dispersion for a color filter. It exists in the curable resin composition for color filters characterized by the above-mentioned (Claim 2).

  Another gist of the present invention is a curable resin composition for a color filter containing a colorant, a dispersant, a binder resin, and a solvent, wherein the ratio of the amount of water to the total amount of components is 0.35% by weight or less. It exists in the curable resin composition for color filters characterized by being (Claim 3).

  Here, it is preferable that phosphoric acid (meth) acrylate is further contained.

  Another gist of the present invention is a method for producing a curable resin composition for a color filter containing a color material, a dispersant, a binder resin, and a solvent, and uses the above-described color material dispersion for a color filter. It exists in the manufacturing method of the curable resin composition for color filters characterized by the above-mentioned (Claim 5).

  Another gist of the present invention resides in a color filter characterized in that it is formed using the above-described curable resin composition for a color filter (claim 6).

  According to another aspect of the present invention, there is provided a liquid crystal display device comprising the above-described color filter.

The curable resin composition for a color filter of the present invention has little increase in viscosity during storage and is excellent in stability over time.
Further, according to the color material dispersion for color filters of the present invention and the method for producing a curable resin composition for color filters using the same, the curable resin composition for color filters having the above-described effects can be efficiently produced. Can be manufactured.
In addition, the color filter of the present invention formed by using the curable resin composition for a color filter of the present invention described above, and the liquid crystal display device of the present invention using the same are in close contact with image pixels formed on a substrate. High performance and excellent performance.

  Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made without departing from the scope of the invention.

[1] Colorant dispersion:
The color material dispersion for a color filter of the present invention (hereinafter abbreviated as “color material dispersion” as appropriate) contains a color material, a dispersant, and a solvent. Furthermore, you may contain other components other than the said component as needed. Hereinafter, each component will be described.

  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”. In the section [1], “total solid content” refers to all components of the color material dispersion of the present invention other than the solvent components described later.

[1-1] (A) Coloring material:
(A) A color material means what colors the color material dispersion liquid of this invention. Pigments and dyes can be used as the color material, but pigments are preferred from the viewpoints of heat resistance and light resistance.

  As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is.

  Specific examples of pigments that can be used are shown below by pigment numbers. In addition, “CI” described below 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. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 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. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

  Examples of green pigments 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. Of these, C.I. I. And CI Pigment Green 7 and 36.

  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. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  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. Of these, C.I. I. And CI pigment oranges 38 and 71.

  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. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

  Further, when the color material dispersion of the present invention is used as a color material dispersion for a black matrix of a color filter, a black color material can be used as the color material. The black color material may be a single color material, or may be a mixture of color materials such as red, green, and blue. These color materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, it is preferable to use the pigment dispersed in an average particle size of 1 μm or less, preferably 0.5 μm or less.

  Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 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. (The numbers in parentheses above mean the color index (CI)).

  Further, other pigments that can be used in combination 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.

  Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine 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 the following.
Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 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, OIL31

Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, SpecialBlack550 , SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Colo Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130 , VULCAN XC72R, ELFTEX-8

Made by Colombian Carbon: Raven11, Raven14, Raven15, Raven16, Raven22, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10 , RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

Moreover, as titanium black, what is produced with the following method is mentioned.
As a method for producing titanium black, a mixture of titanium dioxide and titanium metal is heated and reduced in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing 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, No. 61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), and the like. It is not something.

  On the other hand, examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials.

  As an example of another black pigment, aniline black, an iron oxide black pigment, and organic pigments of three colors of red, green, and blue can be mixed and used as a black pigment.

  In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, or the like can also be used as the pigment.

  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.

  The average particle size of these pigments is usually 1 μm, preferably 0.5 μm or less, more preferably 0.25 μm or less.

  On the other hand, examples of the dye that can be used as the coloring material include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

  Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.

  Other examples of the phthalocyanine dye include C.I. I. Pad blue 5 and the like. Examples of quinoneimine dyes include C.I. I. Basic Blue 3, C.I. I. Basic blue 9 and the like. Examples of quinoline dyes include C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like, and examples of the nitro dye include C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

  The ratio of the color material to the total solid content in the color material dispersion of the present invention is usually 1% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more, and usually 70% by weight or less, preferably The range is 60% by weight or less. If the content ratio of the color material is too small, the coloring power becomes low, the film thickness becomes too thick with respect to the color density, and adversely affects the gap control at the time of forming a liquid crystal cell. On the other hand, when the content ratio of the coloring material is too large, the dispersion stability is deteriorated, and problems such as re-aggregation and thickening may occur.

[1-2] (B) Dispersant:
The colorant dispersion of the present invention contains, for example, a graft copolymer and / or an acrylic block copolymer containing a nitrogen atom as the dispersant (B). Hereinafter, each dispersant will be described in detail.

<1-2-1> Graft copolymer containing nitrogen atom:
As the graft copolymer containing a nitrogen atom, those having a repeating unit containing a nitrogen atom in the main chain are preferred. Among these, it is preferable to have a repeating unit represented by the following formula (I) or / and a repeating unit represented by the formula (II).

（式（Ｉ）中、Ｒ¹は炭素数１〜５のアルキレン基を表わし、Ａは水素原子又は下記式（III）〜（Ｖ）のいずれかを表わす。）

(In formula (I), R ¹ represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or any one of the following formulas (III) to (V).)

In the above formula (I), R ¹ represents a linear or branched alkylene group such as methylene, ethylene or propylene. The carbon number is usually 1 or more, preferably 2 or more, and usually 5 or less, preferably 3 or less. Of these, an ethylene group is preferred.

  In the above formula (I), A represents a hydrogen atom or any one of the structures represented by the following formulas (III) to (V), preferably a structure represented by the formula (III).

In the formula (II), R ^1, A has the same meaning as R ^1, A of formula (I).

In the above formula (III), W ¹ represents a linear or branched alkylene group. The carbon number is usually 2 or more, preferably 4 or more, and usually 10 or less, preferably 7 or less. Preferable specific examples include butylene, pentylene, hexylene and the like.
In the above formula (III), p represents an integer of usually 1 or more, preferably 5 or more, and usually 20 or less, preferably 10 or less.

In the above formula (IV), Y ¹ represents a divalent linking group, and in particular, an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene and an alkyleneoxy group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy. Is preferred.

In the above formula (IV), W ² represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene, butylene, etc., among which an alkylene group having 2 to 3 carbon atoms such as ethylene or propylene. Is preferred.

In the above formula (IV), Y ² is a hydrogen atom or —CO—R ² (wherein R ² is an alkyl having usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. Examples thereof include ethyl, propyl, butyl, pentyl, hexyl and the like, among which ethyl, propyl, butyl, pentyl and the like are preferable.

  In the above formula (IV), q represents an integer of usually 1 or more, preferably 5 or more, and usually 20 or less, preferably 10 or less.

In the above formula (V), W ³ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 50 carbon atoms having 1 to 5 hydroxyl groups. Among these, a C10-20 alkyl group such as stearyl or a C10-20 hydroxyalkyl group having 1-2 hydroxyl groups such as monohydroxystearyl is preferable.

The content of the repeating unit represented by the formula (I) or (II) in the graft copolymer containing a nitrogen atom is preferably higher, and is usually 50 mol% or more, preferably 70 mol% or more. . Only one of the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II) may be contained, or both may be included. When both are contained, the content ratio is not particularly limited, but it is preferable that the repeating unit of the formula (I) is contained in a larger amount. The total number of repeating units represented by formula (I) or formula (II) is usually 1 or more, preferably 10 or more, more preferably 20 or more, and usually 100 or less, preferably 70 or less, more preferably 50. The range is as follows. Moreover, repeating units other than Formula (I) and Formula (II) may be included, and examples of other repeating units include an alkylene group and an alkyleneoxy group. Graft copolymers containing a nitrogen atom, the terminal -NH ₂ and -R ¹ -NH ₂ (wherein R ¹ has the same meaning as R ¹ described in the formula (I) and formula (II) .) Is preferable.

