CN1918250A - Colorant dispersion, colored resin composition, color filter, and liquid crystal display device - Google Patents

Abstract

The invention provides a coloring material dispersion liquid, which can not remain undissolved matter of a coloring resin composition on a non-image part of a substrate when the coloring material dispersion liquid is coated on the substrate, has excellent adhesion with the substrate, does not reduce image forming capability such as curing property, and can manufacture a color filter with high concentration and low film thickness. The colorant dispersion liquid of the present invention comprises a colorant, (B) a dispersant, and (C) a solvent, wherein the dispersant (B) contains at least: a graft copolymer and/or an acrylic block copolymer containing a nitrogen atom, and (b) a polymer obtained by polymerizing a monomer component containing a specific compound as an essential component.

Description

Colorant dispersion, colored resin composition, color filter, and liquid crystal display device

technical field

The present invention relates to a colorant dispersion liquid, a colored resin composition (hereinafter, sometimes referred to as "resist"), a color filter, and a liquid crystal display device. Specifically, it relates to a colorant dispersion that can uniformly form high-density and low-thickness pixels, has little residue on non-image parts after development, and has high pattern adhesion during development. , In addition, when the die coating method is used for coating, it is possible to suppress the occurrence of dry agglomerates at the front end of the die lip, and the colored resin composition using the color material dispersion, the color filter of the pixel formed using the colored resin composition sheet, and a liquid crystal display device having the color filter.

Background technique

Conventionally, pigment dispersion methods, dyeing methods, electrodeposition methods, and printing methods are known as methods for manufacturing color filters used in liquid crystal display devices and the like. Among them, the pigment dispersion method having excellent characteristics in a balanced manner is most widely used from the viewpoints of spectral characteristics, durability, pattern shape, and precision.

In recent years, the trend of technological innovation has developed rapidly, and for color filters, higher transmission and higher density are required. In order to form a high-concentration color filter, it is necessary to increase the concentration of the colorant in the colored resin composition used. On the other hand, components contributing to image forming properties such as photosensitivity, solubility, and curability are relatively reduced, causing a problem that inherent image forming performance is lost. That is, when attempting to reduce the pixel thickness (lower film thickness) by increasing the density, for example, the curability decreases, the surface smoothness of the pixel decreases, and poor alignment of liquid crystals occurs. Moreover, when solubility falls, the undissolved matter of a colored resin composition will remain easily in the non-image part after image development. In addition, when the undissolved matter of the colored resin composition remains on the non-pixel portion of the substrate, the obtained color filter will cause a decrease in transmittance or contrast, and if it remains on the edge of the pattern (pattern engineering) , will cause peeling of the ITO film or deterioration of the sealing performance in the step of forming a liquid crystal unit, etc., so as to affect the subsequent steps.

In order to solve such a problem, attempts have been made to maintain image formability while increasing the colorant concentration by using a dispersant having both a dispersing function and a binder function (see Patent Documents 1 and 2). .

On the other hand, various new technologies are being developed regarding the manufacturing method of the color filter. In the step of forming a pixel, for example, in the step of applying a resist, the mainstream method so far is to drop a resist on the center of the substrate and perform uniformization by spin coating. However, as the size of the substrate increases, the amount of resist used increases, and the constraints on the device of the spin coater (capacity of the motor, etc.) increase. Therefore, recently, the die coating method is being developed. Coating technology, and, has been partially practical.

Patent Document 1: Japanese Patent Laid-Open No. 2001-108817

Patent Document 2: JP-A-2004-46047

Contents of the invention

The problem to be solved by the invention

However, a dispersant having both a dispersing function and a binder function has problems in the following points. Right now,

(i) In a dispersant having both a dispersing function and a binder function, especially in a resist having a high colorant concentration, the dispersing function, the binding agent, etc. The effects of each agent function are not sufficient.

(ii) Therefore, as a result, the conventional dispersant or binder resin is used at the same time, but the proportion of the above-mentioned components in the colorant dispersion liquid or the colored resin composition increases conversely.

This has also become the main reason why the colorant concentration is difficult to increase.

(iii) In addition, when a dispersant and a binder resin having both a dispersing function and a binder function are used, properties such as developability, solubility, and curability may decrease.

In addition, in the technique of applying a resist by the die coating method, in the case of single-leaf coating such as a color filter, the coating method is intermittent coating, and the tip of the lip is repeatedly wetted and dried. When a color resist or a black resist in which a high concentration of pigment is dispersed is dried at the front end of the die lip, the concentration of the pigment increases rapidly, and thus agglomeration of the pigment may occur. These agglomerates adhere to the tip of the die lip, and when the resist is pressed out again, they are peeled off from the tip of the lip and transferred to the substrate. They cannot be easily removed in subsequent steps and remain on the substrate until the end. Such agglomerated blocks become pixel defects of the color filter and cause poor quality. The frequent occurrence of this undesirable phenomenon will reduce the yield of the product, so it becomes one of the phenomena that must be avoided. Therefore, when coating by the die coating method, the generation of impurities due to dry aggregation at the front end of the die lip may not be sufficiently suppressed.

The present invention was made in view of the above-mentioned problems, and its object is as follows.

(1) To provide a colorant dispersion that, when the colorant dispersion is coated on a substrate, little undissolved matter of the colored resin composition remains on the non-image portion of the substrate and is excellent in adhesion to the substrate , and does not reduce the image forming ability such as curability, it is possible to manufacture a color filter with high concentration and low film thickness. In addition, when coating by die coating method, it can suppress the dry aggregation at the front end of the die lip, Therefore, color filters can be manufactured with high yield.

(2) To provide a colored resin composition that, when the composition is coated on a substrate, little undissolved matter of the colored resin composition remains on a non-image portion of the substrate and has excellent adhesion to the substrate, and High density and low film thickness color filters can be produced without deteriorating the image forming ability such as curability. In addition, when coating by the die coating method, dry aggregation at the tip of the die lip can be suppressed, enabling Manufacture color filters with high yield.

(3) To provide a high-quality color filter with high concentration and low film thickness, which does not leave undissolved matter of the colored resin composition on the non-pixel portion of the substrate or dry during die coating Impurities produced by condensation.

(4) To provide a high-quality liquid crystal display device using the color filter substrate described in (3) above.

Solution to the problem

As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, it was found that by combining a dispersant having a specific structure, a stable color material dispersion liquid with a small amount of dispersant added to the color material can be obtained, and by using the dispersion liquid , it is possible to obtain a colored resin composition that does not reduce curability and other image forming capabilities, does not leave undissolved matter on the non-image portion of the substrate, and has excellent adhesion to the substrate and can be uniformly formed. Forms high-density color pixels and suppresses dry aggregates at the front of the die when die coating is used.

The present invention includes a plurality of related inventions, and the gist of each invention is as follows.

(1) A colorant dispersion liquid, which contains (A) colorant, (B) dispersant and (C) solvent, wherein, (B) dispersant contains at least: (a) graft containing nitrogen atom A copolymer and/or an acrylic block copolymer, and (b) a polymer obtained by polymerizing a monomer component in which a compound represented by the following general formula (1) and/or (2) is an essential component.

[chemical formula 1]

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

[chemical formula 2]

(In formula (2), R ^1b represents a hydrogen atom or an alkyl group that may have a substituent, L ³ represents a divalent linking group or a direct bond, X represents a group represented by the following formula (3) or may substituted adamantyl).

[chemical formula 3]

(In formula (3), R ^2b , R ^3b , and R ^4b represent a hydrogen atom, hydroxyl, halogen atom, amino or organic group, L ¹ and L ² represent a divalent linking group, L ¹ , L ² and Two or more of ^L3 may be combined with each other to form a ring).

(2) A colored resin composition comprising (A) a colorant, (B) a dispersant, and (C) a solvent, wherein the (B) dispersant contains at least: (a) a nitrogen atom-containing graft A copolymer and/or an acrylic block copolymer, and (b) a polymer obtained by polymerizing a monomer component in which the compound represented by the above general formula (1) and/or (2) is an essential component.

(3) A color filter in which the colored resin composition described in (2) above is used.

(4) A liquid crystal display device in which the color filter described in (3) above is used.

The effect of the invention

The present invention can achieve the effects listed below.

(1) When the colorant dispersion liquid of the present invention is applied on the substrate, undissolved matter of the colored resin composition will not remain on the non-image portion of the substrate, and the adhesion to the substrate is also excellent, and it will not By reducing the image forming ability such as curability, it is possible to manufacture a color filter with high density and low film thickness. In addition, when coating by die coating method, it is possible to suppress dry aggregation at the tip of the die lip, so that it can be used Manufacturing color filters with high yield.

(2) When the colored resin composition of the present invention is applied on the substrate, undissolved matter of the colored resin composition will not remain on the non-image portion of the substrate, and the adhesiveness with the substrate is also excellent, and it will not By reducing the image forming ability such as curability, it is possible to manufacture a color filter with high density and low film thickness. In addition, when coating by die coating method, it is possible to suppress dry aggregation at the tip of the die lip, so that it can be used Manufacturing color filters with high yield.

(3) The color filter of the present invention does not leave undissolved matter of the colored resin composition on the non-pixel portion of the substrate or impurities generated by drying aggregation during die coating, and due to its high concentration and low film thickness, Therefore it is of high quality.

(4) The liquid crystal display device of the present invention is of high quality because it uses the high-quality color filter described in (3) above.

Detailed ways

Hereinafter, components and the like of the present invention will be described in detail, but these are examples of embodiments of the present invention and are not limited thereto.

[1] Components of colorant dispersion

Hereinafter, each constituent component of the colorant dispersion liquid of the present invention will be described. The colorant dispersion liquid of the present invention contains a colorant, a dispersant, and a solvent as essential components, and, if necessary, other additives other than the above-mentioned components may be blended. Hereinafter, each constituent component will be described.

In addition, "(meth)acrylic acid", "(meth)acrylate", etc. refer to "acrylic acid and/or methacrylic acid" or "acrylate and/or methacrylate", etc., for example, "(meth) ) Acrylic acid" means "acrylic acid and/or methacrylic acid". In addition, in chapter [1], the "total solid content" refers to the total components of the colorant dispersion liquid of the present invention other than the solvent component described later.

[1-1] (A) colorant

(A) The coloring material means what color|colors the coloring material dispersion liquid of this invention. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance, and the like. As the pigment, pigments of various colors such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments, and black pigments can be used. In addition, as its structure, azos, phthalocyanines, quinacridones, benzimidazolones, isoindolines, dioxazines, indanthrene, perylenes can be used Such as organic pigments, and various inorganic pigments. Hereinafter, specific examples of pigments that can be used are indicated by pigment numbers. Here, "C.I." mentioned below refers to a dye index (C.I.).

Examples of red pigments include C.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 ,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179,181,184,185,187,188,190,193,194,200 ,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 . Among these, C.I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254 is preferable, and C.I. Pigment Red 177, 209, 224, 254 is more preferable.

Examples of blue pigments include C.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. Among these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferable, and C.I. Pigment Blue 15:6 is more preferable.

Examples of green pigments include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 . Among these, C.I. Pigment Green 7, 36 is preferable.

Examples of yellow pigments include C.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 ,170,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191:1,192,193,194,195,196,197,198 , 199, 200, 202, 203, 204, 205, 206, 207, 208. Among these, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185 are preferable, and C.I. Pigment Yellow 83, 138, 139, 150, and 180 are more preferable.

Examples of orange pigments include C.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. Among these, C.I. Pigment Orange 38, 71 is preferable.

Examples of purple pigments include C.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. Among these, C.I. Pigment Violet 19 and 23 are preferable, and C.I. Pigment Violet 23 is more preferable.

In addition, when the color material dispersion liquid of the present invention is a color material dispersion liquid for a black matrix of a color filter, a black color material can be used as the color material. As the black coloring material, a black coloring material may be used alone, or a coloring material such as red, green, or blue may be mixed. In addition, these colorants can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic or organic pigments, they are preferably dispersed to have an average particle diameter of 1 μm or less, more preferably 0.5 μm or less.

As the color material that can be mixed and used for the preparation of black color material, for example, Victoria blue (42595), basic Sophora japonica O (41000), cationic brilliant yellow (basic 13), rhodamine 6GCP ( 45160), Rhodamine B (45170), Saffron OK 70:100 (50240), Poppy Red (42080), No.120/Reonore Yellow (21090), Reonore Yellow GRO (21090), Shimular Fast Yellow 8GF(21105), Benzidine Yellow 4T-564D(21095), Shimular Fast Red 4015(12355), Reonore Red 7B4401(15850), Fastgen Blue TGR-L(74160), Reonore Blue SM(26150) , Leonore Blue ES (pigment blue 15:6), Linogen Red GD (pigment red 168) and Leonore Green 2YS (pigment green 36), etc. (Additionally, the numbers in parentheses above indicate dye index (C.I.)].

In addition, for other pigments that can be mixed and used, if they are represented by C.I. numbers, for example, C.I. , 154, 166; C.I. Orange Pigment 36, 43, 51, 55, 59, 61; C.I. Red Pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223 , 224, 226, 228, 240; C.I. Purple Pigment 19, 23, 29, 30, 37, 40, 50; C.I. Blue Pigment 15, 15:1, 15:4, 22, 60, 64; C.I. Green Pigment 7 ; C.I. brown pigments 23, 25, 26, etc.

In addition, examples of black coloring materials that can be used alone include carbon black, acetylene black, lamp black, bone carbon, graphite, iron black, aniline black, trianin black, titanium black, and the like.

Among these, carbon black and titanium black are preferable from the viewpoint of light-shielding ratio and image characteristics. As an example of carbon black, the following carbon black can be mentioned:

Manufactured by 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;

Manufactured by デグサ company: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex G, Printex U, Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color BlackFW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color BlackFW200, Color Black S160, Color Black S170;

Manufactured by キヤボツト: Monarch 120, Monarch 280, Monarch 460, Monarch800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL 99, REGAL 99R, REGAL 415, REGAL 415, REGAL REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, BLACK PEARLS 480, PEARLS 130, VULCAN XC72R, FLFTEX-8;

Manufactured by コロンビヤンカ一ボン Corporation: RAVEN 11, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN 22, RAVEN 30, RAVEN 35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500, RAVEN 780, RAVEN 850, RAVEN890H, RAVEN 1000, RAVEN 1020, RAVEN 1040, RAVEN 1060U, RAVEN1080U, RAVEN 1170, RAVEN 1190U, RAVEN 1250, RAVEN 1500, RAVEN2000, RAVEN 2500U, RAVEN 3500, RAVEN 5000, RAVEN 00V0, RAVEN RA525;

In addition, examples of titanium black include the following.

As the manufacturing method of titanium black, there are the following methods: the method of heating and reducing the mixture of titanium dioxide and metallic titanium under a reducing atmosphere (Japanese Patent Application No. 49-5432); The method of reducing in a reducing atmosphere containing hydrogen (JP-A-57-205322); the method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (JP-A-60-65069, JP-A-61- No. 201610), a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide, and performing high-temperature reduction in the presence of ammonia (JP-A-61-201610), but not limited thereto.

Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials.

As examples of other black pigments, nigrosine, iron oxide-based black pigments, and organic pigments in which red, green, and blue are mixed can be used as black pigments.