  In the graft copolymer containing a nitrogen atom, the main chain may be linear or branched.

  The amine value of the graft copolymer containing a nitrogen atom is usually 5 mgKOH / g or more, preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, and usually 100 mgKOH / g or less, preferably 70 mgKOH / g or less, More preferably, it is the range of 40 mgKOH / g or less. If the amine value is too low, the dispersion stability may decrease and the viscosity may become unstable. Conversely, if the amine value is too high, the residue may increase or the electrical characteristics after the liquid crystal panel is formed may deteriorate.

  The weight average molecular weight measured by GPC of the dispersant is usually 3000 or more, preferably 5000 or more, and usually 100,000 or less, particularly preferably 50000 or less. If the weight average molecular weight is too small, aggregation of the colorant cannot be prevented and the viscosity or gelation may occur. If the weight average molecular weight is too large, the dispersant itself becomes high in viscosity, and the organic solvent This is not preferable because of its poor solubility in water.

  As a method for synthesizing the dispersing agent, a known method can be employed. For example, a method described in JP-B-63-30057 can be used.

  In the present invention, a commercially available graft copolymer having the same structure as described above can also be applied.

<1-2-2> Acrylic block copolymer:
As an acrylic block copolymer, an AB block comprising an A block having a quaternary ammonium base and / or amino group in a side chain and a B block having no quaternary ammonium base and / or amino group. Copolymers and / or B-A-B block copolymers are preferred.

  The A block constituting the block copolymer of the acrylic block copolymer has a quaternary ammonium base and / or an amino group.

The quaternary ammonium base is preferably —N ⁺ R ^1a R ^2a R ^3a · Y ⁻ (where R ^1a , R ^2a and R ^3a are each independently a hydrogen atom, or an optionally substituted cyclic or chain) Or two or more of R ^1a , R ^2a and R ^3a may be bonded to each other to form a cyclic structure, and Y ⁻ represents a counter anion). With the quaternary ammonium base represented. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

In -N ⁺ R ^1a R ^2a R ^3a , the cyclic structure formed by bonding two or more of R ^1a , R ^2a and R ^3a to each other is, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or A condensed ring formed by condensing two of these may be mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following.

（上記式中、Ｒは、Ｒ^1a、Ｒ^2a及びＲ^3aのうち何れかの基を表わす。）

(In the above formula, R represents any group of R ^1a , R ^2a and R ^3a .)

These cyclic structures may further have a substituent.
R ^1a in the ^{-N + R 1a R 2a R 3a} , R 2a, and as R ^3a, and more preferred are an alkyl group having 1 to 3 carbon atoms which may have a substituent group, or substituted It may be a phenyl group which may be substituted, or a benzyl group which may have a substituent.

  As the A block, those containing a partial structure represented by the following formula (VI) are particularly preferable.

（上記式（VI）中、Ｒ^1a、Ｒ^2a、及びＲ^3aは各々独立に、水素原子、又は置換されていてもよい環状若しくは鎖状の炭化水素基を表わす。或いは、Ｒ^1a、Ｒ^2a、及びＲ^3aのうち２つ以上が互いに結合して、環状構造を形成していてもよい。Ｒ^4aは、水素原子又はメチル基を表わす。Ｘは、２価の連結基を表わす。Ｙ^-は、対アニオンを表わす。）

(In the above formula (VI), R ^1a , R ^2a , and R ^3a each independently represent a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, R ^1a , R ^2a And two or more of R ^3a may be bonded to each other to form a cyclic structure, R ^4a represents a hydrogen atom or a methyl group, X represents a divalent linking group, Y ^−. Represents a counter anion.)

In the above formula (VI), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R ^5a —, —COO—R ^6a — (provided that R ^5a and R ^{5 6a} represents a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R ^7a —O—R ^8a —: R ^7a and R ^8a each independently represents an alkylene group. ) And the like, and -COO-R ^6a -is preferred.

Examples of the counter anion Y ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .

The amino group is preferably —NR ^1b R ^2b (wherein R ^1b and R ^2b each independently have a cyclic or chain-like alkyl group which may have a substituent, or a substituent. Represents a good allyl group or an aralkyl group which may have a substituent.

  Among such structures having an amino group, a structure represented by the following formula is particularly preferable as the A block.

（但し、Ｒ^1b及びＲ^2bは、上記のＲ^1b及びＲ^2bとそれぞれ同義であり、Ｒ^3bは、炭素数１以上のアルキレン基を表わし、Ｒ^4bは、水素原子又はメチル基を表わす。）

(However, R ^1b and R ^2b are the same as R ^1b and R ^2b , respectively, R ^3b represents an alkylene group having 1 or more carbon atoms, and R ^4b represents a hydrogen atom or a methyl group.)

Among them, R ^1b and R ^2b are preferably methyl groups, R ^3b is preferably a methylene group and an ethylene group, and R ^4b is preferably a hydrogen atom.

  Specific examples of such a structure having an amino group include structures represented by the following formulae.

  Two or more kinds of partial structures containing the specific quaternary ammonium base and / or amino group as described above may be contained in one A block. In that case, two or more quaternary ammonium bases and / or amino group-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base and / or amino group may be contained in A block, As an example of this partial structure, it is derived from the below-mentioned (meth) acrylic acid ester monomer. Examples include partial structures. The content of such a quaternary ammonium base and / or a partial structure not containing an amino group in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably, the amino group-free partial structure is not contained in the A block.

  On the other hand, as the B block constituting the block copolymer of the dispersant, for example, styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) methacrylate , Isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate (Meth) acrylate monomers such as glycidyl ethyl acrylate and N, N-dimethylaminoethyl (meth) acrylate; (meth) acrylate monomers such as (meth) acrylic chloride; (meth) acrylamide, N-methylolacrylamide, , N-dimethylacrylamide, (meth) acrylamide monomers such as N, N-dimethylaminoethylacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and N-methacryloylmorpholine Examples include polymer structures.

  The B block is particularly preferably a partial structure derived from a (meth) acrylic acid ester monomer represented by the following general formula (VII).

(In the general formula (VII), R ^9a represents a hydrogen atom or a methyl group. R ^10a may have a cyclic or chain alkyl group which may have a substituent, or a substituent. Represents a good allyl group or an aralkyl group which may have a substituent.)

  Two or more kinds of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block. Of course, the B block may further contain a partial structure other than these. When a partial structure derived from two or more monomers is present in a B block that does not contain a quaternary ammonium base, each partial structure is contained in the B block in any form of random copolymerization or block copolymerization. May be. When the B block contains a partial structure other than the partial structure derived from the (meth) acrylate monomer, the content in the B block of the partial structure other than the (meth) acrylate monomer is preferably Is 0 to 99% by weight, more preferably 0 to 85% by weight.

  The acrylic dispersant used in the present invention is an AB block or a B-A-B block copolymer type polymer compound composed of such an A block and a B block, and such a block copolymer. Is prepared, for example, by the living polymerization method shown below.

The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. In the anion living polymerization method, the polymerization active species is an anion, for example, shown in the following scheme. In the scheme below, Ar ¹ and Ar ² each independently represent an arbitrary substituent.

In the radical living polymerization method, the polymerization active species is a radical, and is represented by the following scheme, for example. In the following schemes, Ar ¹ , Ar ² , R ^a , and R ^b each independently represent an arbitrary substituent.

  In synthesizing such an acrylic block copolymer, JP-A-60-89452, JP-A-9-62002, P. Lutz et al, Polymer Bulletin, vol.12, p.79 (1984) ), BC Anderson et al, Macromolecules, vol.14, p.1601 (1981), K. Hatada et al, Polymer Journal, vol.17, p.977 (1985), vol.18, p.1037 (1986) , Koichi et al., Polymer Processing, 36, 366 (1987), Toshinobu Higashimura et al., Polymer Journal, 46, 189 (1989), M. Kuroki et al., Journal of the American Chemical Society, vol.109, p.4737 (1987), Takuzo Aida et al., Synthetic Organic Chemistry, 43, 300 (1985), DY Sogoh et al, Macromolecules, vol.20, p.1473 (1987), Known methods described in K. Matyaszewski et al, Chemical Reviews, vol. 101, p. 2921-2990 (2001) can be employed.

  In addition, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and the BAB block copolymer according to the present invention is preferably 0.1 to 10 mmol, and outside this range. In some cases, good heat resistance and dispersibility cannot be combined.

  Such a block copolymer usually contains an amino group produced in the production process, but its amine value is usually about 1 mg-KOH / g or more and about 100 mg-KOH / g or less. It is. The amine value is a value expressed in mg of KOH corresponding to the acid value after neutralization titration of a basic amino group with an acid.

  Moreover, although the acid value of this block copolymer depends on the presence and type of the acid group that is the basis of the acid value, it is generally preferable that the acid value is low, and is usually 100 mg-KOH / g or less, and its molecular weight is The weight average molecular weight (Mw) in terms of polystyrene measured by GPC is usually in the range of 1000 to 100,000. When the molecular weight of the block copolymer is too small, the dispersion stability is lowered, and when it is too large, the developability and the resolution tend to be lowered.

  In the present invention, a commercially available acrylic block copolymer having the same structure as described above can also be applied.

<1-2-3> Other dispersants:
The colorant dispersion of the present invention may contain other dispersants as necessary in addition to the above dispersants.

  Other dispersants used include, for example, urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modification. A polyester-type dispersing agent etc. can be mentioned. Specific examples of such dispersants are EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei Co., Ltd.), and SOLPERSE (manufactured by Geneca). ), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (manufactured by Ajinomoto Co., Inc.) and the like. These dispersing agents may be used individually by 1 type, and may mix and use 2 or more types by arbitrary combinations and a ratio.

<1-2-4> Content of dispersant:
In the color material dispersion of the present invention, the content of the (B) dispersant is usually 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, based on (A) the color material. The range is usually 300% by weight or less, preferably 100% by weight or less, more preferably 80% by weight or less. When the content of the dispersant is too small, dispersion stability is deteriorated, and problems such as reaggregation and thickening occur. On the other hand, if the amount is too large, the ratio of the pigment is relatively reduced, so the coloring power is low, and the film thickness becomes too thick for the color density. Poor control may occur.

  Among them, the content ratio of the above-mentioned graft polymer and / or acrylic block copolymer containing a nitrogen atom is usually 40% by weight or less, preferably 30% by weight or less, more preferably with respect to (A) the color material. Is 20% by weight or less. When the content ratio of the graft polymer and / or the acrylic block copolymer containing nitrogen atoms is too small, the dispersion is unstable. On the other hand, when the content is too large, the image formability such as curability is lowered.

[1-3] (C) Solvent:
In the color material dispersion of the present invention, the (C) solvent has a function of dissolving or dispersing (A) the color material, (B) the dispersant, and other components blended as necessary, and adjusting the viscosity. Play.

  The type of the solvent is not particularly limited as long as it can dissolve or disperse the coloring material, the dispersant, and other components blended as necessary, and various organic solvents can be used. It is.

  Specific examples of the solvent include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, and apco. # 18 solvent, diisobutylene, amyl acetate, butyl acetate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, soak solvent no. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methyl amyl ketone, methyl isopropyl T, propylpropionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, ethyl lactate, ethyl lactate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3-ethoxypropion Methyl acid, ethyl 3-ethoxypropionate Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol- Examples include t-butyl ether, tripropylene glycol methyl ether, and 3-methyl-3-methoxybutyl acetate.

  In addition to the above examples, alcohols may be mixed as a solvent for the purpose of improving the coating property during die coating. When alcohols are used, there is a high possibility that the viscosity of the curable resin composition will increase as will be described later. Therefore, the effect of the application of the present invention is increased accordingly.

  Examples of preferable alcohols as the solvent include aliphatic alcohols such as propanol, butanol, propylene glycol and butanediol, aromatic alcohols such as benzyl alcohol, alicyclic alcohols such as cyclohexanol, ethylene glycol methyl ether, Examples include glycol ethers such as ethylene glycol ethyl ether, ethylene glycol mono n-butyl ether, propylene glycol methyl ether, and diethylene glycol monoethyl ether. Of these, glycol monoethers are preferred.

  In addition, any one of the various solvents described above may be used alone, or two or more may be used in combination with any combination and composition. In the case of using a plurality of types of solvents, the proportion of alcohols is preferably low, and specifically, the proportion of alcohols in the entire solvent is preferably 40% by weight or less.

  The content of the solvent in the entire colorant dispersion of the present invention is not particularly limited, but is usually 70% by weight or more, preferably 75% by weight or more, more preferably 80% by weight or more, and usually 99% by weight. The range is as follows. If the proportion of the solvent is too large, it is inappropriate to form a color material dispersion because the solid content of the color material, dispersant, etc. is too small. On the other hand, when the ratio of the solvent is too small, the viscosity becomes high and is not suitable for coating.

[1-4] Other components:
Although there is no restriction | limiting in particular as another component mix | blended with the coloring material dispersion liquid of this invention as needed, For example, the following component can be contained.

<1-4-1> Binder resin:
When the colorant dispersion of the present invention is blended in the curable resin composition described below, the colorant dispersion may contain a part of the binder resin described below. The dispersion stability during the production of the colorant dispersion can be improved.

  In this case, the amount of the binder resin used is usually 0% by weight or more, particularly 5% by weight or more, more preferably 10% by weight or more, and usually 100% by weight, based on the color material (A) in the colorant dispersion. In the following, it is preferable that the content be in the range of 80% by weight or less. When the amount of the binder resin used is too large, the color material density decreases, so that a sufficient color density cannot be obtained.

<1-4-2> Dispersing aid:
Examples of the dispersion aid include pigment derivatives. As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine And derivatives such as pigments. 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, 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, anthraquinone pigment sulfonic acid derivatives, quinacridone pigment sulfonic acid derivatives, and diketopyrrolopyrrole pigment sulfonic acid. And sulfonic acid derivatives of dioxazine pigments.

  The amount of the pigment derivative used is usually 0.1% by weight or more, preferably 0.3% by weight or more, more preferably 0.5% by weight or more, based on the total solid content of the colorant dispersion of the present invention. Usually, it is 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less. If the amount of the pigment derivative used is too small, the dispersion stability deteriorates and problems such as reaggregation and thickening occur. On the contrary, if the amount is too large, the contribution to the dispersion stability is saturated, and on the contrary, the color purity may be lowered.

[1-5] Water content of colorant dispersion:
The color material dispersion of the present invention is characterized in that the ratio of the water content to the total component amount is 0.6% by weight or less. Among these, 0.5% by weight or less is preferable, and 0.4% by weight or less is more preferable. This is an extremely low value compared with the water content of the conventional color material dispersion. By keeping the water content of the coloring material dispersion low in this way, when a curable resin composition (the curable resin composition of the present invention) is prepared using the colorant dispersion as described later, the water content is reduced. Therefore, it is possible to improve the temporal stability. On the other hand, the lower limit is not particularly limited, but is usually 0.01% by weight or more. The water content of the colorant dispersion can be measured using various moisture meters (for example, KF moisture meter CA-100 manufactured by Dia Instruments).

[1-6] Method for producing colorant dispersion:
Various methods can be adopted as a method for producing the color material dispersion of the present invention, and an example thereof is shown below.

  First, a predetermined amount of each of the color material, the solvent, and the dispersant is weighed, and in the dispersion treatment step, the color material is dispersed to obtain a liquid color material 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 color material is made into fine particles, so that the curable resin composition using the color material dispersion of the present invention has improved coating properties and the transmittance of the product color filter substrate.

  When the color material is subjected to a dispersion treatment, the binder resin or the dispersion aid may be used in combination as appropriate. For example, 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. Note that the dispersion time varies depending on the composition of the color material dispersion (color material, solvent, dispersant, etc.), the size of the sand grinder apparatus, and the like.