In addition, as the pigment, barium sulfate, lead sulfate, titanium oxide, lead yellow, red iron oxide, chromium oxide, and the like can be used.

A plurality of the above-mentioned various pigments may be used at the same time. For example, to adjust chromaticity, a green pigment and a yellow pigment may be used as pigments at the same time, or a blue pigment and a purple pigment may be used as pigments at the same time.

In addition, the average particle diameter of these pigments is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less. In addition, dyes that can be used as coloring materials include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, Methyl dyes, etc.

Examples of azo-based fuels include C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, and C.I. Direct Yellow 12. C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Mordant Red 7, C.I. Mordant Yellow 5, C.I. Mordant Black 7

Examples of anthraquinone dyes include C.I. Vat Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, and C.I. Disperse Blue 60 etc.

In addition, examples of phthalocyanine dyes include C.I. Vat Blue 5 and the like, examples of quinone imine dyes include C.I. Basic Blue 3 and C.I. Basic Blue 9, and quinoline dyes. , for example, C.I. Solvent Yellow 33, C.I. Acid Yellow 3, C.I. Disperse Yellow 64, etc., as nitro dyes, for example, C.I. Acid Yellow 1, C.I. Acid Orange 3, C.I. Disperse Yellow 42, etc. .

The ratio of the coloring material in the coloring material dispersion liquid of the present invention to the total solid content is usually 10 to 90% by weight, preferably 30 to 90% by weight, more preferably 50 to 90% by weight. When the content ratio of the coloring material is too small, the tinting strength becomes low, and the film thickness becomes too thick relative to the color density, which adversely affects gap control when liquid crystal cells are formed. Conversely, when the content ratio of the coloring material is too high, the dispersion stability deteriorates, and there is a risk of causing problems such as re-agglomeration and thickening.

[1-2] (B) Dispersant

In the colorant dispersion liquid of the present invention, as (B) dispersant, it must contain: (a) graft copolymer and/or acrylic block copolymer containing nitrogen atoms, and (b) specific compound as an essential component Polymers formed by the polymerization of monomer components. Next, each dispersant will be described in detail.

[1-2-1] Graft copolymers containing nitrogen atoms

The nitrogen atom-containing graft copolymer as the component (a) preferably has a repeating unit containing a nitrogen atom in the main chain. Among them, it is preferable to have a repeating unit represented by formula (I) and/or a repeating unit represented by formula (II).

[chemical formula 4]

(In the formula, 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-mentioned formula (I), R ₁ represents a linear or branched alkylene group with 1 to 5 carbon atoms, such as methylene, ethylene, and propylene, preferably with 2 to 3 carbon atoms, more preferably Ethylene is preferred. A represents a hydrogen atom or any one of the following formulas (III) to (V), preferably formula (III).

[chemical formula 5]

In the above (II), R ₁ and A have the same meanings as R ₁ and A in the formula (I).

[chemical formula 6]

In the above formula (III), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms, among which, an alkylene group having 4 to 7 carbon atoms such as a butylene group, a pentylene group, and a hexylene group is preferred. alkyl. p represents an integer of 1-20, preferably an integer of 5-10.

[chemical formula 7]

In the above-mentioned formula (IV), _Y represents a divalent linking group, among which, an alkylene group having 1 to 4 carbon atoms such as ethylene group and propylene group, and a carbon group such as ethyleneoxy group or propyleneoxy group are preferred. Alkyleneoxy group having 1 to 4 atoms. _W2 represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene, butylene, among which ethylene, propylene and the like are preferably 2 to 3 carbon atoms. of alkylene. Y ₂ represents a hydrogen atom or -CO-R ₂ (R ₂ represents an alkyl group with 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, among which ethyl, propyl, butyl are preferred , pentyl and other alkyl groups with 2 to 5 carbon atoms). q represents an integer of 1-20, preferably an integer of 5-10.

[chemical formula 8]

In the above formula (V), W _represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 hydroxyl groups and having 1 to 50 carbon atoms, among which stearyl and other carbon atoms are preferred. C10-20 hydroxyalkyl groups having 1-2 hydroxyl groups such as 10-20 alkyl groups and monohydroxystearyl groups.

The content of the repeating unit represented by the formula (I) or (II) in the graft copolymer of the present invention is preferably higher, usually 50 mol % or more, preferably 70 mol % or more. Both the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II) may be present at the same time. The content ratio is not particularly limited, but the repeating unit represented by the formula (I) is preferably contained in a large amount. The total number of repeating units represented by formula (I) or formula (II) is usually 1-100, preferably 10-70, more preferably 20-50. In addition, repeating units other than formula (I) and formula (II) may be contained, and examples of other repeating units include an alkylene group, an alkyleneoxy group, and the like. The graft copolymer of the present invention preferably has -NH ₂ and -R ₁ -NH ₂ (R ₁ has the same meaning as above R ₁ ) at its terminal.

In addition, as long as it is the graft copolymer of the present invention, the main chain may be linear or branched.

The amine value of the graft copolymer of the present invention is usually 5 to 100 mgKOH/g, preferably 10 to 70 mgKOH/g, more preferably 15 to 40 mgKOH/g or less. When the amine value is too low, the dispersion stability may decrease and the viscosity may become unstable. Conversely, when it is too high, the residue may increase, and the electrical characteristics after forming a liquid crystal panel may decrease.

The weight-average molecular weight measured by GPC as the above-mentioned dispersant is preferably 3,000 to 100,000, particularly preferably 5,000 to 50,000. When the weight average molecular weight is less than 3,000, aggregation of the colorant cannot be prevented, and high viscosity or gelation may occur in some cases. When it exceeds 100,000, the viscosity itself becomes high, and the solubility to organic solvents is insufficient, so it is not preferable. .

A known method can be used for the synthesis method of the above-mentioned dispersant, for example, the method described in JP-A-63-30057 can be used.

In the present invention, commercially available graft copolymers having the same structure as those described above can be used.

[1-2-2] Acrylic block copolymer

The acrylic block copolymer as the component (a) is preferably an A-B block copolymer and/or a B-A-B block copolymer containing an A block and a B block, wherein the A block has a quaternary ammonium salt on the side chain groups and/or amino groups, while the B block does not have quaternary ammonium salt groups and/or amino groups.

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

The quaternary ammonium salt group preferably has -N ⁺ R _1a R _2a R _3a · Y ^- (here, R _1a , R _2a and R _3a each independently represent hydrogen, or a cyclic or chain hydrocarbon group that may be substituted. Or, Two or more of R _1a , R _2a and R _3a may combine with each other to form a ring structure. ^{Y -} represents a quaternary ammonium salt group represented by an anion). The quaternary ammonium salt group can be directly combined on the main chain, or can be combined on the main chain through a divalent linking group.

In -N ⁺ R _1a R _2a R _3a , as the cyclic structure formed by combining two or more of R _1a , R _2a and R _3a with each other, for example, 5- to 7-membered rings containing Nitrocyclic single ring or a condensed ring formed by the fusion of two of them. The nitrogen-containing heterocyclic ring is preferably non-aromatic, more preferably a saturated ring. Specifically, the following structures can be mentioned.

[chemical formula 9]

(In the above formula, R represents any group among R _1a to R _3a ).

These cyclic structures may also have substituents.

R _1a , R _2a and R _3a in -N ⁺ R _1a R _2a R _3a are more preferably an alkyl group having 1 to 3 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a phenyl group which may have a substituent. Benzyl with substituents.

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

[chemical formula 10]

(In the above general formula (VI), R ^1d , R ^2d and R ^3d each independently represent a hydrogen atom or a cyclic or chain hydrocarbon group that may be substituted. Or it may be R ^1d , R ^2d and R ^3d Two or more can be bonded to each other to form a ring structure. R ^4d represents a hydrogen atom or a methyl group. X represents a divalent linking group, Y ^- represents an anion).

In the above general 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 ^5d -, -COO- R ^6d -(Here, R ^5d and R ^6d represent a direct bond, an alkylene group with a carbon number of 1-10, or an ether group with a carbon number of 1-10 (-R ^7d -OR ^8d -: R ^7d and R ^8d each independently represent an alkylene group)), preferably -COO-R ^6d -.

In addition, examples of the counter anion Y ^- include Cl ^- , Br ^- , I ^- , ClO ₄ ^- , BF ₄ ^- , CH ₃ COO ^- , PF ₆ ^- and the like.

The amino group can be mentioned, preferably -NR ^1e R ^2e (here, R ^1e and R ^2e each independently represent a cyclic or chain alkyl group that may have a substituent, an allyl group that may have a substituent (aryl), or Aralkyl group which may have a substituent), more preferably an amino group represented by the following formula.

[chemical formula 11]

(Here, R ^1e and R ^2e have the same meaning as R ^1e and R ^2e described above, R ^3e represents an alkylene group having 1 or more carbon atoms, and R ^4e represents a hydrogen atom or a methyl group).

Among them, R ^1e and R ^2e are preferably methyl groups, R ^3e is preferably methylene or ethylene, and R ^4e is preferably a hydrogen atom. Examples of such compounds include substituents represented by the following formulae.

[chemical formula 12]

As described above, the partial structure containing a specific quaternary ammonium salt group and/or amino group may contain two or more types in one A block. In this case, the partial structure containing two or more kinds of quaternary ammonium salt groups and/or amino groups may be contained in any form of random copolymerization or block copolymerization in the A block. In addition, a partial structure that does not contain the quaternary ammonium salt group and/or amino group may also be included in the A block. As an example of this partial structure, the following (meth)acrylate-based monomers can be mentioned. part of the structure, etc. The content of such partial structures not containing quaternary ammonium salt groups and/or amino groups in the A block is preferably 0-50% by weight, more preferably 0-20% by weight, but most preferably no Such partial structures do not contain quaternary ammonium groups and/or amino groups.

On the other hand, as the B block of the block copolymer constituting the dispersant, for example, styrene-based monomers such as styrene and α-methylstyrene; (meth)methyl acrylate, (meth)acrylate Base) ethyl acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Glycidyl (meth)acrylate, Benzyl (meth)acrylate, Hydroxyethyl (meth)acrylate, Glycidyl ethacrylate, N,N-Dimethylaminoethyl (meth)acrylate (meth)acrylic ester monomers such as (meth)acryloyl chloride and other (meth)acrylate monomers; (meth)acrylamide, N-methylolacrylamide, N,N-dimethyl Acrylamide, N, N-dimethylaminoethylacrylamide and other (meth)acrylamide monomers; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonate glycidyl ether; A polymer structure obtained by copolymerizing comonomers such as acryloylmorpholine.

The B block is particularly preferably a partial structure derived from a (meth)acrylate-based monomer represented by the following general formula (VII).

[chemical formula 13]

(In the above general formula (VII), R ^9d represents a hydrogen atom or a methyl group. R ^10d represents a cyclic or chain alkyl group that may have a substituent, an allyl group that may have a substituent, or an arane group that may have a substituent base).

One B block may contain two or more partial structures derived from the above-mentioned (meth)acrylate monomers. Of course, the B block may also contain partial structures other than these. When two or more partial structures derived from monomers exist in the B block not containing a quaternary ammonium salt group, each partial structure may be included in the B block in any form of random copolymerization or block copolymerization. When the B block contains a partial structure other than the partial structure derived from the above-mentioned (meth)acrylate monomer, in the B block, the content of the partial structure derived from the (meth)acrylate monomer It is preferably 0 to 99% by weight, more preferably 0 to 85% by weight.

The acrylic dispersant used in the present invention is an A-B block or B-A-B block copolymerized polymer compound including such an A block and a B block. Such a block copolymer can be produced by, for example, the living polymerization method shown below.

Living polymerization methods include: anionic living polymerization method, cationic living polymerization method, and free radical living polymerization method. In the anionic living polymerization method, the polymerization active center (active species) is an anion, for example, as shown in the following flow chart.

[chemical formula 14]

               (Anionic living polymerization method)

exist

                 单体②：

     时Monomer ①:

Monomer ②:

hour

In the radical living polymerization method, the polymerization active center is a radical, for example, as shown in the following flow chart.

[chemical formula 15]

(Free radical living polymerization method: nitroxyl method)

exist

单体②： 时Monomer ①:

Monomer ②: hour

[chemical formula 16]

(Free radical living polymerization method: ATRP method)

exist

Monomer ①: Monomer ②: hour

When synthesizing such acrylic block copolymer, can adopt JP-A 60-89452 or JP-P 9-62002; P.Lutz, P.Masson et al, Polym.Bull.12,79(1984) ; B.C.Anderson, G.D.Andrews et al, Macromolecules, 14, 1601(1981); K.Hatada, K.Ute et al, Polym.J.17, 977(1985), 18, 1037(1986); Koichi, Polymer Processing, 36, 366 (1987); Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers, 46, 189 (1989), M.Kuroki, T.Aida, J.Am.Chem.Sic, 109, 4737(1987); Takuichi Aida, Shohei Inoue, Organic Synthetic Chemistry, 43, 300(1985); D.Y.Sogoh, W.R.Hertler et al, Macromolecules, 20, 1473(1987); K.Matyaszewski et al, Chem.Rev . Known methods described in 2001, 101, 2921-2990 and the like.

In addition, the amount of quaternary ammonium salt groups in 1 g of the A-B block copolymer and B-A-B block copolymer according to the present invention is usually preferably 0.1 to 10 mmol, and outside this range, good heat resistance and dispersibility cannot be achieved.

In addition, such a block copolymer usually contains amino groups generated during the production process, but its amine value is about 1 to 100 mg-KOH/g. In addition, the amine value is the neutralization titration of the basic amino group with an acid, and it corresponds to the value represented by the mg number of KOH.

In addition, although the acid value of the block copolymer depends on the presence or absence and the type of the acidic group which is the basis of the acid value, it is generally preferably lower, usually 100 mg-KOH/g or less, and its molecular weight is measured by GPC The polystyrene-equivalent weight average molecular weight (Mw) of is usually in the range of 1,000 to 100,000. When the molecular weight of the block copolymer is too small, the dispersion stability decreases, and when it is too large, developability and resolution tend to decrease.

In the present invention, commercially available acrylic block copolymers having the same structure as those described above can be used.

[1-2-2] (b) A polymer obtained by polymerizing a monomer component containing a specific compound as an essential component

The polymer obtained by polymerizing a monomer component that contains a specific compound as an essential component as the component (b) refers to the polymerization of a monomer component that contains a compound represented by the following general formula (1) and/or (2) as an essential component made polymer.

[chemical formula 17]

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

[chemical formula 18]

(In formula (2), R ^1b represents a hydrogen atom or an alkyl group that may have a substituent, L ³ represents a divalent linking group or a direct bond, X represents a group represented by the following formula (3) or may have adamantyl substituent).

[chemical formula 19]

(In formula (3), R ^2b , R ^3b and R ^4b represent a hydrogen atom, a hydroxyl group, a halogen atom, an amino group or an organic group, L ¹ and L ² represent a divalent linking group, L ¹ , L ² and L Two or more of ³ may be bonded to each other to form a ring).

Next, the above-mentioned polymer (b) will be described.

[1-2-2-1] About the compound of the above general formula (1)

In the above-mentioned general formula (1) representing the above-mentioned ether dimer, the hydrocarbon group having 1 to 25 carbon atoms that may have substituents represented by R ^1a and R ^2a is not particularly limited, and examples thereof include , Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-pentyl, stearyl, lauryl, 2-ethylhexyl, etc. linear or branched Alkyl; aryl such as phenyl; cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl (tricyclodecanyl), isobornyl, adamantyl, 2-methyl-2-adamantyl Alicyclic groups such as; 1-methoxyethyl, 1-ethoxyethyl and other alkyl groups substituted by alkoxy groups; benzyl groups and other alkyl groups substituted by aryl groups, etc. Among these, in terms of heat resistance, primary or secondary carbon substituents such as methyl group, ethyl group, cyclohexyl group, and benzyl group that are difficult to detach with acid or heat are particularly preferable. In addition, R ^1a and R ^2a may be the same substituent or different substituents.

Specific examples of the aforementioned ether dimers include, for example, dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl-2,2' -[Oxobis(methylene)]bis-2-acrylate, Di(n-propyl)-2,2'-[Oxobis(methylene)]bis-2-acrylate, Di(iso Propyl)-2,2'-[Oxobis(methylene)]bis-2-acrylate, Di(n-butyl)-2,2'-[Oxobis(methylene)]bis- 2-acrylate, bis(isobutyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(tert-butyl)-2,2'-[oxobis (Methylene)]bis-2-acrylate, bis(tert-amyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, bis(stearyl)-2 , 2'-[Oxobis(methylene)]bis-2-acrylate, bis(lauryl)-2,2'-[oxobis(methylene)]bis-2-acrylate, di (Ethylhexyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(1-methoxyethyl)-2,2'-[oxobis(methylene) Methyl)]bis-2-acrylate, bis(1-ethoxyethyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, dibenzyl-2, 2'-[Oxobis(methylene)]bis-2-acrylate, Diphenyl-2,2'-[Oxobis(methylene)]bis-2-acrylate, Dicyclohexyl- 2,2'-[Oxobis(methylene)]bis-2-acrylate, Bis(tert-butylcyclohexyl)-2,2'-[Oxobis(methylene)]bis-2-acrylate , Bis(dicyclopentadienyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(tricyclodecanyl)-2,2'-[oxobis (Methylene)]bis-2-acrylate, bis(norbornyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, diadamantyl-2,2 '-[Oxobis(methylene)]bis-2-acrylate, bis(2-methyl-2-adamantyl)-2,2'-[oxobis(methylene)]bis- 2-Acrylate etc. Among them, dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxybis(methylene)]bis -2-acrylate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-acrylate, dibenzyl-2,2'-[oxybis(methylene) ] Bis-2-acrylate. These ether dimers may be only one kind, or may be two or more kinds.

The above-mentioned polymer (b) contains at least the above-mentioned ether dimer as an essential component, and can be easily obtained by polymerizing a monomer component described later. At this time, the cyclization reaction of the ether dimer proceeds simultaneously with the polymerization to form a tetrahydrofuran ring structure.

The ratio of the above-mentioned ether dimer in the monomer components to obtain the above-mentioned polymer (b) is not particularly limited, and may be 2 to 60% by weight, preferably 5 to 55% by weight, more preferably 5% by weight, in the total monomer components. ~50% by weight. When the amount of the ether dimer is too large, it may be difficult to obtain a low-molecular-weight substance during polymerization, or it may become easy to gel. On the other hand, if it is too small, the coating properties such as transparency and heat resistance may deteriorate. insufficient.

[1-2-2-2] About the compound of the above general formula (2), (3)

In the above general formula (2), R ^1b preferably represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group.

In addition, in the above general formula (2), the organic groups of R ^2b , R ^3b , and R ^4b include, for example, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkoxy, alkylthio group, acyl group, carboxyl group, acyloxy group, etc., preferably an alkyl group with 1 to 18 carbon atoms, a cycloalkyl group with 3 to 18 carbon atoms, an alkenyl group with 2 to 18 carbon atoms, an alkenyl group with 3 to 18 carbon atoms Cycloalkenyl group, alkoxy group with 1 to 15 carbon atoms, alkylthio group with 1 to 15 carbon atoms, acyl group with 1 to 15 carbon atoms, carboxyl group with 1 carbon atom, carboxyl group with 1 to 5 carbon atoms The acyloxy group is more preferably an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms.

Preferred substituents for R ^2b , R ^3b , and R ^4b are hydrogen atoms, hydroxyl groups, and alkyl groups having 1 to 10 carbon atoms.

L ¹ and L ² are not particularly limited as long as they are divalent linking groups, and L ³ is not particularly limited as long as it is a divalent linking group or a direct bond, but one of L ¹ or L ² is preferably A linking group having 1 or more carbon atoms, and preferably L ¹ to L ³ are each independently a direct bond, an alkylene group having 1 to 15 carbon atoms, -O-, -S-, -C(=O )-, an alkenylene group having 1 to 15 carbon atoms, a phenylene group, or a combination thereof.

As a preferable combination of L ¹ to L ³ , L ³ is a direct bond, an alkylene group having 1 to 5 carbon atoms, and a ring formed by bonding with R ^3b or R ^4b , and L ¹ and L ² are carbon atoms 1 to 5 alkylene groups.

Moreover, the compound represented by the following general formula (4) is mentioned as a preferable thing of the said general formula (3).

[chemical formula 20]

(In formula (4), R ^2b , R ^3b , R ^4b , L ¹ , L ² have the same meaning ^as R ^2b , R ^3b , R ^4b , L 1 , and L ² in formula (3), and R ^5b , R ^6b represents a hydrogen atom, a hydroxyl group, a halogen atom, an acyl group, an organic group).

In the above general formula (4), the organic groups of R ^5b and R ^6b include, for example, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkoxy, alkylthio, acyl, Carboxyl, acyloxy, etc., preferably an alkyl group with 1 to 18 carbon atoms, a cycloalkyl group with 3 to 18 carbon atoms, an alkenyl group with 2 to 18 carbon atoms, and a cycloalkenyl group with 3 to 18 carbon atoms , alkoxy group with 1 to 15 carbon atoms, alkylthio group with 1 to 15 carbon atoms, acyl group with 1 to 15 carbon atoms, carboxyl group with 1 carbon atom, acyloxy group with 1 to 5 carbon atoms , more preferably an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms.

Preferred substituents for R ^5b and R ^6b are hydrogen atoms, hydroxyl groups, and alkyl groups having 1 to 10 carbon atoms.

In addition, the alkyl group of R ^1b , each organic group of R ^2b to R ^4b , the divalent linking group of L ¹ to L ³ , and the adamantyl group of X are each independently and may have a substituent, specifically, the following substituents.

Halogen atom; hydroxyl; nitro; cyano; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, tert-amyl, n-hexyl, n-heptyl , n-octyl, tert-octyl, and other straight-chain or branched alkyl groups with 1 to 18 carbon atoms; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc., with 3 to 18 carbon atoms Cycloalkyl; linear or branched alkenyl groups with 2 to 18 carbon atoms such as vinyl, propenyl, and hexenyl; cycloalkenyl groups with 3 to 18 carbon atoms such as cyclopentenyl and cyclohexenyl; Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, tert-pentoxy, n-hexyloxy, n-heptyloxy , n-octyloxy, tert-octyloxy and other straight-chain or branched alkoxy groups with 1 to 18 carbon atoms; methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, S-butylthio, tert-butylthio, pentylthio, tert-pentylthio, n-hexylthio, n-heptylthio, n-octylthio, tert-octylthio and other straight-chain or branched ones with 1 to 18 carbon atoms Alkylthio; aryl groups with 6 to 18 carbon atoms, such as phenyl, tolyl, xylyl, and phenyl; aralkyl groups with 7 to 18 carbon atoms, such as benzyl and phenethyl; ethyleneoxy, propylene Straight-chain or branched alkenyloxy groups with 2 to 18 carbon atoms, such as oxy and hexenyloxy groups; straight-chain or branched alkenyl groups with 2 to 18 carbon atoms, such as vinylthio, propenylthio, and hexenylthio groups Alkenylthio; Acyl group represented by -COR ¹⁷ ; Carboxyl group; Acyloxy group represented by -OCOR ¹⁸ ; Amino group represented by -NR ¹⁹ R ²⁰ ; Amido group represented by -NHCOR ²¹ ; Carbamic acid represented by -NHCOR ²² Ester group; Carbamoyl group represented by -CONR ²³ R ²⁴ ; Carboxylate group represented by -COOR ²⁵ ; Sulfamoyl group represented by -SO ₃ NR ²⁶ R ²⁷ ; Sulfonate group represented by -SO ₃ R ²⁸ ; -Thienyl, 2-pyridyl, furyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, morpholino, pyrrolidinyl, sulfolane and other saturated or unsaturated heterocycles group, trimethylsilyl group and other trialkylsilyl groups, etc.

In addition, R ¹⁷ to R ²⁸ each represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group.

In addition, the positional relationship of the above-mentioned substituents is not particularly limited, and when there are a plurality of substituents, they may be of the same kind or different.

Specific examples of the compound represented by the general formula (2) include the following:

[chemical formula 21]

[chemical formula 22]

The proportion of the above-mentioned general formula (2) in the monomer component when obtaining the above-mentioned polymer (b) according to the present invention is not particularly limited, and may be 0.5 to 60% by weight in the total monomer component, preferably 1 to 55% by weight. % by weight, more preferably 5 to 50% by weight. When it is too large, the dispersion stability of the dispersion may decrease when used as a dispersant. On the other hand, when it is too small, the adaptability to scum may decrease.

[1-2-2-3] About (b) Polymer

The aforementioned polymer (b) is preferably a polymer having an acid group. Thus, the obtained curable resin composition can be made into a curable resin composition that can utilize acid groups and epoxy groups to react to generate ester bond crosslinking reactions (hereinafter referred to simply as acid-epoxy curing), or A composition in which uncured parts can be developed with an alkaline developer. The above-mentioned acid group is not particularly limited, and examples thereof include carboxyl groups, phenolic hydroxyl groups, and carboxylic acid anhydride groups. These acid groups may be only one kind, or may be two or more kinds.

In order to introduce an acid group into the above-mentioned polymer, for example, a monomer having an acid group and/or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as a "monomer for introducing an acid group") may be used ) are polymerized as monomer components. In addition, when a monomer capable of introducing an acid group after polymerization is used as a monomer component to introduce an acid group, it is necessary to perform, for example, a treatment for imparting an acid group as described later after the polymerization.

As the monomer having the above-mentioned acid group, for example, a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid, a monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, Monomers having a carboxylic acid anhydride group, such as maleic anhydride and itaconic anhydride, among these, (meth)acrylic acid is particularly preferable. Examples of monomers capable of imparting acid groups after polymerization include, for example, monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, and glycidyl (meth)acrylate having an epoxy group. monomers, monomers having isocyanate groups such as 2-isocyanatoethyl (meth)acrylate, etc. These monomers for introducing acid groups may be only one type, or two or more types may be used.

When the monomer component for obtaining the above-mentioned polymer contains the above-mentioned acid group-introducing monomer, the content ratio is not particularly limited, but may be 5 to 70% by weight, preferably 10 to 60% by weight, in the total monomer components.

The aforementioned polymer may be a polymer having a radically polymerizable double bond.

In order to introduce a radically polymerizable double bond into the above-mentioned polymer, for example, a monomer capable of imparting a radically polymerizable double bond after polymerization (hereinafter sometimes referred to as "a monomer for introducing a radically polymerizable double bond) may be used. "body") is polymerized as a monomer component, and then the treatment for imparting a radically polymerizable double bond as described later is performed.

As the above-mentioned monomer capable of imparting a radically polymerizable double bond after polymerization, for example, monomers having carboxyl groups such as (meth)acrylic acid and itaconic acid; monomers having acid anhydrides such as maleic anhydride and itaconic anhydride; Monomer; glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, o-(or m-, or p-)vinylbenzyl glycidyl ether, etc. have epoxy Group monomers, etc. These monomers for introducing a radical polymerizable double bond may be only one kind or two or more kinds.

When the monomer component for obtaining the above-mentioned polymer contains the above-mentioned monomer for introducing a radically polymerizable double bond, its content ratio is not particularly limited, and it can be 5 to 70% by weight in the total monomer component, preferably 10 to 70%. 60% by weight.

When the compound of the above general formula (1) is used as an essential monomer component, the polymer (b) is preferably a polymer having an epoxy group.

In order to introduce an epoxy group into the above-mentioned polymer (b), for example, a monomer having an epoxy group (hereinafter also referred to as a "monomer for introducing an epoxy group") may be used as a monomer component. polymerization.

As the above-mentioned monomer having an epoxy group, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, ortho-(or meta-, or p-) Vinylbenzyl glycidyl ether and the like. These monomers for introducing epoxy groups may be only one or two or more.

When the monomer component for obtaining the above-mentioned polymer contains the above-mentioned monomer for introducing epoxy groups, the content ratio is not particularly limited, but it is 5 to 70% by weight, preferably 10 to 60% by weight, of the total monomer components. %.

The monomer component for obtaining the above-mentioned polymer may contain other copolymerizable monomers as necessary, in addition to the above-mentioned essential components and monomers.

As above-mentioned other copolymerizable monomers, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( n-butyl methacrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylate (meth)acrylates such as benzyl acrylate and 2-hydroxyethyl (meth)acrylate; aromatic vinyl compounds such as styrene, vinyltoluene, and α-methylstyrene; N-phenyl maleic acid N-substituted maleimides such as imide and N-cyclohexylmaleimide; butadiene or substituted butadiene compounds such as butadiene and isoprene; ethylene, propylene, vinyl chloride, Vinyl or substituted vinyl compounds such as acrylonitrile; vinyl esters such as vinyl acetate, etc. Among these, methyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and styrene are preferable because transparency is good and heat resistance is not easily impaired. In particular, when used as a dispersant, these other copolymerizable monomers may be used alone or in combination of two or more.

In addition, especially when the polymer (b) is used as a dispersant, benzyl (meth)acrylate is preferably used, and in this case, it can be 1 to 70% by weight, preferably 5 to 60% by weight, in the total monomer components. .

When the monomer component for obtaining the above-mentioned polymer contains the above-mentioned other copolymerizable monomers, the content ratio is not particularly limited, but is preferably 95% by weight or less, more preferably 85% by weight or less.

The polymerization method of the above-mentioned monomer components is not particularly limited, and various conventionally known polymerization methods can be used, but the solution polymerization method is particularly preferable. In addition, the polymerization temperature or polymerization concentration (polymerization concentration=[total weight of monomer components/(total weight of monomer components+solvent weight)]×100) depends on the type and ratio of monomer components to be used, and the target polymer The molecular weight varies, but the preferred polymerization temperature is 40-150°C, the polymerization concentration is 5-50%, more preferably the polymerization temperature is 60-130°C, and the polymerization concentration is 10-40%.

Moreover, when using a solvent for polymerization, the solvent used for a general radical polymerization reaction can be used as a solvent. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ; Ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and other esters; Methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl Alcohols such as ethers; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; chloroform; dimethyl sulfoxide, etc. These solvents may be used alone or in combination of two or more.