  In order to keep the water content of the color material dispersion within the above range, dehydration may be performed using various means. Dehydration may be performed on each component before mixing each component, or may be performed after mixing each component and dispersing the coloring material. When dehydration is performed before mixing each component, it is particularly preferable to dehydrate the color material.

Examples of the dehydration means include a method using a porous material such as molecular sieve, silica gel, and alumina, and a dehydrating agent such as sodium sulfite (Na ₂ SO ₃ ) and calcium chloride. In this case, these porous materials and dehydrating agents are added to each component before mixing and the colorant dispersion after mixing, mixed by a technique such as stirring, and then dehydrated. What is necessary is just to remove by means, such as filtration. In addition, dehydration may be performed by heating and / or depressurizing each component or color material dispersion.

  The detailed conditions of dehydration are not particularly limited, and may be adjusted as appropriate according to the dehydration technique and dehydration timing. For example, when a molecular sieve is mixed with the mixed color material dispersion to perform dehydration, Molecular Sieves 3A 1/16 (manufactured by Wako Pure Chemical Industries, Ltd.) or the like is used as the molecular sieve. This is usually mixed in a proportion of 0.5% by weight or more, preferably 1% by weight or more, and usually 30% by weight or less, preferably 20% by weight or less, and usually 1 hour or more, preferably May be stirred for 3 hours or longer, usually 30 hours or shorter, preferably 20 hours or shorter.

[1-7] Others:
The color material dispersion of the present invention can be used for various applications, and among them, it is preferably used as a curable resin composition for the purpose of forming a pixel image of a color filter.

[2] Curable resin composition The curable resin composition for a color filter of the present invention (hereinafter abbreviated as "the curable resin composition of the present invention" as appropriate) comprises a colorant, a dispersant, a binder resin, and a solvent. contains. Furthermore, you may contain a monomer, a photoinitiator, and another component as needed.

Hereinafter, each component will be described.
In the section [2], “total solid content” refers to all components of the curable resin composition of the present invention other than the solvent component described later.

[2-1] Binder resin:
Examples of the binder resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, and JP2000. -56118, JP2003-233179, JP2004-224894, JP2004-300203, JP2004-300204, etc. Among them, a polymer compound containing no nitrogen atom is preferable, and (W): 5 to 90 mol% of an epoxy group-containing (meth) acrylate, and (X): other copolymerizable with the (W) component 10 to 95 mol% of the radical polymerizable compound of the epoxy group contained in the resulting copolymer is 10 to 100 mol% Photosensitivity obtained by adding (Z) polybasic acid anhydride to 10 to 100 mol% of the hydroxyl group produced when (Y) unsaturated monobasic acid is added to (Y), and (Y) component is added. Resins are preferred.

  (W): 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-hydroxy Examples thereof include butyl (meth) acrylate glycidyl ether, and glycidyl (meth) acrylate is particularly preferable. These (W) components may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  (W): Copolymerization ratio of epoxy group-containing (meth) acrylate (copolymerization ratio when copolymerizing (W) component and (X) component to produce a copolymer. Hereinafter, simply referred to as “copolymerization ratio”) ) Is usually 5 mol% or more as described above, preferably 20 mol% or more, more preferably 30 mol% or more, and as described above, usually 90 mol% or less, It is 80 mol% or less, More preferably, it is the range of 70 mol% or less. If this ratio is too large, the component (X) may be reduced, and heat resistance and strength may be reduced. If the ratio is too small, the addition amount of the polymerizable component and the alkali-soluble component becomes insufficient.

  On the other hand, the copolymerization ratio of the other radical polymerizable compound that can be copolymerized with the component (X) :( W) is 10 mol% or more as described above, preferably 20 mol% or more, more preferably 30 mol. % Or more and 95 mol% or less as described above, preferably 80 mol% or less, more preferably 70 mol% or less. If this ratio is too large, the amount of the (W) component is decreased, so that the addition amount of the polymerizable component and the alkali-soluble component is insufficient, and if it is too small, the heat resistance and strength are lowered, which is not preferable.

  As another radical polymerizable compound that can be copolymerized with the component (X) :( W), one or more of mono (meth) acrylates having a structure represented by the following formula (1) are used. Is preferred.

(In the formula (1), R ^{4 to} R ⁷ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl, etc., and R ⁸ and R ⁹ each represent a hydrogen atom. , or a methyl group, an ethyl group, the ring or represents an alkyl group having 1 to 3 carbon atoms such as propyl, or linked good .R ⁸ and R ⁹ may form a ring is formed by connecting Is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.)

  In the said Formula (1), the mono (meth) acrylate which has a structure represented by following formula (2), (3) or (4) is preferable. By introducing these structures into the binder resin, it is possible to increase heat resistance and strength. Of course, these mono (meth) acrylates may be used alone or in combination of two or more.

  As the mono (meth) acrylate having the structure represented by the chemical formula (1), various known ones can be used, and those represented by the following chemical formula (5) are particularly preferable.

（式（５）中、Ｒ¹⁰は水素原子又はメチル基を表わし、Ｒ¹¹は前記の化学式（１）で表わされる構造を表わす。）

(In formula (5), R ¹⁰ represents a hydrogen atom or a methyl group, and R ¹¹ represents a structure represented by the chemical formula (1)).

  The content of the mono (meth) acrylate having the structure of the above formula (1) in the copolymerization monomer is usually 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, and usually 90 It is in the range of not more than mol%, preferably not more than 70 mol%, more preferably not more than 50 mol%.

  Moreover, it does not specifically limit as radically polymerizable compounds other than the above, The specific example is enumerated below.

Styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives of styrene;
Dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, 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, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, (meth) acrylic Isobornyl acid, adamantyl (meth) acrylate, (meth) acrylic acid Allyl sulfonate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl (meth) acrylate, piperonyl (meth) acrylate, (meth ) Salicyl acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, (meta ) Cresyl acrylate, (meth) acrylic acid-1,1,1-trifluoroethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro (meth) acrylate -Iso-propyl, triphenylmethyl (meth) acrylate, (meth (Meth) acrylic acid esters such as cumyl acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate Kind;
(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 amides such as N-di-iso-propylamide, (meth) acrylic acid anthracenyl amide;
Vinyl compounds such as (meth) acrylic acid anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate;
Unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate;
Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide;
N- (meth) acryloylphthalimide and the like.

  In order to impart more excellent heat resistance and strength, it is effective to use at least one selected from styrene, benzyl (meth) acrylate and monomaleimide as the (X) component. In this case, at least one copolymerization ratio selected from styrene, benzyl (meth) acrylate and monomaleimide is usually 1 mol% or more, especially 3 mol% or more, and usually 70 mol% or less, especially 50 mol% or less. It is preferable that it is the range of these.

  A known solution polymerization method is applied to the copolymerization reaction between the component (W) and the component (X). 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.

Specific examples thereof include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, butyl cellosolve acetate;
Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, butyl carbitol acetate;
Propylene glycol monoalkyl ether acetates;
Acetates 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, cyclohexanone;
Hydrocarbons such as benzene, toluene, xylene, octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; lactate esters such as methyl lactate, ethyl lactate and butyl lactate;
Examples include dimethylformamide and N-methylpyrrolidone.

  These solvents may be used alone or in combination of two or more. The amount of these solvents used is usually 30 parts by weight or more, preferably 50 parts by weight or more, and usually 1000 parts by weight or less, preferably 800 parts by weight or less with respect to 100 parts by weight of the resulting copolymer. . When the amount of the solvent used is outside this range, it is 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 can be used.

  Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.

  Specific examples of the radical polymerization initiator include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, and t-butyl peroxy. 2-ethylhexanoate, 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) peroxydicarbonate Diisopropyl peroxydicarbonate, 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, azobisisobutyronitrile, azobiscarbonamide, etc., and one of radical polymerization initiators having an appropriate half-life depending on the polymerization temperature Species or two or more species are selectively used.