When polymerizing the above-mentioned monomer components, if necessary, a generally used polymerization initiator may be added. The polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, dicumyl hydroperoxide, di-tert-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t- Organic peroxides such as butyl peroxyisopropyl carbonate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate; 2,2'-Azo Diisobutyronitrile, 1,1'-azobis(cyclohexanenitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-Methyl propionate) and other azo compounds. These polymerization initiators may be used alone or in combination of two or more. In addition, the amount of the initiator used can be appropriately set according to the combination of monomers used or reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but it never gels and can obtain a weight average molecular weight of From the viewpoint of several thousands to tens of thousands of polymers, it may be 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on the total monomer components.

When polymerizing the above-mentioned monomer components, in order to adjust the molecular weight, if necessary, a generally used chain transfer agent may be added. Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, thioglycolic acid, and methyl thioglycolate, and α-methylstyrene dimer. However, it is preferable that the chain transfer effect is high. , n-dodecyl mercaptan and mercaptoacetic acid that can reduce residual monomers and are easily available. When using a chain transfer agent, its amount can be appropriately set according to the combination of monomers used, reaction conditions, molecular weight of the target polymer, etc., and is not particularly limited, but it never gels and can obtain a weight-average From the viewpoint of a polymer having a molecular weight of several thousand to several tens of thousands, it is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on the total monomer components.

In addition, when the compound of the above-mentioned general formula (1) is used as an essential monomer component, it is considered that in the above-mentioned polymerization reaction, the cyclization reaction of the ether dimer proceeds simultaneously, but at this time the ether dimer The cyclization rate does not necessarily have to be 100 mol%.

When obtaining the above-mentioned polymer (b), when an acid group is introduced by using the above-mentioned monomer capable of imparting an acid group as a monomer component, it is necessary to perform a treatment for imparting an acid group after polymerization. The treatment for imparting an acid group may vary depending on the type of monomer used to impart an acid group. For example, when a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate is used, addition such as Acid anhydrides such as succinic anhydride, tetrahydrophthalic anhydride, and maleic anhydride can be added with, for example, N-methylaminobenzoic acid, N -A compound having an amino group and an acid group such as methylaminophenol, or, for example, succinic anhydride, tetrahydrophthalic anhydride, maleic acid, etc. For acid anhydrides such as acid anhydrides, when a monomer having an isocyanate group such as 2-isocyanatoethyl (meth)acrylate is used, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid can be added.

When obtaining the above-mentioned polymer (b), when using the above-mentioned monomer capable of imparting a radically polymerizable double bond as a monomer component, and thus introducing a radically polymerizable double bond, it is necessary to perform Treatment of polymeric double bonds. The treatment for imparting a radically polymerizable double bond differs depending on the type of monomer used to impart a radically polymerizable double bond. For example, a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid is used At this time, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, o-(or m-, or p-)vinylbenzyl glycidyl ether, etc. can be added Compounds with epoxy groups and radically polymerizable double bonds can be added with 2-hydroxyethyl (meth)acrylate, etc. and radically polymerizable double bond compound, using glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, o-(or m-, or p-)vinylbenzyl In the case of a monomer having an epoxy group such as glycidyl ether, a compound having an acid group and a radically polymerizable double bond such as (meth)acrylic acid can be added.

The weight average molecular weight of the polymer (b) is not particularly limited, but is preferably 2,000 to 200,000, more preferably 5,000 to 100,000. When the weight average molecular weight exceeds 200,000, the viscosity becomes too high, making it difficult to form a coating film. On the other hand, when it is less than 2,000, it tends to be difficult to express sufficient heat resistance.

When the above polymer (b) has an acid group, the acid value is preferably 30 to 500 mgKOH/g, more preferably 50 to 400 mgKOH/g. When the acid value of the polymer (b) is less than 30 mgKOH/g, it is difficult to apply to alkali development, and when it exceeds 500 mgKOH/g, the viscosity becomes too high, and it tends to be difficult to form a coating film.

In addition, the polymer obtained by polymerizing the compound represented by the general formula (1) of the component (b) as an essential monomer component is a known compound, for example, JP-A-2004-300203 and A compound described in JP-A-2004-300204.

In addition, the component (b) can be used in [2-1] in addition to, or instead of, a polymer obtained by polymerizing a compound represented by the general formula (1) and/or (2) as an essential monomer component. "5-90 mol% of (W): epoxy group-containing (meth)acrylate, 10-95 mol% of (X): other free substances that can be copolymerized with (W)" will be described later in the chapter. (Y) unsaturated monobasic acid is added to 10 to 100 mol% of the epoxy groups contained in the obtained copolymer, and the hydroxyl group generated when the above-mentioned (Y) component is added A resin obtained by adding (Z) polybasic acid anhydride to 10 to 100 mol% of the resin”.

[1-2-3] Other dispersants

The dispersant used in the colorant dispersion liquid of the present invention may contain other dispersants as necessary in addition to the above-mentioned dispersants.

As other dispersants that can be used, for example, polyurethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene diester-based dispersants, Sorbitan fatty acid ester dispersant, aliphatic modified polyester dispersant, etc. Specific examples of such dispersants are represented by trade names, for example, EFKA (manufactured by EFKA Chemicals BV), Disperbyk (manufactured by Byk-Chemie GmbH), Disparon (manufactured by Kusumoto Chemicals Co., Ltd.), SOLSPERSE (manufactured by Zeneca Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), Ajisper (manufactured by Ajinomoto Co., Ltd.), and the like. These polymer dispersants may be used alone or in combination of two or more.

In the colorant dispersion of the present invention, the content of the (B) dispersant is usually 90% by weight or less, preferably 65% by weight or less, more preferably 50% by weight or less, based on the colorant (A) . When the content ratio of the dispersant is too small, dispersion stability deteriorates, and problems such as re-agglomeration and thickening occur. On the contrary, if it is too much, the ratio of the pigment will be relatively reduced, so the coloring power will be reduced, and the film thickness will be too thick relative to the color concentration. When used in a color filter, a cell gap may appear in the process of forming a liquid crystal unit. poor control.

(a) The proportion of the nitrogen atom-containing graft polymer and/or acrylic block copolymer is usually 40% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less, based on the colorant. (a) When the content ratio of the dispersant is too small, the dispersion liquid is unstable, and conversely, when too large, image forming properties such as curability decrease.

(b) The content ratio of the polymer obtained by polymerizing the compound represented by the general formula (1) and/or (2) as an essential monomer component is usually 55% by weight or less, preferably 35% by weight with respect to the coloring material % or less, more preferably 30% by weight or less. (b) When the content ratio of the dispersing agent is too small, the dispersion liquid becomes unstable, and conversely, when too large, image forming properties such as curability decrease.

[1-3] (C) Solvent

The colorant dispersion liquid of the present invention is usually prepared by dissolving or dispersing the above-mentioned solid components in (C) solvent.

(C) The solvent functions to dissolve or disperse (A) the color material, (B) the dispersant, and other components mixed as necessary in the color material dispersion liquid of the present invention to adjust the viscosity.

As the solvent, for example, diisopropyl ether, mineral spirits, n-pentane, pentyl ether, ethyl octanoate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate Esters, n-Octane, Varsol#2, APCO#18 Solvent, Diisobutylene, Amyl Acetate, Butyl Acetate, APCO Thinner, Butyl Ether, Diisobutyl Ketone, Methylcyclohexene, Methyl Nonyl Ketone , Propyl Ether, Dodecane, Socal 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, methoxymethyl pentanone, 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, dicyclohexane, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methyl amyl ketone, methyl isopropyl ketone, propyl propionate, Propylene glycol tert-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, 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, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 3-methoxypropionate Ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diethylene glycol dimethyl ether, ethylene glycol acetate, ethyl carbitol, butyl carbitol , Ethylene glycol monobutyl ether, propylene glycol tert-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate, etc. These solvents may be used alone or in combination of two or more.

The content of the above-mentioned solvent in the entire colorant dispersant of the present invention is not particularly limited, but is usually 99% by weight or less, and usually 70% by weight or more, preferably 75% by weight or more, more preferably 80% by weight or more. When the proportion of the solvent is too high, the solid content such as the coloring material and the dispersant becomes too small, and it is not suitable to form a coloring material dispersion liquid. On the other hand, when the proportion of the solvent is too small, the viscosity becomes high, making it unsuitable for coating.

[1-4] Other ingredients

In the colorant dispersion liquid of the present invention, there are no particular limitations on the optional other components, and for example, the following components may be contained.

[1-4-1] Binder resin

When the pigment dispersion liquid of the present invention is blended in the colored resin composition described later, the color material dispersion liquid of the present invention may contain a part of the binder resin described later. By including such a binder resin, the production cost can be improved. Dispersion stability of the inventive colorant dispersion.

In this case, the amount of the binder resin to be added is preferably 5 to 100% by weight, particularly preferably 10 to 80% by weight, based on the (A) color material in the color material dispersion liquid. When the amount of the binder resin added is less than 5% by weight, the effect of improving the dispersion stability is insufficient, and when it exceeds 100% by weight, since the colorant concentration decreases, sufficient color concentration cannot be obtained.

[1-4-2] Dispersion aid

As the dispersion aid, for example, pigment derivatives may be mentioned. Examples of pigment derivatives include azos, phthalocyanines, quinacridones, benzimidazolones, quinophthalones, isoindolinones, dioxazines, anthraquinones, and indanes. Derivatives of shilin pigments, perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, and dioxazine pigments. As the substituents of these pigment derivatives, sulfonic acid group, sulfonamide group and its quaternary salt, phthalimide methyl group, dialkylaminoalkyl group, hydroxyl group, carboxyl group, amido group, etc. Or a group bonded to the pigment skeleton through an alkyl group, an aryl group, a heterocyclic group, etc., preferably a sulfonamide group and its quaternary salt, 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 may be used. Specific examples of pigment derivatives include, for example, sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, and sulfonic acid derivatives of anthraquinone pigments. Sulfonic acid derivatives, sulfonic acid derivatives of quinacridone pigments, sulfonic acid derivatives of diketopyrrolopyrrole pigments, sulfonic acid derivatives of dioxazine pigments, and the like.

The amount of the pigment derivative added is usually 0.1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, based on the total solid content of the colorant dispersion liquid of the present invention. When the added amount of the pigment derivative is small, the dispersion stability is poor, and problems such as re-agglomeration and thickening occur. On the contrary, even if it is too much, the effect on dispersion stability is saturated, which will lead to the reduction of color purity.

[1-5] Manufacturing method of colorant dispersion liquid

Various methods can be employed as a method for producing the color material dispersion liquid of the present invention, and an example thereof is shown below.

First, predetermined amounts of the colorant, solvent, and dispersant are weighed, and in the dispersion treatment step, the colorant is dispersed to prepare a liquid colorant dispersion. In this dispersion treatment step, a conditioner, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, and the like can be used. Since the colorant is micronized by performing this dispersion treatment, the coating properties of the colored resin composition using the colorant dispersion liquid of the present invention are improved, and the transmittance of the color filter substrate as a product is improved.

When the color material is dispersed, it is appropriate to use the above-mentioned binder resin, dispersion aid, and the like in combination. For example, when the dispersion treatment is performed using a sand mill, it is preferable to use glass beads or zirconia beads with a particle diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set in the range of 0°C to 100°C, preferably in the range of room temperature to 80°C. In addition, the dispersion time varies depending on the composition of the color material dispersion (color material, solvent, dispersant, etc.) and the size of the sand mill device, so appropriate adjustment is necessary.

[2] Colored resin composition

Next, the colored resin composition of the present invention will be described.

The above-mentioned colorant dispersion liquid of the present invention can be used in various applications, but among them, it is preferably used as a colored resin composition for the purpose of forming a pixel image of a color filter or the like. As the colored resin composition, a binder resin, a monomer, a photopolymerization initiator, and other solid components can be blended together with the pigment dispersion liquid of the present invention. Hereinafter, each constituent component will be described.

In addition, in chapter [2], the "total solid content" refers to all components of the colored resin composition of the present invention other than the solvent component described later.

[2-1] Binder resin

As the binder resin, for example, JP-A-7-207211, JP-8-259876, JP-10-300922, JP-11-140144, JP-11-174224 , JP-A-2000-56118, JP-A-2003-233179, JP-A-2004-224894, JP-A-2004-300203, JP-A-2004-300204, etc., But among them preferably the macromolecular compound not containing nitrogen atom, more preferably the resin of record in the Japanese publication No. 2004-300203 and Japanese publication 2004-300204, and the resin obtained by the following method: 5～90 mol% ( W): epoxy group-containing (meth)acrylate, 10 to 95% by mole (X): other radically polymerizable compounds that can be copolymerized with (W) component, and contained in the obtained copolymer Add (Y) unsaturated monobasic acid to 10 to 100 mol% of the epoxy groups contained, and add (Z) polybasic acid to 10 to 100 mol% of the hydroxyl groups generated when the above-mentioned (Y) component is added. A photosensitive resin obtained from acid anhydride.

In addition, as the resins described in the above-mentioned JP-A-2004-300203 and JP-A-2004-300204, the specific compounds described in [1-2-2] (b) of the specification of the present application are essential. A polymer obtained by polymerizing the monomer components of the ingredients.

In addition, as (W): epoxy group-containing (meth)acrylates, for example, glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, ( (3,4-Epoxycyclohexyl)methyl methacrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, etc. Among them, glycidyl (meth)acrylate is preferable. These (W) components may be used individually by 1 type or in mixture of 2 or more types.

(W): The copolymerization ratio of epoxy group-containing (meth)acrylate (the copolymerization ratio when the (W) component and (X) component are copolymerized to produce a copolymer. Hereinafter, it is simply referred to as "copolymerization ratio") as above It is described as 5 to 90 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%. When this ratio is too large, (X) component will decrease and heat resistance or strength may fall, and when it is too small, since the addition amount of a polymeric component and an alkali-soluble component becomes insufficient, it is unpreferable.

On the other hand, (X): the copolymerization ratio of other radically polymerizable compounds that can be copolymerized with the component (W) is 10 to 95 mol % as described above, preferably 20 to 80 mol %, more preferably 30 to 70 mol % %. When this ratio is too large, since (W) component will decrease, the addition amount of a polymeric component and an alkali-soluble component will become insufficient, and when it is too small, heat resistance and intensity|strength may fall, and it is unpreferable.

As this (X): another radically polymerizable compound which can be copolymerized with the (W) component, it is preferable to use one or two of mono(meth)acrylates having a structure represented by the following general formula (5). more than one species.

[chemical formula 23]

(In formula (5), R ^4c to R ^9c respectively represent a hydrogen atom, or an alkyl group with 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group, and R ^10c and R ^11c represent a hydrogen atom or a methyl group, respectively. C1-3 alkyl groups such as radicals, ethyl groups, propyl groups, etc., may also be connected to form a ring. The ring formed by the connection of R ^10c and R ^11c is preferably an aliphatic ring, which may be any of saturated or unsaturated One, preferably having 5 to 6 carbon atoms).

In the said general formula (5), the mono(meth)acrylate which has the structure represented by following general formula (6), (7) or (8) is preferable. By introducing these structures into the binder resin, heat resistance or strength can be enhanced. Of course, these mono(meth)acrylates may be used individually by 1 type, and may mix and use 2 or more types.

[chemical formula 24]

As the mono(meth)acrylate having the structure represented by the above chemical formula (5), various known mono(meth)acrylates can be used, but the mono(meth)acrylic acid represented by the following chemical formula (9) is particularly preferable. ester.

[chemical formula 25]

(In formula (9), R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents the above chemical formula (5)).

The content of the mono(meth)acrylate having the structure of the above chemical formula (5) in the comonomer is usually 5 to 90 mol%, preferably 10 to 70 mol%, more preferably 15 to 50 mol%.

In addition, the radically polymerizable compound other than the above is not particularly limited, but specific examples thereof include,

Styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives of styrene;

Dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, and chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid - n-propyl, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, ( Neopentyl methacrylate, Isoamyl (meth)acrylate, Hexyl (meth)acrylate, 2-Ethylhexyl (meth)acrylate, Lauryl (meth)acrylate, (Meth)acrylic acid Lauryl ester, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, (meth)acrylate ) isophorone acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate , Anthracene (meth)acrylate, Anthraquinone (meth)acrylate, Piperonyl (meth)acrylate, Salicyl (meth)acrylate, Fufuryl (meth)acrylate, Furfuryl (meth)acrylate , Tetrahydrofuryl (meth)acrylate, pyryl (meth)acrylate, benzyl (meth)acrylate, phenethyl (meth)acrylate, cresyl (meth)acrylate, (meth)acrylic acid- 1,1,1-trifluoroethyl ester, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoroisopropyl (meth)acrylate, triphenyl (meth)acrylate methyl methyl ester, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (methyl) (meth)acrylates such as 2-hydroxypropyl acrylate;

(Meth)acrylamide, (meth)acrylic acid N,N-diformamide, (meth)acrylic acid N,N-diacetamide, (meth)acrylic acid N,N-dipropionamide, (methyl) Acrylic acid N,N-diisopropanamide, (meth)acrylic acid anthracene amide and other (meth)acrylamides; (meth)acryloyl anilide, (meth)acrylonitrile, acrolein, vinyl chloride, partial chloride Vinyl compounds such as ethylene, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate;

Diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate and other unsaturated dicarboxylic acid diesters;

Monomaleimide such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide Amines;

N-(meth)acryloylphthalimide, etc.

In order to impart better heat resistance and strength, it is effective to use at least one selected from styrene, benzyl (meth)acrylate, and monomaleimide as the (X) component.

At this time, the copolymerization ratio of at least one selected from styrene, benzyl (meth)acrylate and monomaleimide is preferably 1-70 mol%, more preferably 3-50 mol%.

A known solution polymerization method is applied to the copolymerization reaction of (W)component and (X)component. The solvent to be used is not particularly limited as long as it is an inactive solvent for radical polymerization, and generally used organic solvents can be used.

Specific examples thereof include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, acetic acid cellosolve, and butyl cellosolve acetate; diethylene glycol monomethyl ether Acetate, carbitol acetate, butyl carbitol acetate and other diethylene glycol monoalkyl ether acetates; propylene glycol monoalkyl ether acetates;

Dipropylene glycol monoalkyl ether acetates and other acetates;

Ethylene glycol dialkyl ethers;

Methyl carbitol, ethyl carbitol, butyl carbitol and other diethylene glycol dialkyl ethers;

Triethylene glycol dialkyl ethers;

Propylene glycol dialkyl ethers;

Dipropylene glycol dialkyl ethers;

1,4-dioxane, tetrahydrofuran and other ethers;

Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones;

Hydrocarbons such as benzene, toluene, xylene, octane, decane, etc.; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha, etc.; lactic acid such as methyl lactate, ethyl lactate, and butyl lactate Esters;

Dimethylformamide, N-methylpyrrolidone, etc.

These solvents may be used alone or in combination of two or more. The usage-amount of these solvents is 30-1000 weight part normally with respect to 100 weight part of copolymers obtained, Preferably it is 50-800 weight part. When the amount of the solvent used is out of this range, it is difficult to control the molecular weight of the copolymer.

The radical polymerization initiator that can be used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and generally used organic peroxide catalysts or azo compounds can be used.

Examples of organic peroxide catalysts include ketone peroxides, peroxyketals, hydrogen peroxide, diallyl peroxides, diacyl peroxides, peroxyesters, peroxyketals, and peroxides. Dicarbonate substances.

Specific examples of the radical polymerization initiator include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-tert-butyl peroxide, and tert-butyl benzyl peroxide. ester, tert-hexylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, tert-hexylperoxy-2-ethylhexanoate, 1,1-bis(tert-butylperoxy )-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyl-3,3-isopropylhydroperoxide, tert-butyl Dicumyl peroxide, dicumyl peroxide, dicumyl peroxide, acetyl peroxide, bis(4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl Base peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexyl Alkane, 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azocarboxylic acid amide, etc., one or two can be selected according to the polymerization temperature Use more than one free radical polymerization initiator with an appropriate half-life.

The usage-amount of a radical polymerization initiator is 0.5-20 weight part with respect to 100 weight part of total amounts of (W) component and (X) component which are monomers used for a copolymerization reaction, Preferably it is 1-10 weight part.

The copolymerization reaction can be carried out by dissolving the monomer used in the copolymerization reaction and the radical polymerization initiator in a solvent, and raising the temperature while stirring, or adding the monomer added with the radical polymerization initiator dropwise to the heated and stirred solvent. to proceed. Moreover, you may add a monomer dropwise to the solvent which added the radical polymerization initiator and heated up. The reaction conditions can be freely changed according to the target molecular weight.

(Y)component added to the epoxy group contained in the copolymer of (W)component and (X)component is an unsaturated monobasic acid. As the (Y) component, well-known substances can be used, and unsaturated carboxylic acids having ethylenically unsaturated double bonds can be mentioned. As specific examples, acrylic acid, methacrylic acid, crotonic acid, ortho-, m- , p-vinylbenzoic acid, α-position haloalkyl, alkoxy, halogen, nitro, cyano substituents of (meth)acrylic acid, etc. Monocarboxylic acids, etc. Among them, acrylic acid and/or methacrylic acid are preferable. These (Y) components may be used individually by 1 type, and may mix and use 2 or more types.

The (Y) component can be added to 10 to 100 mol% of the epoxy groups contained in the copolymer obtained by the copolymerization of the (W) component and (X) component, but it is preferably added at 30 to 100 mol%. In mol%, it is more preferable to add in 50 to 100 mol%. When the addition ratio of this (Y) component is too small, there exists a possibility that adverse effects by the residual epoxy group, such as stability over time, may arise.

As a method of adding (Y) component and the copolymer of (W) component and (X) component, a well-known method can be employ|adopted.

Known substances can be used as (Z) polybasic acid anhydride added to the hydroxyl group generated when the copolymer of (Y) component, (W) component and (X) component is added, maleic anhydride, succinic anhydride, Dibasic anhydrides such as acid anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexachloronorbornene diacid anhydride; trimellitic anhydride, pyromellitic anhydride, diphenylmethane Polybasic acid anhydrides such as ketone tetracarboxylic anhydride and biphenyl tetracarboxylic anhydride. Among them, tetrahydrophthalic anhydride and/or succinic anhydride are preferred. (Z) The component may be used individually by 1 type, and may mix and use 2 or more types. By adding such components, the binder resin used in the present invention can be made alkali-soluble.

(Z) component can add 10-100 mol% of the hydroxyl group which arises when adding (Y) component, Preferably it can add 20-90 mol%, More preferably, it can add 30-80 mol%. When this addition ratio is too large, the remaining film rate at the time of image development may fall, and when it is too small, solubility may become insufficient.

A well-known method can be employ|adopted as a method of adding (Z)component to the hydroxyl group which arises when (Y)component and the copolymer of (W)component and (X)component are added.

In addition, in the present invention, in order to further improve the photosensitivity, after adding (Z) polybasic acid anhydride, glycidyl (meth)acrylate or a polyacrylic acid having a polymerizable unsaturated group may be added to a part of the generated carboxyl groups. Glycidyl ether compound, or, in order to improve the developability, after adding (Z) polybasic acid anhydride, a glycidyl ether compound not having a polymerizable unsaturated group may be added to a part of the generated carboxyl group, or may be added into both. Specific examples of glycidyl ether compounds not having a polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group (trade names manufactured by Nagase Chemicals Ltd.: Denacol EX-111, Denacol EX-121, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192) etc.

In addition, these resin structures are described in, for example, JP-A-8-297366 or JP-A-2001-89533, and are already known.

The polystyrene-equivalent weight-average molecular weight (Mw) measured by GPC as such a binder resin is preferably 3,000 to 100,000, particularly preferably 5,000 to 50,000. When the molecular weight is less than 3,000, heat resistance and film strength are poor, and when it exceeds 100,000, the solubility to a developing solution is insufficient, which is not preferable. In addition, the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) is preferably 2.0 to 5.0.

Such binder resins may be used alone or in combination of two or more.

In particular, when such a binder resin is used together with a urethane-based dispersant or an acrylic dispersant to be described later, undissolved matter will not remain on the non-image portion of the substrate, and adhesiveness to the substrate can be formed. Excellent high-density color pixel effect is therefore preferred.

Such a binder resin is usually contained in the total solid content of the colored resin composition of the present invention in an amount of 0.1 to 80% by weight, preferably in a range of 1 to 60% by weight. When the content of the binder resin is smaller than this range, the film becomes brittle, and the adhesiveness with the substrate may decrease. Conversely, when the range is larger than this range, the penetrability of the developing solution to the exposed part becomes high, and the surface smoothness or sensitivity of the pixel may be deteriorated.

[2-2] Photopolymerization initiators

A photopolymerization initiator is usually used as a mixture (photopolymerization initiators) with additives such as accelerators and, if necessary, sensitizing dyes. Photopolymerization initiators are components that directly absorb light, or cause decomposition or dehydrogenation reactions through photosensitization to generate polymerization active radicals.

As the photopolymerization initiator constituting the photopolymerization initiator component, for example, metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197, Or N-aryl-α-amino acids such as hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, N-phenylglycine, N-aryl - Radical activators such as α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone compounds, oxime ester initiators described in JP-A-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) Base)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)- 4,6-bis(trichloromethyl)-s-triazine and other halomethylated triazine derivatives;

2-Trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl) Vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuryl)vinyl)-1,3,4-oxadiazole Halomethylated oxadiazole derivatives such as oxadiazole and 2-trichloromethyl-5-furyl-1,3,4-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 imidazole derivatives such as (4'-methoxyphenyl)-4,5-diphenylimidazole dimer;

Benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether and other benzoin alkyl ethers;

2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and other anthraquinone derivatives;

Benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone Benzophenone derivatives such as ketones and 2-carboxybenzophenone;

2,2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methyl phenylacetone, 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 (p-butylphenyl) ketone and other acetophenone derivatives;

Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, Thioxanthone derivatives such as 2,4-diisopropylthioxanthone;

Benzoate derivatives such as p-dimethylaminobenzoic acid ethyl ester and p-diethylaminobenzoic acid ethyl ester; 9-phenylacridine, 9-(p-methoxyphenyl) acridine and other acridine Pyridine derivatives; phenazine derivatives such as 9,10-dimethylbenzophenazine;

Anthrone derivatives such as benzoanthrone;

Dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyl titanium, dicyclopentadienyl bis(2,3,4,5,6-pentafluorophenyl-1-yl)titanium , Dicyclopentadienyl bis (2,3,5,6-tetrafluorophenyl-1-yl) titanium, dicyclopentadienyl bis (2,4,6-trifluorophenyl-1-yl) Titanium, dicyclopentadienylbis(2,6-difluorophen-1-yl)titanium, dicyclopentadienylbis(2,4-difluorophen-1-yl)titanium, dimethylcyclo Pentadienylbis(2,3,4,5,6-pentafluorophen-1-yl)titanium, bis(methylcyclopentadienyl)bis(2,6-difluorophen-1-yl) Titanium, dicyclopentadienylbis(2,6-difluoro-3-(pyl-1-yl)-benzene-1-yl)titanium and other titanocene derivatives;

2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinyl Phenyl)butanone-1, 2-benzyl-2-dimethylamino-1-(morpholinylphenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4 -Dimethylaminoisoamylbenzoate, 4-Diethylaminoacetophenone, 4-Dimethylaminopropiophenone, 2-Ethylhexyl-1,4-dimethylaminobenzoate , 2,5-bis(4-diethylaminobenzyl)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylaminobenzoyl) Amino) chalcone and other α-aminoalkylphenone compounds;

1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(o-benzoyl oxime) (1,2-octanedione1-[4-(phenylthio)phenyl]2-( O-benzoyloxime)), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(o-acetyloxime) (ethanone 1 -[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]1-(O-acetyloxime)) and other oxime ester compounds.

As the accelerator constituting the photopolymerization initiator components, for example, N,N-dimethylaminobenzoic acid alkyl esters such as N,N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzene Thiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole and other heterocyclic mercapto compounds, or aliphatic polyfunctional mercapto compounds.

These photoinitiators and accelerators may be used individually by 1 type, respectively, and may mix and use 2 or more types.

Specific photopolymerization initiator components include, for example, dialkylphenylethyl ethers described on pages 16-26 of "Fine Chemical" (1991, March 1, Vol. 20, No. 4). Ketones, benzoin, thioxanthone derivatives, etc., and hexaaryldiimidazoles, S-trihalomethyltri Azines, titanocene and xanthene dyes described in JP-A-4-221958, JP-A-4-219756, etc., combinations of addition-polymerizable ethylene pigments having amino or carbamate groups A system of compounds with a saturated double bond, etc.

The compounding ratio of the said photoinitiator type component is 0.1-40 weight% normally in the total solid content of a colored resin composition, Preferably it is 0.5-30 weight%. When the content ratio is markedly low, it may cause a decrease in sensitivity to exposure light. Conversely, if it is markedly high, the solubility of the unexposed portion to the developing solution may decrease, which may cause poor development.

If necessary, in order to increase the sensitivity, a sensitizing dye corresponding to the wavelength of the image exposure light source may be blended into the photopolymerization initiator component. Examples of these sensitizing dyes include xanthene-based dyes described in JP-A-4-221958 and JP-A-4-219756, and those described in JP-A-3-239703 and JP-A-5-289335. Heterocyclic coumarin dyes, 3-oxocoumarin compounds described in JP-A-3-239703, JP-A-5-289335, methylenepyrrole dyes described in JP-A-6-19240, and JP-A-47-2528, JP-A-54-155292, JP-A-45-37377, JP-48-84183, JP-52-112681, JP-58-15503, JP-A 60-88005, JP-59-56403, JP-2-69, JP-57-168088, JP-5-107761, JP-5-210240, JP-4-288818 Dyes having a dialkylaminobenzene skeleton as described in

Among these sensitizing dyes, amino group-containing sensitizing dyes are preferable, and compounds having amino groups and phenyl groups in the same molecule are more preferable. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone , 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone and other benzophenone compounds; 2-(p-dimethyl Aminophenyl)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-di Methylaminophenyl) benzothiazole, 2-(p-diethylaminophenyl)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. contain p- Dialkylaminophenyl compounds, etc. Most preferred of these are 4,4'-dialkylaminobenzophenones. The sensitizing dye may be used alone or in combination of two or more.

The proportion of the sensitizing dye of the present invention in the coloring composition for color filters is usually 0 to 20% by weight, preferably 0.1 to 15% by weight, and more preferably 0.2 to 20% by weight of the total solid content of the colored resin composition. 10% by weight.