  The amount of the radical polymerization initiator used is usually 0.5 parts by weight or more, preferably 1 part by weight with respect to 100 parts by weight of the monomer used for the copolymerization reaction, that is, the (W) component and the (X) component. In addition, the range is usually 20 parts by weight or less, preferably 10 parts by weight or less.

  The copolymerization reaction may be carried out by dissolving the monomer and radical polymerization initiator used in the copolymerization reaction in a solvent and stirring them, or the monomer added with the radical polymerization initiator is heated and stirred. You may carry out by dripping in a solvent. Further, the monomer may be added dropwise while the radical polymerization initiator is added to the solvent and the temperature is raised. The reaction conditions can be freely changed according to the target molecular weight.

  The (Y) component added to the epoxy group contained in the copolymer of the (W) component and the (X) component is an unsaturated monobasic acid. As the component (Y), known compounds can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond. Specific examples include acrylic acid, methacrylic acid, crotonic acid, o-, Examples thereof include monocarboxylic acids such as m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano substitution. Of these, acrylic acid and / or methacrylic acid are preferred. These (Y) components may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The (Y) component is usually 10 mol% or more, preferably 30 mol% or more, more preferably of the epoxy group contained in the copolymer obtained by the copolymerization reaction of the (W) component and the (X) component. It is added to 50 mol% or more and usually 100 mol% or less. If the addition ratio of the component (Y) is too small, there is a concern about adverse effects due to residual epoxy groups such as stability over time.

  As a method of adding the (Y) component to the copolymer of the (W) component and the (X) component, a known method can be employed.

  As the (Z) polybasic acid anhydride to be added to the hydroxyl group produced when the (Y) component is added to the copolymer of the (W) component and the (X) component, known ones can be used, Dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic And polybasic acid anhydrides such as acid anhydrides and biphenyltetracarboxylic acid anhydrides. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferable. As the component (Z), one type may be used alone, or two or more types may be mixed and used. By adding such components, the binder resin used in the present invention can be rendered alkali-soluble.

  (Z) component is usually 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more, and usually 100 mol% or less of the hydroxyl group produced when component (Y) is added. Preferably it is added to 90 mol% or less, more preferably 80 mol% or less. 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 becomes insufficient.

  As a method of adding the (Z) component to the hydroxyl group produced when the (Y) component is added to the copolymer of the (W) component and the (X) component, a known method can be adopted. .

  In the present invention, in order to further improve the photosensitivity, after adding (Z) polybasic acid anhydride, a glycidyl ether compound having a glycidyl (meth) acrylate or a polymerizable unsaturated group in a part of the generated carboxyl group is added. In order to add or improve developability, after adding (Z) polybasic acid anhydride, a glycidyl ether compound having no polymerizable unsaturated group may be added to a part of the generated carboxyl group, Both of these may be added. Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group or an alkyl group (manufactured by Nagase Chemical Industries, Ltd., trade names: Denacol EX-111, Denacol EX-121, Denacol) EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192) and the like.

  These resin structures are described in, for example, JP-A-8-297366 and JP-A-2001-89533, and are already known.

  The polystyrene-reduced weight average molecular weight (Mw) measured by GPC of such a binder resin is usually 3000 or more, preferably 5000 or more, and usually 100,000 or less, especially 50000 or less. If the molecular weight is too small, the heat resistance and the film strength are inferior, and if it is too large, the solubility in the developer is insufficient, which is not preferable. The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 2.0 to 5.0.

  Such binder resin may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  Such a binder resin is particularly excellent in adhesion to the substrate without remaining undissolved matter in the non-image area on the substrate, in combination with a urethane-based dispersant and an acrylic dispersant described later. The effect that a high density color pixel can be formed is preferable.

  Such a binder resin is usually 0.1% by weight or more, preferably 1% by weight or more, and usually 80% by weight or less, preferably 60% by weight or less in the total solid content of the curable resin composition of the present invention. It is contained in the range. When the content of the binder resin is less than this range, the film becomes brittle and the adhesion to the substrate may be lowered. On the other hand, when the amount is larger than this range, the permeability of the developing solution to the exposed portion increases, and the surface smoothness and sensitivity of the pixel may deteriorate.

[2-2] Photopolymerization initiator system:
The photopolymerization initiator is usually used as a mixture (photopolymerization initiator system) with an accelerator and an additive such as a sensitizing dye added as necessary. The photopolymerization initiator system is a component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.

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

  Specific examples of the polymerization 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- (4 '-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl -Acetophenone derivatives such as (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;
Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentagenyl-Ti-bis-phenyl, di-cyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl -1-yl, di-cyclopentagenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentagenyl-Ti-bis-2,4,6-tri Fluorophen-1-yl, di-cyclopentagenyl-Ti-2,6-dipuruolophen-1-yl, di-cyclopentagenyl-Ti-2,4-di-fluorophen-1-yl, Di-methylcyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentagenyl-Ti-bis-2,6-di-fluoropheny -1 Yl, di - cyclopentadienyl -Ti-2,6-di - fluoro-3- (pill-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- Oxime ester compounds such as 3-yl]-, 1- (O-acetyloxime) and the like.

  Examples of the accelerator constituting the photopolymerization initiator system component include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, and 2-mercaptobenzoxazole. A mercapto compound having a heterocyclic ring such as 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.

  Specific examples of the photopolymerization initiator component include dialkyl acetophenone, benzoin, and thioxanthone derivatives described in “Fine Chemical”, March 1, 1991, Volume 20, No. 4, pages 16 to 26, for example. In addition, the hexaarylbiimidazole series, the S-trihalomethyltriazine series, JP-A-4-221958, JP-A-4-221958, and the like described in JP-A-58-403023 and JP-B-45-37377. Examples thereof include a combination of titanocene and a xanthene dye, an addition-polymerizable ethylenic saturated double bond-containing compound having an amino group or a urethane group, which is described in JP-A-4-219756.

  The blending ratio of the photopolymerization initiator component is usually 0.1% by weight or more, preferably 0.5% by weight or more, and usually 40% by weight or less in the total solid content of the curable resin composition of the present invention. The range is preferably 30% by weight or less. If the blending ratio is extremely low, the sensitivity to the exposure light may be lowered. Conversely, if the blending ratio is extremely high, the solubility of the unexposed portion in the developer is lowered, and development failure may be induced.

  If necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source can be added to the photopolymerization initiator system component for the purpose of increasing the sensitivity. These sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and 3-ketocoumarin compounds described in Kaihei 3-239703 and 5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP 47-2528, JP 54-155292, JP 45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-6988, JP-A-57-168088. No. 5, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818. Mention may be made of a dye or the like having a skeleton.

  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) benzo Thiazole, 2- (p-die Ruaminophenyl) 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 curable resin composition of the present invention is usually 0% by weight or more, preferably 0.1% by weight or more, more preferably 0. 0% by weight in the total solid content of the curable resin composition. It is in the range of 2% by weight or more, usually 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less.

[2-3] Monomer:
The monomer is not particularly limited as long as it contains a photopolymerizable low molecular weight compound that can be polymerized, and is preferably a polyfunctional monomer having a functional group, and has at least one ethylenic double bond. Further preferred is an addition-polymerizable compound (hereinafter referred to as “ethylenic compound”). Moreover, the monomer may have an acid group.

  The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiator described later when the curable resin composition of the present invention is irradiated with actinic rays. is there. The term “monomer” in the present invention means a concept relative to a so-called polymer substance, and in addition to “monomer” in a narrow sense, “dimer”, “trimer”, “oligomer”. Means a concept that also includes

  Examples of the ethylenic compound having an acid group include an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid and a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an aromatic polyhydroxy compound and an unsaturated compound. Esters obtained by esterification with unsaturated carboxylic acid, unsaturated carboxylic acid and polyvalent carboxylic acid, and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, and polyisocyanate compounds Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting a (meth) acryloyl-containing hydroxy compound.

  Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, ilotonic acid, maleic acid and the like.

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, penta Acrylic esters such as erythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate and the like can be mentioned. 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, and pyrogallol triacrylate.

  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. Representative examples include 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 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; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanate; aromatic diisocyanate such as toluene diisocyanate, diphenylmethane diisocyanate, and the like, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3-hydroxy (1 , 1,1-Trimethacryloyloxymethyl) propane and other (meth) acryloyl group-containing hydroxy compounds And the like.

  In addition, as examples of the ethylenic compound used in the present invention, acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are also useful.

  In the present invention, the monomer is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. The acid group may be introduced by reacting the group with a non-aromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  In the present invention, the monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and 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.

  The acid value of the polyfunctional monomer having an acid group is usually 0.1 mg-KOH / g or more, especially 5 mg-KOH / g or more, and usually 40 mg-KOH / g or less, especially 30 mg-KOH / g or less. preferable. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. 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 essential.

  In the present invention, more preferred polyfunctional monomers having acid groups are 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.

  The blending ratio of these polyfunctional monomers is usually 5% by weight or more, preferably 10% by weight or more, and usually 80% by weight or less, preferably 70% by weight in the total solid content of the curable resin composition of the present invention. The ratio to the colorant is usually 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more, and usually 200% by weight or less, preferably 100% by weight or less. It is in the range of weight percent or less. The blending ratio of the polyfunctional monomer is appropriately adjusted according to the type of color material of the curable resin composition and the acid value of the polyfunctional monomer used.

[2-4] Organic carboxylic acid, organic carboxylic anhydride:
The curable resin composition of the present invention may further contain an organic carboxylic acid and / or an organic carboxylic acid anhydride in addition to the above components.

<2-4-1> Organic carboxylic acid:
Examples of the organic carboxylic acid include aliphatic carboxylic acids and / or aromatic carboxylic acids. Specific examples of the aliphatic carboxylic acid include monoacids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid, glycolic acid, acrylic acid, and methacrylic acid. Carboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethyl Examples thereof include dicarboxylic acids such as succinic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, and fumaric acid, and tricarboxylic acids such as tricarbaryl acid, aconitic acid, and camphoric acid. Specific examples of aromatic carboxylic acids include benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid, phthalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, and merophanic acid. , Pyromellitic acid, phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidenacetic acid, coumaric acid, umbelic acid, etc. Examples thereof include carboxylic acids in which a carboxyl group is directly bonded to a group, and carboxylic acids in which a carboxyl group is bonded to a phenyl group through a carbon bond.

  Among the organic carboxylic acids, monocarboxylic acids and dicarboxylic acids are preferable, and malonic acid, glutaric acid, and glycolic acid are more preferable, and malonic acid is particularly preferable.

  The molecular weight of the organic carboxylic acid is usually 50 or more and usually 1000 or less. If the molecular weight of the organic carboxylic acid is too large, the effect of improving the soiling is insufficient, and if it is too small, the addition amount may be reduced or process contamination may occur due to sublimation or volatilization.

<2-4-2> Organic carboxylic acid anhydride:
Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and / or aromatic carboxylic acid anhydrides, and specific examples of aliphatic carboxylic acid anhydrides include acetic anhydride, trichloroacetic anhydride, and trifluoro anhydride. Acetic acid, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2, Examples include aliphatic carboxylic acid anhydrides such as 3-dicarboxylic acid. Specific examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.

  Among the organic carboxylic acid anhydrides, maleic anhydride, succinic anhydride, itaconic anhydride, and citraconic anhydride are preferable, and maleic anhydride is more preferable.

  The molecular weight of the organic carboxylic acid anhydride is usually 800 or less, preferably 600 or less, more preferably 500 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid anhydride is too large, the effect of improving background stains is insufficient. If the molecular weight is too small, there is a possibility that the amount added may be reduced or process contamination may occur due to sublimation or volatilization.

  One of these organic carboxylic acids and organic carboxylic acid anhydrides may be used alone, or two or more thereof may be mixed and used.

  The addition amount of these organic carboxylic acid and organic carboxylic acid anhydride is usually 0.01% by weight or more, preferably 0.03% by weight or more, respectively, in the total solid content of the curable resin composition of the present invention. Preferably it is 0.05 weight% or more, and is 10 weight% or less normally, Preferably it is 5 weight% or less, More preferably, it is the range of 3 weight% or less. If the addition amount is too small, a sufficient addition effect cannot be obtained. If the addition amount is too large, surface smoothness and sensitivity are deteriorated, and undissolved peeling pieces may be generated.

[2-5] Other solid content:
The curable resin composition of the present invention may further contain components other than the above components as necessary. Examples of such components include surfactants, thermal polymerization inhibitors, plasticizers, phosphate acrylates, storage stabilizers, surface protective agents, adhesion improvers, development improvers, and the like.

<2-5-1> Surfactant:
Various types of surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as surfactants. It is preferable to use it.

  The addition amount of the surfactant is usually 0.001% by weight or more, preferably 0.005% by weight or more, more preferably 0.01% by weight or more with respect to the total solid content in the curable resin composition of the present invention. Particularly preferably, it is 0.03% by weight or more, and usually 10% by weight or less, preferably 1% by weight or less, preferably 0.5% by weight or less, particularly preferably 0.3% by weight or less. If the addition amount of the surfactant is less than the above range, the smoothness and uniformity of the coating film cannot be expressed, and if it is large, the smoothness and uniformity of the coating film cannot be expressed and other characteristics may be deteriorated. .

<2-5-2> Thermal polymerization inhibitor:
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like. The addition amount of the thermal polymerization inhibitor is preferably in the range of 0 to 3% by weight with respect to the total solid content of the curable resin composition of the present invention.

<2-5-3> 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. The amount of the plasticizer added is preferably 10% by weight or less based on the total solid content of the curable resin composition of the present invention.

<2-5-4> Phosphate acrylate:
The curable resin composition of the present invention preferably contains phosphoric acid acrylate. Phosphoric acid acrylate is a color filter using the curable resin composition of the present invention, which improves the removal of non-image areas at the time of developing a resist, prevents the occurrence of background stains, and improves the adhesion of fine line images. It has a function to improve and develop high image reproducibility. In addition, when the curable resin composition contains phosphoric acid acrylate, there is a high possibility that the viscosity will increase as described above, so that the effect of the application of the present invention is increased accordingly.

  Phosphoric acid (meth) acrylate is a phosphoric ester compound having one or more (meth) acryloyl groups, and examples thereof include those represented by the following general formula (6).

In formula (6), R ¹² represents hydrogen or a methyl group.
R ¹³ represents an alkylene group having 1 to 15 carbon atoms which may have a substituent. Examples of the substituent that the alkylene group may have include an alkyl group having 1 to 15 carbon atoms, an alkyleneoxy group having 1 to 15 carbon atoms, and a halogen group (bromine atom, chlorine atom, etc.).
a represents an integer of 1 to 3.
n represents an integer of 0 to 10.

More specifically, the following compounds etc. can be mentioned, for example.

  The amount of phosphate acrylate used is usually 0.1% by weight or more, preferably 0.3% by weight or more, and usually 30% by weight or less, based on the total solid content in the curable resin composition of the present invention. Preferably it is 20 weight% or less, More preferably, it is the range of 10 weight% or less. If the amount of phosphoric acid acrylate used is too small, it is not preferable because the adhesiveness deteriorates and high image reproducibility cannot be obtained. Conversely, if the amount is too large, the adhesiveness increases too much, and soiling is likely to occur. Again, it is not preferable for the reason.

<2-5-5> Others:
In addition, a storage stabilizer, a surface protective agent, an adhesion improver, a development improver, and the like can be added as necessary. The amount of these components added is preferably 20% by weight or less based on the total solid content of the curable resin composition of the present invention.

[2-6] Water content of curable resin composition:
The curable resin composition of the present invention is characterized in that the ratio of water content to the total amount of components is 0.35% by weight or less. Among these, 0.2% by weight or less is preferable, and 0.1% by weight or less is more preferable. This is an extremely low value compared to the water content of the conventional curable resin composition. By keeping the water content of the curable resin composition low in this manner, an increase in viscosity during storage can be suppressed, and stability over time can be improved. The lower limit is not particularly limited, but is usually 0.01% by weight or more. The water content of the color material dispersion can be measured using various moisture meters (for example, KF moisture meter CA-100 manufactured by Dia Instruments Co., Ltd.) in the same manner as the measurement of the water content of the color material dispersion. It is.

  The reason why the above effect is obtained by setting the water content of the curable resin composition within the above range is not clear, but is presumed as follows.

  That is, since water has polarity, it has an action of inhibiting the adsorption of the coloring material such as a pigment and the dispersing agent in the ink (coloring material dispersion) or resist (curable resin composition) system. Therefore, when the water content of the curable resin composition is high, the dispersion effect of the color material is hindered by the action of moisture, and the color material is re-aggregated to increase the viscosity.

  In addition, since phosphoric acid acrylates and alcohols are relatively high in polarity, if they are present in the ink (coloring material dispersion) or resist (curable resin composition) system, the colorant re-aggregates in the same way as water. It is considered to have an inviting action. Therefore, it is considered that the effect of the application of the present invention is increased accordingly.

[2-7] Preparation of curable resin composition:
Next, a method for preparing the curable resin composition of the present invention will be described.

  Solvent, binder resin, polyfunctional monomer, photopolymerization initiator system component, and other components blended as necessary, etc. in the colorant dispersion obtained by the dispersion treatment or the like described in [1-6] above Are mixed to obtain a uniform dispersion solution. In addition, in each process of a dispersion | distribution process and mixing, since fine refuse may mix, it is preferable to filter the obtained curable resin composition with a filter etc.

  In order to keep the water content of the curable resin composition within the above range, a method using a coloring material dispersion that is a raw material of the curable resin composition and other components having a low water content, and these components are used. A method of performing dehydration after mixing is considered. In the former case, since the water content of the curable resin composition is mainly derived from the color material dispersion liquid, it is preferable to use at least a color material dispersion liquid having a low water content, that is, the color material of the present invention described above. It is preferable to use a dispersion. On the other hand, in the case of dehydrating the curable resin composition after mixing, examples of the method include the method described above for the color material dispersion.

[3] Color filter:
Next, the color filter of the present invention will be described.
If the color filter of this invention is formed using the curable resin composition of this invention mentioned above, the structure will not be restrict | limited in particular. Hereinafter, although the structural example of the color filter of this invention is demonstrated, the structure of the color filter of this invention is not necessarily restrict | limited to what is demonstrated below.

  The color filter is usually manufactured by forming a black matrix on a transparent substrate and then sequentially forming red, green, and blue pixel images.

  The curable resin composition of the present invention is usually used as at least one pixel image forming coating liquid of black, red, green, and blue. For black resists, for red, green, and blue color resists, on a resin black matrix forming surface formed on the transparent substrate, or a metal formed using a chromium compound or other light shielding metal material A pixel image of each color is formed on the black matrix forming surface by performing coating, heat drying, image exposure, development, and thermosetting.

[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, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, and poly (meth). Examples thereof include thermosetting resin sheets such as acrylic resins, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.

  Thin film formation of various resins such as corona discharge treatment, ozone treatment, silane coupling agent, and urethane-based resin is necessary on transparent substrates and black matrix forming substrates described later for improving surface properties such as adhesion. Processing may be performed.

  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. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01 micrometer or more normally, Preferably it is 0.05 micrometer or more, Usually, 10 micrometers or less, Preferably it is the range of 5 micrometers or less.

[3-2] Black matrix:
The black matrix is formed on a transparent substrate using a light-shielding metal thin film or a photosensitive black composition for black matrix. As the light shielding metal material, chromium compounds such as metal chromium, chromium oxide, and chromium nitride, nickel and tungsten alloy, 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 curable resin composition on the thin film, the coating film is exposed and developed using a photomask having a repetitive pattern such as a stripe, a mosaic, and a triangle to form a resist image. Thereafter, this coating film can be etched to form a black matrix.

  On the other hand, when a black composition for black matrix is used, a black matrix is formed using a curable resin composition containing a black color material. For example, single or plural black color materials such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, or red, green, blue, etc., 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 curable resin composition containing a black color material by mixing the above.

[3-3] Formation of pixels:
<3-3-1> Formation of coating film:
On a transparent substrate provided with a black matrix, a curable resin composition containing a color material of one color of red, green, and blue is applied and dried, and then a photomask is overlaid on the formed coating film. A pixel image is formed by performing image exposure, development, and heat curing or photocuring as necessary through a photomask to form a colored layer of the pixel image. A color filter image can be formed by performing this operation for each of the three color curable resin compositions of red, green, and blue.

  The curable resin composition for the color filter 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. In particular, the die coating method significantly reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. To preferred.

  If the thickness of the coating film is too thick, pattern development becomes difficult and it may be difficult to adjust the gap in the liquid crystal cell forming process. Expression may be impossible. The thickness of the coating film is usually in the range of 0.2 μm or more, especially 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, especially 10 μm or less, more preferably 5 μm or less as the film thickness after drying. is there.

<3-3-2> Drying of coating film:
The coating film formed by applying the curable resin composition to the transparent substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after preliminary drying, two-stage drying is performed by heating again and drying. The conditions for the preliminary drying can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying temperature is selected in the range of usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 80 ° C. or lower, preferably 70 ° C. or lower, depending on the type of the solvent component, the performance of the dryer used. The drying time is selected in the range of usually 15 seconds or more, preferably 30 seconds or more, and usually 5 minutes or less, preferably 3 minutes or less, depending on the type of the solvent component, the performance of the dryer used, the drying temperature, and the like. It is.

  The temperature condition for reheat drying is preferably higher than the pre-drying temperature. Specifically, it is usually 50 ° C. or higher, particularly 70 ° C. or higher, particularly 70 ° C. or higher, and usually 200 ° C. or lower, especially 160 ° C. Hereinafter, the range of 130 ° C. or lower is particularly preferable. The drying time depends on the heating temperature, but is usually 10 seconds or more, preferably 15 seconds or more, and usually 10 minutes or less, preferably 5 minutes or less. The higher the drying temperature, the better the adhesion to the transparent substrate. However, if the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. The coating film may be dried by a reduced pressure drying method in which the temperature is not increased and drying is performed in a reduced pressure chamber.

<3-3-3> Exposure step:
Image exposure is performed by superimposing a negative matrix pattern on the dried coating film of the curable resin composition and irradiating an ultraviolet or visible light source through the mask pattern. Under the present circumstances, in order to prevent the fall of the sensitivity of the curable resin composition film | membrane by oxygen as needed, you may expose, after forming oxygen barrier layers, such as a polyvinyl alcohol layer, on the curable resin composition film | membrane.

  The light source used for image exposure is not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp. And lamp light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

<3-3-4> Development step:
Development can be performed after the image exposure using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. 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 used individually by 1 type, and 2 or more types may be mixed and used for them.

  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, sulfosuccinate esters, amphoteric surfactants such as alkylbetaines, amino acids, etc. They may be used alone or in combination of two or more.

  Examples of the organic solvent include one or more of isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, and the like. The organic solvent may be used alone or in combination with an aqueous solution.

  There are no particular restrictions on the conditions for the development process. Specifically, the development temperature is usually 10 ° C. or higher, preferably 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, more preferably 40 ° C. or lower. The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

<3-3-5> Thermosetting treatment:
The color filter substrate after development is usually subjected to heat curing treatment or light curing treatment, preferably heat curing treatment.

  As thermosetting treatment conditions, the temperature is usually 100 ° C. or higher, preferably 150 ° C. or higher, and usually 280 ° C. or lower, preferably 250 ° C. or lower. The time is usually 5 minutes or longer and 60 minutes or shorter. Chosen by

  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 patterning order of the three colors red, green, and blue is not limited to the order described above.