[2-3] Monomer

The monomer is not particularly limited as long as it is photopolymerizable and contains a polymerizable low-molecular compound, but it is preferably a polyfunctional monomer with a functional group, and more preferably a monomer with at least one ethylenic double bond. Addition-polymerized compound (hereinafter referred to as "ethylene compound"). In addition, 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 coloring composition for color filter of the present invention is irradiated with active light. In addition, the "monomer" in the present invention is a concept relative to a so-called polymer substance, and includes "dimer", "trimer" and "oligomer" in addition to a narrowly defined monomer.

As the ethylenic compound having an acid group, for example, 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 Esters of unsaturated carboxylic acids, esters obtained by esterification of polyhydroxy compounds such as unsaturated carboxylic acids and polycarboxylic acids and the above-mentioned aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, polyisocyanate compounds and The ethylenic compound having a urethane skeleton obtained by reacting a hydroxyl compound of an acryloyl group, etc.

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

Examples of esters of aliphatic polyols and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. , Pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerin acrylate and other acrylates. In addition, methacrylate in which the acrylic acid moiety of these acrylates is replaced by a methacrylic acid moiety, an itaconic acid ester in which a crotonic acid moiety is replaced, or a crotonic acid ester in which a crotonic acid moiety is replaced, or Maleic esters of the maleic acid moiety, etc.

Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, Pyrogallol triacrylate, etc.

The ester obtained by esterification reaction of an unsaturated carboxylic acid, a polycarboxylic acid, and a polyhydroxy compound does not need to be a single thing, and may be a mixture. Representative examples include condensation products of acrylic acid, phthalic acid and ethylene glycol, condensation products of acrylic acid, maleic acid and diethylene glycol, and condensation products of methacrylic acid, terephthalic acid and pentaerythritol. Compounds, acrylic acid, adipic acid, butanediol and glycerin condensation products, etc.

Examples of ethylenic compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a hydroxyl compound containing a (meth)acryloyl group include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and the like. Aliphatic diisocyanates; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate; and 2-hydroxyethyl acrylate, 2 -Hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloyloxymethyl)propane, 3-hydroxy(1,1,1-trimethacryloyloxymethyl)propane And other reactants containing (meth)acryloyl hydroxyl compounds.

As examples of other ethylenic compounds used in the present invention, acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate, etc. useful.

In the present invention, the monomer is a polyfunctional monomer, and may have acid groups such as carboxyl, sulfonic, and phosphoric acid groups. Therefore, as mentioned above, when the ethylenic compound is a mixture, as long as it has an unreacted carboxyl group, it can be used as it is, but if necessary, it is also possible to mix the hydroxyl group of the above-mentioned ethylenic compound with a non-aromatic carboxylic acid anhydride reaction to introduce acid groups. In this case, specific examples of non-aromatic carboxylic anhydrides that can be used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, to acid anhydride.

In the present invention, the monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, preferably one having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. Polyfunctional monomers, particularly preferably, in the ester, the aliphatic polyol 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 of them may be mixed and used. In addition, if necessary, a polyfunctional monomer not having an acid group and a polyfunctional monomer having an acid group may be used together as monomers.

The preferable acid value of the polyfunctional monomer which has an acid group is 0.1-40 mg-KOH/g, Especially preferably, it is 5-30 mg-KOH/g. When the acid value of the polyfunctional monomer is too low, the developing solubility property is lowered, and when it is too high, it is difficult to manufacture or handle, photopolymerization performance is lowered, and curability such as surface smoothness of pixels is deteriorated. Therefore, when two or more polyfunctional monomers having different acid groups are used together, or when polyfunctional monomers having no acid groups are used together, the acid groups of all the polyfunctional monomers must be adjusted within the above-mentioned range.

In the present invention, more preferable polyfunctional monomers having an acid group are dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate sold as TO 1382 manufactured by Toagosei Co., Ltd. A mixture of succinates as the main ingredient. Other polyfunctional monomers other than this polyfunctional monomer can also be used in combination.

The mixing ratio of these polyfunctional monomers is usually 5 to 80% by weight, preferably 10 to 70% by weight, in the total solid content of the colored resin composition of the present invention, and is 5 to 200% by weight as a ratio to the color material. %, preferably 10 to 100% by weight, more preferably 20 to 80% by weight. The compounding ratio of a polyfunctional monomer can be adjusted suitably according to the kind of the coloring material of a coloring composition, or the acid value of the polyfunctional monomer used.

[2-4] Organic carboxylic acid, organic carboxylic acid anhydride

The coloring composition for color filters of the present invention may 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 organic carboxylic acids include aliphatic carboxylic acids and/or aromatic carboxylic acids. Specific examples of the aliphatic carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, hexanoic acid, diethylacetic acid, heptanoic acid, caprylic acid, glycolic acid, acrylic acid, formic acid, Acrylic acid and other monocarboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brazilian acid, methylmalonic acid , ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid Dicarboxylic acids such as fumaric acid, tricarboxylic acids such as propanetricarboxylic acid, aconitic acid, and camphortricarboxylic acid, etc. In addition, examples of the aromatic carboxylic acid specifically include benzoic acid, phenylacetic acid, p-isopropylbenzoic acid, 2,3-dimethylbenzoic acid, 3,5-dimethylbenzoic acid, benzenedi Formic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic acid, trimellitic acid, pyromellitic acid, phenylacetic acid, hydrogenated atropic acid, hydrogenated cinnamic acid, Mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, quamalic acid, umbelliferic acid and other carboxylic acids directly bonded to the carboxyl group on the phenyl group and through Carboxylic acid, etc., where the carbon bond binds the carboxyl group on the phenyl group.

Among the above-mentioned organic carboxylic acids, monocarboxylic acids and dicarboxylic acids are preferable, and among them, malonic acid, glutaric acid, and glycolic acid are more preferable, and malonic acid is particularly preferable.

The above-mentioned organic carboxylic acid has a molecular weight of 1,000 or less, and usually 50 or more. When the molecular weight of the above-mentioned organic carboxylic acid is too large, the effect of improving scum is insufficient, and when it is too small, reduction of the added amount and process contamination may be caused due to sublimation, volatilization, and the like.

[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 examples of aliphatic carboxylic acid anhydrides specifically include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, Phthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, glutaric anhydride, 1,2-cyclohexenedioic anhydride, n-octadecylsuccinic anhydride, 5-norbornene-2, Aliphatic carboxylic acid anhydrides such as 3-dicarboxylic acid anhydride. Specific examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.

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

The molecular weight of the above-mentioned organic carboxylic acid anhydride is usually 800 or less, preferably 600 or less, more preferably 500 or less, and usually 50 or more. When the molecular weight of the above-mentioned organic carboxylic acid anhydride is too large, the scum improvement effect is insufficient, and when it is too small, reduction of the added amount and process contamination may be caused due to sublimation, volatilization, and the like.

These organic carboxylic acids and organic carboxylic acid anhydrides may be used alone or in combination of two or more.

These organic carboxylic acids and organic carboxylic anhydrides are added in an amount of usually 0.01% by weight or more, preferably 0.03% by weight or more, more preferably 0.05% by weight or more, and usually 10% by weight in the total solid content of the colored resin composition of the present invention. % by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less. When the added amount is too small, a sufficient effect of addition cannot be obtained, and when too large, surface smoothness or sensitivity deteriorates, and undissolved peeling pieces may be generated.

[2-5] Other solid components

In the colored resin composition of the present invention, solid components other than the above-mentioned components may be blended as needed. Examples of such components include surfactants, thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protective agents, adhesion enhancers, and development improvers.

[2-5-1] Surfactant

As the surfactant, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used, but nonionic surfactants are preferred because they are less likely to adversely affect the properties. active agent.

The amount of the surfactant added is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, preferably 0.01 to 0.5% by weight, most preferably 0.03 to 0.3% by weight, based on the total solid content of the colored resin composition of the present invention. %. When the addition amount of the surfactant is smaller than the above range, the smoothness and uniformity of the coating film cannot be expressed, and when it is too large, other characteristics may deteriorate in addition to the smoothness and uniformity of the coating film.

[2-5-2] Thermal polymerization inhibitor

As the thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-tert-butyl-p-cresol, β-naphthol and the like can be used. The addition amount of a thermal-polymerization inhibitor is the range of 0-3 weight% with respect to the total solid content in the colored resin composition of this invention.

[2-5-3] Plasticizer

As plasticizers, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate , tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerol, etc. The addition amount of these plasticizers is 10 weight% or less with respect to the total solid content in the colored resin composition of this invention.

[2-5-4] Others

Moreover, a storage stabilizer, a surfactant, an adhesion improving agent, a development improving agent, etc. can be added as needed. The addition amount of these components is 20 weight% or less with respect to the total solid content in the colored resin composition of this invention.

[2-6] Preparation of coloring composition

Next, a specific example of the production method of the colored resin composition of the present invention will be described.

In the colorant dispersion obtained by the dispersion treatment described in [1-5] above, a solvent, a binder resin, a polyfunctional monomer, a photopolymerization initiator component, and other components mixed as necessary are mixed to prepare into a uniform dispersed solution. In addition, since fine impurities may be mixed in each step of the dispersion treatment step and the mixing step, it is preferable to filter the obtained colored resin composition through a filter.

[3] Manufacture of color filters

Next, a specific example of the manufacturing method of the color filter of the present invention will be described.

Color filters are manufactured by placing a black matrix on a transparent substrate, and then forming red, green, and blue pixel images in sequence.

The coloring composition for color filters of the present invention is used as a coating liquid for forming at least one pixel image of black, red, green, and blue. For the black resist, it is on the transparent substrate, and for the red, green, and blue color resists, it is on the resin black matrix forming surface formed on the transparent substrate, or using chromium compounds, other light-shielding metal materials Various treatments such as coating, heating and drying, image exposure, development, and thermal curing are performed on the formed surface of the formed metallic black matrix to form pixel images of various colors.

[3-1] Transparent substrate (support)

The material of the transparent substrate of the color filter is not particularly limited as long as it is transparent and has appropriate strength. Examples of materials include polyester resins such as polyethylene terephthalate; polyolefin resins such as polypropylene and polyethylene; thermoplastic resins such as polycarbonate, polymethyl methacrylate, and polysulfone. Sheets made of resin, sheets of thermosetting resins such as epoxy resins, unsaturated polyester resins, and poly(meth)acrylic resins, or various glasses. Among them, glass and heat-resistant resins are preferable from the viewpoint of heat resistance.

In order to improve surface physical properties such as adhesiveness, corona discharge treatment, ozone treatment, silane coupling agent, polyurethane resin and other thin film formation treatment can be performed on these transparent substrates and the black matrix formation substrate described later, if necessary. .

The thickness of the transparent substrate is usually set in the range of 0.05 to 10 mm, preferably in the range of 0.1 to 7 mm. In addition, when the thin film formation process of various resins is performed, the film thickness is usually 0.01-10 micrometers, Preferably it is the range of 0.05-5 micrometers.

[3-2] Black matrix

The black matrix is formed on a transparent substrate using a light-shielding metal film or a photosensitive black composition for a black matrix. As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide, and chromium nitride, alloys of nickel and tungsten, etc. may be used, and these may be laminated in a multilayer form.

These light-shielding metal films are usually formed by sputtering, a desired pattern is formed on the film by a positive photoresist, and then, an etching solution mixed with cerium ammonium nitrate and perchloric acid and/or nitric acid is used for chromium, and for For other materials, use an etching solution suitable for the material to etch, and finally, use a special stripper to strip the positive photoresist, thereby forming a black matrix.

In this case, first, a thin film of these metals or metal/metal oxides is formed on a transparent substrate by vapor deposition, sputtering, or the like. Next, after forming a coating film of the coloring composition on the film, the coating film is exposed and developed using a photomask having repeating patterns such as lines, mosaics, and triangles to form a resist image. Then, the coating film may be etched to form a black matrix.

On the other hand, when using the black composition used for a black matrix, the black matrix is formed using the colored resin composition containing a black coloring material. For example, one or more of black pigments such as carbon black, graphite, iron black, aniline black, Xeronine black, titanium black, etc. can be used, or, by mixing red pigments appropriately selected from inorganic or organic pigments and dyes, , green, blue, etc., to form a black matrix in the same manner as the method for forming pixel images of red, green, and blue described below.

[3-3] Pixel formation

[3-3-1] Formation of coating film

On a transparent substrate provided with a black matrix, a coloring composition containing one of red, green, and blue colorants is coated, and after drying, a photomask is laminated on the formed coating film, and the photomask is passed through the photomask Image exposure, development, and thermal curing or photocuring as necessary are performed to form a pixel image, and a colored layer of the pixel image is produced. This operation can be performed on three-color coloring compositions of red, green, and blue, respectively, thereby forming a color filter image.

The coating of the coloring composition for the color filter is by, for example, a spin coating method, a wire-wound bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, a spray coating method, or a spray coating method. Ink method and so on. Among them, if the die coating is used, the amount of coating liquid used can be greatly reduced, and there is no influence of mist attached to the spin coating method at all, and the occurrence of foreign matter can be suppressed. From a comprehensive point of view, is preferred.

When the thickness of the coating film is too thick, it may be difficult to develop the pattern and also to adjust the gap in the step of forming a liquid crystal unit. When it is too thin, it may be difficult to increase the colorant concentration, and the desired color expression may not be obtained. The thickness of the coating film is usually preferably in the range of 0.2 to 20 μm, more preferably in the range of 0.5 to 10 μm, and particularly preferably in the range of 0.8 to 5 μm, in terms of the film thickness after drying.

[3-3-2] Drying of coated film

Drying of a coating film formed by coating a coloring composition on a transparent substrate is preferably a drying method using a hot plate, an IR oven, or a convection oven. Usually, after the pre-drying, the secondary drying of heat drying is performed again. The pre-drying conditions can be appropriately selected according to the type of the above-mentioned solvent component, the performance of the drier to be used, and the like. The drying time can be selected according to the type of solvent component, the performance of the drying machine used, etc., usually at a temperature of 40°C to 80°C, within a range of 15 seconds to 5 minutes, preferably at a temperature of 50°C to 70°C, within 30 seconds to 3 minutes. Minute range selection.

In addition, the temperature condition of the reheat drying is preferably 50°C to 200°C higher than the predrying temperature, preferably 70°C to 160°C, particularly preferably 70°C to 130°C. Moreover, although drying time depends on heating temperature, it is normally 10 seconds - 10 minutes, and the range of 15 seconds - 5 minutes is preferable especially. The higher the drying temperature, the better the adhesiveness to the transparent substrate. However, if it is too high, the binder resin will be decomposed, thermal polymerization will be induced, and poor development may occur. In addition, for drying of the coating film, a reduced-pressure drying method in which drying is performed in a reduced-pressure chamber without raising the temperature can also be used.

[3-3-3] Exposure steps

The image exposure is performed by superimposing a negative matrix pattern on the coating film of the dried coloring composition, and irradiating a light source of ultraviolet light or visible light through the mask pattern. At this time, in order to prevent the sensitivity reduction of the colored composition film due to oxygen, if necessary, an oxygen blocking layer such as a polyvinyl alcohol layer may be formed on the colored composition film before exposure.

The light source used for image exposure is not particularly limited, and examples thereof include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, and fluorescent lamps. Lamp light source or laser light source such as argon ion laser, YAG laser, excimer laser, nitrogen laser, lithium cadmium laser, semiconductor laser, etc. Optical filters can also be used when irradiating with light of a specific wavelength.