<3-3-6> Formation of transparent electrode:
The color filter according to the present invention forms a transparent electrode such as ITO on the image as it is, and is used as a part of a color display, a liquid crystal display device, etc., but it has surface smoothness and durability. In order to enhance, 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] Liquid crystal display device (panel):
Next, the manufacturing method of the liquid crystal display device (panel) of this invention is demonstrated.
If the liquid crystal display device of this invention is provided with the color filter of this invention mentioned above, the structure will not be restrict | limited in particular. Hereinafter, although the structural example of the liquid crystal display device of this invention is demonstrated, the structure of the liquid crystal display device of this invention is not necessarily restrict | limited to what is demonstrated below.

  In the liquid crystal display device of the present invention, an alignment film is usually formed on the color filter of the present invention, spacers are dispersed on the alignment film, and then bonded to a counter substrate to form a liquid crystal cell. The liquid crystal is injected into the cell and connected to the counter electrode.

  As the alignment film, a resin film such as polyimide is suitable. 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 usually several tens of nm. The alignment film is cured by thermal baking, and then surface-treated by irradiation with ultraviolet rays or a rubbing cloth to process the surface state so that the tilt of the liquid crystal can be adjusted.

  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 photolithography, 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 to 8 μm. 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 ultraviolet (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 decompression is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The type of liquid crystal is not particularly limited, and conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds are used, and any of lyotropic liquid crystals, thermotropic liquid crystals, and the like may be used. 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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded. In the following description, “parts” represents parts by weight and “%” represents percent by weight unless otherwise specified.

[Examples 1 to 5]
[Preparation of ink]
An ink (coloring material dispersion) was prepared with the composition shown in Table 1 below.

  A color material dispersion was prepared by filling 225 parts by weight of zirconia beads having a diameter of 0.5 mm into a stainless steel container, adding each of the components shown in Table 1 above, and dispersing for 6 hours in a paint shaker.

[Dehydration of ink]
The ink obtained by the above procedure was dehydrated by the following procedure.
(1) Molecular sieve (Molecular Sieves 3A 1/16: Wako Pure Chemical Industries, Ltd.) was vacuum-dried in an oven at 200 ° C. for 5 hours.
(2) Add 5% by weight of molecular sieve to the ink and stir for about 7 hours (Examples 1 to 4), or add 10% by weight of molecular sieve to the ink and stir for about 10 hours ( Example 5) As a result, the ink was dehydrated.
(3) The dehydrated ink was filtered through a filter to remove the molecular sieve.

[Measurement of water content of ink]
For the ink after dehydration (color material dispersion liquid of Examples 1 to 5) obtained by the above procedure, the moisture content was measured by the Karl Fischer method under the following conditions.
-Apparatus: Dia Instruments KF moisture meter CA-100
・ Injection volume: 40-50 μL
・ Anode / catholyte: Aquamicron AS / CXU
・ End Sens. : 0.1 μg / sec

  The obtained water content is shown in Table 3 below. The water content of the color material dispersions of Examples 1 to 5 was 0.07% to 0.498%.

[Preparation of resist]
A resist (curable resin composition) having the composition shown in Table 2 below was prepared using each of the colorant dispersions of Examples 1 to 5 described above.

  Moreover, about Examples 2-5, in addition to each component of the said composition, phosphoric acid acrylate (PM-2: made by Nippon Kayaku Co., Ltd.) is 1 weight% in order with respect to the total solid, 0.7 It added so that it might become a ratio of weight%, 0.7 weight%, and 1 weight%.

[Measurement of moisture content of resist]
About the resist (curable resin composition of Examples 1-5) obtained by the above procedure, the moisture content was measured on the above-mentioned conditions by the Karl Fischer method.

  The obtained water content is shown in Table 3 below. The moisture content of the curable resin compositions of Examples 1 to 5 was 0.05% to 0.32%.

[Comparative Examples 1-4]
[Preparation of ink and measurement of water content]
An ink was prepared by the same procedure as in each example. With respect to the obtained inks (coloring material dispersion liquids of Comparative Examples 1 to 4), the water content was measured by the same method as in each example without dehydration. The obtained water content is shown in Table 3 below. The moisture content of the curable resin compositions of Comparative Examples 1 to 4 was 0.05% to 0.32%.

[Preparation of resist and measurement of water content]
Inks were prepared using the colorant dispersions of Comparative Examples 1 to 4 described above in the same procedure as in each Example. Moreover, about Comparative Examples 1-3, in addition to each component of the said composition, phosphoric acid acrylate (PM-2: Nippon Kayaku Co., Ltd. product) is 1 weight% in order with respect to the total solid, 0.7 It added so that it might become a ratio of weight% and 1weight%.

  About the obtained resist (curable resin composition of Comparative Examples 1-4), the moisture content was measured with the method similar to each Example. The obtained water content is shown in Table 3 below. The moisture content of the curable resin compositions of Comparative Examples 1 to 4 was 0.40% to 0.52%.

[Evaluation of resist]
About the curable resin composition of Examples 1-5 and Comparative Examples 1-4, the viscosity change and adhesiveness were evaluated by the following procedures, respectively.

(Measurement of viscosity change)
The curable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 were stored at 5 ° C. under normal pressure, and the viscosities at 1 month, 2 months, and 3 months were measured under the following conditions.
・ Equipment: Toki Sangyo Co., Ltd. RE80L viscometer ・ Measurement temperature: 23 ° C.
・ Sample volume: 1.0ml
-The value at a rotation speed of 20 rpm was determined as the viscosity.

  The obtained results are shown in Table 3 below. It turns out that the curable resin composition of Examples 1-5 has few ratios of a viscosity change compared with the curable resin composition of Comparative Examples 1-4.

[Adhesion evaluation]
The adhesiveness of the curable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 was evaluated by the following procedure.

(1) The glass substrate for liquid crystal (AN-100 manufactured by Asahi Glass Co., Ltd.) was washed, the resist was applied with a spin coater, and dried at 80 ° C. for 3 minutes by a hot plate.
(2) The sample was exposed at 60 mj / cm ² through a mask pattern with a high-pressure mercury lamp, and developed using a 0.04 wt% aqueous potassium hydroxide solution at a developer temperature of 23 ° C.
(3) After development, the substrate was rinsed with sufficient water and then dried with clean air.
(4) Then, it post-baked for 30 minutes in 230 degreeC oven. The film thickness after drying was about 1.5 μm.
(5) The pattern on the substrate was observed with a microscope, and the length of the minimum fine line maintaining the linearity was measured. This value was used as an index of adhesion.

  The obtained results are shown in Table 3 below. It turns out that the curable resin composition of Examples 2-5 also has few ratios of a viscosity change, maintaining the adhesive improvement effect of phosphoric acid acrylate.

  The present invention is suitably used in the field of color filters and liquid crystal display devices using the same.

Claims (7)

  A color material dispersion for a color filter comprising a color material, a dispersant, and a solvent, wherein the ratio of the water content to the total amount of the component is 0.6% by weight or less. Dispersion.   A color filter curable resin composition containing a color material, a dispersant, a binder resin, and a solvent, wherein the color filter dispersion material is formed using the color filter color material dispersion according to claim 1, Curable resin composition for color filters.   A color filter curable resin composition containing a colorant, a dispersant, a binder resin, and a solvent, wherein the ratio of water content to the total amount of components is 0.35% by weight or less. Curable resin composition for filters.   The curable resin composition for a color filter according to claim 2 or 3, further comprising phosphoric acid (meth) acrylate.   A method for producing a color filter curable resin composition comprising a color material, a dispersant, a binder resin, and a solvent, wherein the color filter color material dispersion according to claim 1 is used. A method for producing a curable resin composition for a color filter.   A color filter formed using the curable resin composition for a color filter according to any one of claims 2 to 4.   A liquid crystal display device comprising the color filter according to claim 6.