[3-3-4] Development step

The development can be performed using an organic solvent or an aqueous solution containing a surfactant and a basic compound after the above image exposure. In this aqueous solution, an organic solvent, a buffer, a complexing agent (a complexing agent), a dye or a pigment may also be contained.

Examples of basic 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, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide and other inorganic basic compounds, or mono-, di-, or triethanolamine, mono-, di-, or trimethyl Amine, mono-, di-, or triethylamine, mono-, or diisopropylamine, n-butylamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, tetra Organic basic compounds such as methyl ammonium hydroxide (TMAH), choline, etc. These basic compounds may be used alone or in combination of two or more.

Examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglycerol alkyl Nonionic surfactants such as esters, anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkylsulfonates, sulfosuccinates, etc. Active agents, alkyl betaines, amino acids and other amphoteric surfactants. These may be used individually by 1 type, and may mix and use 2 or more types.

Examples of the organic solvent include one or two or more of isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. The organic solvent can be used alone or simultaneously with the aqueous solution.

The conditions of the developing treatment are not particularly limited, but the developing temperature is usually in the range of 10°C to 50°C, preferably 15°C to 45°C, particularly preferably 20°C to 40°C, and the developing method can be dipping developing method, spray developing method, Any method such as a brush developing method and an ultrasonic developing method may be used.

[3-3-5] Thermal curing treatment

Usually, thermal curing treatment or photocuring treatment is performed on the color filter substrate after development, and thermal curing treatment is preferably performed.

The temperature of the thermal curing treatment condition is selected in the range of 100-280°C, preferably in the range of 150-250°C, and the time is selected in the range of 5-60 minutes.

Through this series of steps, an image forming a pattern of one color is completed. This step is repeated in sequence to form (black,) red, green, blue patterns, thereby forming a color filter. In addition, the order of forming the three color patterns of red, green, and blue is not limited to the above order.

[3-3-6] Formation of transparent electrodes

The color filter according to the present invention has a transparent electrode such as ITO formed on the image in its original state and is used as a part of a color display, a liquid crystal display device, etc. Provide surface coatings such as polyamide and polyimide on it.

In addition, in some applications such as in-plane alignment driving method (IPS mode), transparent electrodes may not be formed.

[4] Liquid crystal display device (panel)

Next, a specific example of a method for manufacturing a liquid crystal display device (panel) according to the third aspect of the present invention will be described.

The liquid crystal display device of the present invention is generally manufactured according to the following method: an alignment film is formed on the above-mentioned color filter of the present invention, and spacers (spacers) are dispersed on the alignment film, and a liquid crystal cell is formed by laminating with a counter substrate, and Liquid crystal is injected into the formed liquid crystal cell, and then the opposite electrode is connected.

As the alignment film, resin films such as polyimide are preferable. To form an alignment film, a gravure printing method and/or a flexographic printing method is generally used, and the thickness of the alignment film is usually set to several 10 nm. After curing the alignment film by thermal baking, surface treatment is performed by ultraviolet irradiation or treatment with a rubbing cloth, and processed into a surface state capable of adjusting the inclination of the liquid crystal.

As the spacer, a spacer having a size suitable for the gap with the opposing substrate is used, and usually, 2 to 8 μm is preferable. A photosensitive spacer (PS) of a transparent resin film can be formed on the color filter substrate by photolithography and used instead of the spacer.

As the opposing substrate, an array substrate is generally used, and a TFT (Thin Film Transistor) substrate is particularly preferable.

The gap for bonding to the counter substrate varies depending on the application of the liquid crystal panel, but is usually selected in the range of 2 to 8 μm. After bonding to the counter substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. The sealing material is cured by ultraviolet (UV) irradiation and/or heating to seal the periphery of the liquid crystal cell.

After the liquid crystal cell with the periphery sealed is cut into panel units, the liquid crystal is injected into the liquid crystal cell by depressurizing in a vacuum chamber and dipping the liquid crystal injection hole in the liquid crystal and leaking into the chamber. The degree of vacuum in the liquid crystal cell is usually 1×10 ^-2 Pa to 1×10 ^-7 Pa, preferably 1×10 ^-3 Pa to 1×10 ^-6 Pa. In addition, it is preferable to heat the liquid crystal cell during depressurization, and the heating temperature is usually 30°C to 100°C, more preferably 50°C to 90°C. Heating at the time of depressurization is kept in the range of usually 10 to 60 minutes, and then immersed in liquid crystal. In the liquid crystal cell into which the liquid crystal has been injected, the liquid crystal injection port is sealed by curing the UV curable resin, thereby completing the liquid crystal display device (panel).

In addition, the type of liquid crystal is not particularly limited, conventionally known liquid crystals such as aromatics, aliphatics, and polycyclic compounds may be used, and any of lyotropic liquid crystals and thermotropic liquid crystals may be used. Among the thermotropic liquid crystals, nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals are known, and any of them may be used.

Example

Hereinafter, the present invention will be described more specifically by way of examples and comparative examples. In addition, the present invention is not limited to the description of the following examples unless the gist is exceeded.

<Examples 1 to 6 and Comparative Examples 1 to 6>

[1] (a) Synthesis of nitrogen-atom-containing graft copolymers or acrylic block copolymers (dispersants A to C)

[1-1] Synthesis Example 1: Synthesis of Dispersant A

Mix 50 parts by weight of polyethyleneimine with a molecular weight of about 5000 and 40 parts by weight of polycaprolactone with n=5 and 300 parts by weight of propylene glycol monomethyl ether acetate, and stir at 150 ° C under a nitrogen atmosphere 3 hours. The dispersant thus synthesized had a weight average molecular weight Mw of about 9,000 as measured by GPC.

[1-2] Synthesis Example 2: Synthesis of Dispersant B

50 parts by weight of polyethyleneimine with a molecular weight of about 5000, 40 parts by weight of polycaprolactone with n=5 and 6 parts by weight of stearic acid are mixed with 300 parts by weight of propylene glycol monomethyl ether acetate, and Stir at 150°C for 3 hours under nitrogen atmosphere.

The dispersant thus synthesized had a weight average molecular weight Mw of about 9300 as measured by GPC.

[1-3] Synthesis Example 3: Synthesis of Dispersant C

50 parts by weight of polyethyleneimine with a molecular weight of about 10000, 40 parts by weight of polycaprolactone with n=5 and 6 parts by weight of stearic acid were mixed with 300 parts by weight of propylene glycol monomethyl ether acetate, Stir at 150°C for 3 hours under nitrogen atmosphere. The dispersant thus synthesized had a weight average molecular weight Mw of about 19,000 as measured by GPC.

[1-4] Synthesis Example 4: Synthesis of Dispersant D

A solution degassed with 0.5 mg of the following compound in butyl acrylate (10 ml) was heated at 80°C for 2 hours, followed by heating at 120°C for 0.5 hour. Removal of volatile components yielded oligomers with an average Mn=11. A degassed solution of 200 mg of this oligomer and 10 ml of dimethylaminoethyl methacrylate was heated at 120° C. for 1 hour. The colorless rubber-like substance obtained by removing volatile components was a block copolymer having Mn=8100 and an amine value of 86 mg-KOH/g.

[chemical formula 26]

[2] (b) Synthesis of polymers (dispersants G, H) obtained by polymerizing the compound represented by the general formula (1) as an essential monomer component

[2-1] Synthesis Example 5: Synthesis of Dispersant G

A separable flask with a cooling tube was prepared as a reaction tank, 400 parts by weight of propylene glycol monomethyl ether acetate was charged, nitrogen substitution was carried out, and the temperature of the reaction tank was raised to 90°C by heating with an oil bath while stirring.

On the other hand, in the monomer tank, add 40 parts by weight of dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, 32 parts by weight of methacrylic acid, 66 parts by weight Parts of methyl methacrylate, 62 parts by weight of benzyl methacrylate, 2.6 parts by weight of tert-butyl peroxy-2-ethylhexenoate, 40 parts by weight of propylene glycol monomethyl ether acetate, in In the chain transfer agent tank, add 5.2 parts by weight of n-dodecane mercaptan, 27 parts by weight of propylene glycol monomethyl ether acetate, after the temperature of the reaction tank is stabilized at 90°C, start to carry out from the monomer tank and the chain transfer agent tank. Add dropwise to initiate polymerization. While maintaining the temperature at 90°C, the dropwise addition was performed over 135 minutes, and 60 minutes after the completion of the dropwise addition, the temperature was raised, and the reaction tank was adjusted to 110°C. After maintaining at 110° C. for 3 hours, it was cooled to room temperature to obtain a 30% by weight polymer solution having a weight average molecular weight of 17,000 and an acid value of 103 mgKOH/g.

[2-2] Synthesis Example 6: Synthesis of Dispersant H

Prepare a detachable flask with a cooling tube as a reaction tank. On the other hand, prepare a monomer tank in which 60 parts of dimethyl-2,2'-[oxobis(methylene )] bis-2-acrylate, 60 parts of methacrylic acid, 80 parts of benzyl methacrylate, 4 parts of tert-butylperoxy-2-ethylhexenoate (manufactured by NOF Corporation) "Perbutyl O"), 60 parts of propylene glycol monomethyl ether acetate, prepare the chain transfer agent dropping tank, the chain transfer agent dropping tank is stirred and mixed with 8 parts of n-dodecane mercaptan, 32 parts of propylene glycol monomethyl ether Methyl ether acetate.

After adding 375 parts of propylene glycol monomethyl ether acetates to the reaction tank and performing nitrogen substitution, it heated with an oil bath, stirring, and raised the temperature of the reaction tank to 90 degreeC. After the temperature of the reaction tank was stabilized at 90° C., dropwise addition from the monomer tank and the chain transfer agent tank was started to start polymerization. While maintaining the temperature at 90°C, the dropwise addition was performed over 135 minutes, and 60 minutes after the completion of the dropwise addition, the temperature was raised, and the reaction tank was adjusted to 110°C. After maintaining at 110° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen=5/95 (v/v) was started. Then, add 56 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 0.8 parts of triethylamine in the reaction tank, directly The reaction was carried out at 110°C for 9 hours. Then, 128 parts of diglyme was added and cooled to room temperature to obtain a polymer solution with a concentration of 30%. The polymer had a weight average molecular weight of 19000 and an acid value of 71 mgKOH/g.

[3] (b) Synthesis of polymers (dispersants I to K) obtained by polymerizing monomer components in which the compound represented by the general formula (2) is an essential component

[3-1] Synthesis Example 7: Synthesis of Dispersant I

212.28 parts of propylene glycol monomethyl ether acetate and 9 parts of V-59 (an azo polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) were added to the reaction vessel, and the temperature was raised to 80° C. under a nitrogen atmosphere for 2 hours. 46.2 parts of a 40% solution of a compound represented by the following formula (hereinafter referred to as "compound A") in methyl ethyl ketone, 83.03 parts of benzyl methacrylate, 31.45 parts of methyl methacrylate, and 27.05 parts of methacrylic acid were added dropwise, Stirring was further performed for 4 hours to obtain a polymerization reaction liquid. The weight average molecular weight measured by GPC of the binder resin thus obtained was 15,000 in terms of polystyrene, and the acid value was 107 when it neutralized and titrated with KOH.

<Compound A>

[chemical formula 27]

[3-2] Synthesis Example 8: Synthesis of Dispersant J

220.73 parts of propylene glycol monomethyl ether acetate and 10 parts of V-59 (an azo polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) were added to the reaction vessel, and the temperature was raised to 80° C. under a nitrogen atmosphere for 2 hours. 32.13 parts of a 40% solution of methyl ethyl ketone, 57.76 parts of benzyl methacrylate, 21.88 parts of methyl methacrylate, and 44.21 parts of methacrylic acid were added dropwise, and stirred for another 4 hours to obtain a polymerization reaction solution .

Then, add 23.30 parts of benzyl methacrylate, 0.2 parts of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 0.4 parts of triethylamine in the reaction tank, directly in The reaction was carried out at 110°C for 9 hours. Then, 128 parts of diglyme was added and cooled to room temperature to obtain a polymer solution with a concentration of 40%. The polymer had a weight average molecular weight of 12000 and an acid value of 127 mgKOH/g.

[3-3] Synthesis Example 9: Synthesis of Dispersant K

220.73 parts of propylene glycol monomethyl ether acetate and 10 parts of V-59 (an azo polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) were added to the reaction vessel, and the temperature was raised to 80° C. under a nitrogen atmosphere for 2 hours. 32.13 parts of a 40% solution of a compound represented by the following formula (hereinafter referred to as "compound B") in propylene glycol monomethyl ether acetate, 57.76 parts of benzyl methacrylate, 21.88 parts of methyl methacrylate, 44.21 parts part of methacrylic acid, and then stirred for 4 hours to obtain a polymerization reaction liquid.

Then, add 23.30 parts of benzyl methacrylate, 0.2 parts of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 0.4 parts of triethylamine in the reaction tank, directly in The reaction was carried out at 110°C for 9 hours. Then, 128 parts of diglyme was added and cooled to room temperature to obtain a polymer solution with a concentration of 40%. The polymer had a weight average molecular weight of 13000 and an acid value of 113 mgKOH/g.

<Compound B>

[chemical formula 28]

[4] Other dispersants (synthesis of dispersants L and M)

[4-1] Synthetic agent 10: Synthesis of dispersant L

145 parts by weight of propylene glycol monomethyl ether acetate was stirred while nitrogen substitution, and the temperature was raised to 80°C. 20 parts by weight of polymethyl methacrylate macromonomer, 15 parts of 2-hydroxyethyl methacrylate, 10 parts of benzyl methacrylate and 35 parts of methacrylic acid were added dropwise thereto, and the stirring was continued for 2 hours. Then, add 155 parts by weight of propylene glycol monomethyl ether acetate, add 0.2 parts by weight of p-methoxyphenol, 1.5 parts by weight of triphenylphosphine and dissolve, then add 31 parts by weight of (3,4-epoxycyclohexyl ) methacrylate, reacted at 85° C. for 24 hours to obtain a dispersed resin solution with ethylenically unsaturated groups on the side chain. The dispersion resin thus obtained had a weight average molecular weight Mw of about 14,000 as measured by GPC.

[4-2] Synthesis Example 11: Synthesis of Dispersant M

35 parts of propylene glycol monomethyl ether acetate, 8.8 parts of 1-methoxy-2-propanol, 1.5 parts of V-59 (an azo polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) were added to the reaction vessel ), heated up to 80°C under a nitrogen atmosphere, and added dropwise 9.5 parts of benzyl methacrylate, 6.5 parts of methyl methacrylate, 3.5 parts of 2-hydroxyethyl methacrylate, and 10.7 parts of methacrylic acid over 2 hours. Stirring was further performed for 4 hours to obtain a polymerization reaction liquid. Add 25.5 parts of propylene glycol monomethyl ether acetate to the polymerization reaction solution, add 0.05 parts of p-methoxyphenol, 0.3 parts of triphenylphosphine and dissolve them, then add 17.5 parts of (3,4-epoxy ring Hexyl) methacrylate was reacted at 85°C for 24 hours to obtain a dispersed resin solution with ethylenically unsaturated groups on the side chain. The binder resin thus obtained had a weight average molecular weight Mw of about 18,000 as measured by GPC, and an acid value of 50 when neutralized and titrated with KOH. The rate of introduction of carboxylic acid by (3,4-epoxycyclohexyl)methacrylate was 66% from the acid values before and after the reaction.

[5] Preparation of Pigment Dispersion

[5-1] Examples 1-4, 9-19, Comparative Examples 1, 3, 4

7.20 parts by weight of C.I. Pigment Green 36 as a colorant, 3.09 parts by weight of C.I. Pigment Yellow 150, 60.00 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and solid content in terms of dispersant A total of 1.29 parts by weight of the dispersant (a) or dispersant E described in Table-1, 3.43 parts by weight of the dispersant (b) or dispersant L, M described in Table-1, 225 parts by weight of the diameter of 0.5mm The zirconia beads were dispersed for 6 hours with a paint shaker to prepare a green pigment dispersion.

[5-2] Examples 5-8, Comparative Examples 2, 5, 6

6.00 parts by weight of C.I. Pigment Green 36 as a coloring material, 2.57 parts by weight of C.I. Pigment Yellow 150, 60.00 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and solid content in terms of dispersant A total of 2.14 parts by weight of the dispersant (a) or dispersant F described in Table-1, 4.29 parts by weight of the dispersant (b) or dispersant L, M described in Table-1, 225 parts by weight of the diameter of 0.5mm The zirconia beads were dispersed with a pigment mixer for 6 hours to prepare a green pigment dispersion.

[5-3] Embodiment 20, 21, Comparative Example 7

9.74 parts by weight of C.I. Pigment Blue 15:6 as a colorant, 60.00 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and a total of 2.37 parts by weight in terms of solid content as a dispersant were filled in a stainless steel container. The dispersant (a) recorded in -1, the dispersant (b) recorded in Table-1 of 3.16 parts by weight or the dispersant M, the diameter of 225 parts by weight are zirconia beads of 0.5 mm, dispersed for 6 hours with a pigment shaker, Prepare a blue pigment dispersion.

[6] Viscosity change of pigment dispersion

The viscosity (20 rpm) of the pigment dispersion liquid after it left still for 7 days in the thermostat of 23 degreeC immediately after manufacture was measured with Toki Sangyo Co., Ltd. E type "RE-80L". Comparing the viscosities of the pigment dispersion liquids of Examples and Comparative Examples and the rate of change in viscosity within 7 days, those of 1.7% or more were regarded as ○, those of 1.7% or more but less than 5% were regarded as △, and those of 5% or more but less than 10% were regarded as × , more than 10% as ××. The results are shown in Table-1.

[Table 1]

Table 1 Dispersant (a) Dispersant (b) other dispersants Pigment dispersion Colored resin composition (resist) Dispersant Proportion relative to colorant (%) Dispersant Proportion relative to colorant (%) Dispersant Proportion relative to colorant (%) Viscosity change resolubility Surface smoothness (Ra) Scum crumble Example 1 A 12.5 G 33.3 - - ○ ○ 3.3 ○ ○ Example 2 B 12.5 G 33.3 - - ○ ○ 2.9 ○ ○ Example 3 C 12.5 G 33.3 - - ○ ○ 3.2 ○ ○ Example 4 D. 12.5 h 33.3 - - ○ ○ 4.5 ○ ○ Example 5 A 25 G 50 - - ○ ○ 4.7 △ ○ Example 6 B 25 G 50 - - ○ ○ 5.2 △ ○ Example 7 C 25 G 50 - - ○ ○ 5.5 △ ○ Example 8 D. 25 h 50 - - ○ ○ 5.8 ○ ○ Example 9 A 12.5 G 33.3 - - ○ ○ 3.5 ○ ◎ Example 10 B 12.5 G 33.3 - - ○ ○ 3.2 ○ ◎ Example 11 C 12.5 G 33.3 - - ○ ○ 4.0 ○ ◎ Example 12 D. 12.5 h 33.3 - - ○ ○ 3.0 ○ ◎ Example 13 A 12.5 I 33.3 - - ○ ○ 3.4 ○ ○ Example 14 B 12.5 I 33.3 - - ○ ○ 3.3 ○ ○ Example 15 C 12.5 I 33.3 - - ○ ○ 3.7 ○ ○ Example 16 D. 12.5 J 33.3 - - ○ ○ 4.8 ○ ○ Example 17 C 12.5 J 33.3 - - ○ ○ 3.3 ○ ○ Example 18 C 12.5 I 33.3 - - ○ ○ 3.1 ○ ○ Example 19 A 12.5 K 33.3 - - ○ ○ 4.0 ○ ◎ Example 20 A 25 I 33.3 - - ○ ○ 2.1 ○ ◎ Example 21 A 25 K 33.3 - - ○ ○ 1.9 ○ ◎ Comparative example 1 - - G 33.3 E1) 12.5 ×× - - - - Comparative example 2 - - G 50 F2) 25.0 ×× - - - - Comparative example 3 A 12.5 - - L 33.3 x x - △ ○ Comparative example 4 A 12.5 - - m 33.3 x x - △ △ Comparative Example 5 A 25 - - L 50 ○ △ 5.8 x ◎ Comparative example 6 A 25 - - m 50 ○ △ 5.1 x ○ Comparative Example 7 A 25 - - m 33.3 x x 2.4 △ ◎

¹⁾ Dispersant E represents polyether phosphoric acid amine salt "DA375" manufactured by Kusumoto Kasei Co., Ltd.

²⁾ Dispersant F represents "Disperbyk161" manufactured by Byk-Chemicals.

[7] Preparation of colorant resin composition

Mix other ingredients in the above pigment dispersion,

(i) Examples 1-4, 13-17, 19, Comparative example 1, 3, 4 The colored resin composition shown in Table-2 was prepared.

(ii) Examples 5-8, Comparative Examples 2, 5, and 6 The colored resin compositions shown in Table-3 were prepared.

(iii) Examples 9-12 Colored resin compositions shown in Table-4 were prepared.

(iv) Examples 20, 21, and Comparative Example 7 Colored resin compositions shown in Table-5 were prepared.

In addition, in Example 18, it carried out similarly to Example 15 except having used the dispersing agent I instead of the binder X of Example 15 as a binder resin.

[Table 2]

Table-2 (Examples 1-4, 13-17, 19, Comparative Examples 1, 3, 4) type of ingredient The details of the ingredient Compounding amount (parts by weight) colorant The above pigment dispersion 58.35 solvent Propylene Glycol Monomethyl Ether Acetate 34.99 Dispersant Recorded in Table-1 binder resin Binder Resin X ^* 3.51 monomer dipentaerythritol hexaacrylate 3.16 Photopolymerization initiator type component 1 2-Mercaptobenzothiazole 0.69 Photopolymerization initiator type component 2 Methyl p-dimethylaminobenzoate 0.69 Photopolymerization initiator type component 3 Michler's ketone 0.69

[Note] ^* Binder resin X: A compound in which 3,4-epoxycyclohexylmethyl methacrylate was added to a copolymer of benzyl methacrylate/methacrylic acid=7/3, Mw=25000 , the acid value is 100mg-KOH/g.

[table 3]

Table-3 (Examples 5-8, Comparative Examples 2, 5, 6) type of ingredient The details of the ingredient Compounding amount (parts by weight) colorant The above pigment dispersion 70.01 solvent Propylene Glycol Monomethyl Ether Acetate 25.19 Dispersant Recorded in Table-1 binder resin Binder Resin X ^* 1.54 monomer dipentaerythritol hexaacrylate 2.87 Photopolymerization initiator type component 1 2-Mercaptobenzothiazole 0.63 Photopolymerization initiator type component 2 Methyl p-dimethylaminobenzoate 0.63 Photopolymerization initiator type component 3 Michler's ketone 0.63

[Note] ^* Binder resin X: A compound in which 3,4-epoxycyclohexylmethyl methacrylate was added to a copolymer of benzyl methacrylate/methacrylic acid=7/3, Mw=25000 , the acid value is 100mg-KOH/g.

[Table 4]

Table-4 (Example 9～12) type of ingredient The details of the ingredient Compounding amount (parts by weight) colorant The above pigment dispersion 58.35 solvent Propylene Glycol Monomethyl Ether Acetate 34.99 Dispersant Recorded in Table-1 binder resin Binder Resin Y ^** 3.51 monomer dipentaerythritol hexaacrylate 3.16 Photopolymerization initiator type component 1 2-Mercaptobenzothiazole 0.69 Photopolymerization initiator type component 2 Methyl p-dimethylaminobenzoate 0.69 Photopolymerization initiator type component 3 Michler's ketone 0.69

[Note] ^** Binder resin Y: The resin in Synthesis Example 6 (dispersant H) was used as the binder resin.

[table 5]

Table-5 (embodiment 20, 21, comparative example 7) type of ingredient The details of the ingredient Compounding amount (parts by weight) colorant The above pigment dispersion 31.7 solvent Propylene Glycol Monomethyl Ether Acetate 57.4 Dispersant Recorded in Table-1 binder resin Binder Resin X ^** 7.68 monomer dipentaerythritol hexaacrylate 4.54 Photopolymerization initiator type component 1 2-Mercaptobenzothiazole 0.71 Photopolymerization initiator type component 2 Methyl p-dimethylaminobenzoate 0.71 Photopolymerization initiator type component 3 Michler's ketone 0.71

[8] Evaluation of resolubility

As an alternative method for evaluating the presence or absence of impurity defects in the die coating method, the following resolubility evaluation was performed.

The colored resin compositions of the respective examples and comparative examples were coated on a 50 mm square glass substrate by a spin coating method with a dry film thickness of 2.5 μm, and air-dried for 60 minutes. Then, 6.25 g of the solvent forming the coloring composition was immersed for 3 minutes to redisperse it, and 10 minutes after the start of immersion, the particle size distribution was measured with Microtrac UPA manufactured by Nikkiso, and the volume average particle size mv was calculated. Those whose volume average particle diameter mv was less than 200 nm were rated as ◯, and those whose volume average particle diameter mv was 200 nm or more were rated as ×. The results are shown in Table-1.

In addition, when the incidence of impurity defects in the die coating method is 0, the volume average particle diameter mv corresponding to resolubility is 200 nm or less.

As can be seen from Table-1, the volume average particle diameter mv was less than 200 nm in all the colored resin compositions of Examples. In addition, Comparative Examples 1 and 2 were poor in dispersibility and could not be evaluated. From the above results, it was confirmed that the invention of the present application can suppress impurity defects caused by die coating.

[9] Manufacture of color filters

The coloring composition was applied by spin coating on each of glass substrates on which chrome was vapor-deposited, and prebaked for 3 minutes on a hot plate at 80°C. During coating, the rotational speed was adjusted so that the color coordinate y=0.595 after drying.

In addition, regarding Examples 20, 21, and Comparative Example 7, the rotational speed was adjusted so that the color coordinate y=0.12.

Next, the sample was exposed at 60 mj/cm ² through a mask pattern from a high-pressure mercury lamp, and then developed at a developer temperature of 23° C. using a 0.04 wt % potassium hydroxide aqueous solution. After developing, rinse with sufficient water and dry with clean air. Then, post-baking was performed for 30 minutes in an oven at 230°C. The film thickness after drying was about 1.8 μm.

[10] Evaluation of pixel surface smoothness

The arithmetic mean roughness (Ra) of 12.5 μm square was measured for each pixel of the color filter obtained in the above [9] using an atomic force microscope SPA300 manufactured by Seiko Instruments. The results are shown in Table-1. In addition, Comparative Examples 1 to 4 were poor in dispersibility and could not be evaluated.

[11] Scum Evaluation

The sample obtained in the above [9] was wiped 10 times with a dust-free cloth impregnated with 100% by weight ethanol (Traysee MK dust-free cloth manufactured by Toray Co., Ltd.). The above-mentioned dust-free cloth was fixed to the front end of a 1 cm x 1 cm resin-made square material, and used by impregnating it with 0.1 cc of ethanol using a water suction tube. Adhesion of the pigment to the lint-free cloth was observed visually, and whether or not the coloring composition remained in the non-image portion after development was evaluated by the following criteria. The results are shown in Table-1.

○: Adhesion of the pigment to the dust-free cloth was not observed at all

△: Adhesion of a little pigment to the dust-free cloth was found

×: Adhesion of the pigment to the dust-free cloth is clearly observed

It can be confirmed from Table-1 that no or a little residue was found by visual inspection in the color filter using the colored resin composition of the example. On the contrary, Comparative Examples 1 and 2 had poor dispersibility and could not be evaluated. In the colored resin compositions of Examples 5 and 6, residues were clearly observed visually.

[12] Evaluation of "cutout"

Observing 20 lines alternately having lines of width 50 μm and length of 500 μm and spaces on the sample obtained in [9] above, the linearity was slightly poor and the lines had pits (= cutoffs) of 2 μm or more were counted. the number of .

◎: less than 20

○: 21 to 50 pieces

△: 51 to 100 pieces

×: 101 or more

In summary, it can be confirmed from Table-1 that the dispersion stability of the colorant dispersion liquid of the present invention is good (no viscosity change), and the impurity defect suppression effect, curability, scum prevention effect and cut-off effect of the colored resin composition of the present invention are confirmed. The preventive effect is also excellent.

Although the present invention was described using specific embodiments, it is obvious to those skilled in the art that various changes and modifications can be made without departing from the intention and scope of the present invention.

In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2004-327629) filed on November 11, 2004, and the Japanese Patent Application (Japanese Patent Application No. 2005-249271) filed on August 30, 2005, all of which are cited content.

Industrial Applicability

From the following reasons (1) to (4), the present invention is highly likely to be industrially applicable in various fields of colorant dispersion liquid, photosensitive coloring composition, color filter, and liquid crystal display device.

(1) According to the present invention, it is possible to provide a colorant dispersion that, when coated on a substrate, does not leave undissolved matter of the colored resin composition on the non-image portion of the substrate, and is compatible with the substrate. Adhesiveness is also excellent, and it does not reduce the image forming ability such as curability, and can manufacture a color filter with high concentration and low film thickness. In addition, when coating by die coating method, it can suppress the The dry condensation at the front end makes it possible to manufacture color filters with high yield.

(2) According to the present invention, it is possible to provide a colored resin composition that does not leave undissolved matter of the colored resin composition on the non-image portion of the substrate when the composition is coated on the substrate, and the adhesion to the substrate is It is also excellent, and does not reduce the image forming ability such as curability, and can manufacture color filters with high concentration and low film thickness. In addition, when coating by die coating method, it can suppress the front end of the die lip. Dried and coagulated, color filters can be manufactured with high yield.

(3) According to the present invention, it is possible to provide a high-quality color filter with high concentration and low film thickness, which does not leave undissolved matter of the colored resin composition or die-coating on the non-pixel portion of the substrate. Impurities produced due to drying and condensation during cloth.

(4) According to the present invention, a high-quality liquid crystal display device using the color filter substrate described in (3) above can be provided.

Claims (8)

1. colorant dispersion liquid, this dispersion liquid contains (A) colorant, (B) dispersion agent and (C) solvent, wherein, (B) dispersion agent contains at least: (a) contain the graft copolymer of nitrogen-atoms and/or acrylic block copolymer and (b) with the compound of following general formula (1) and/or (2) expression serve as must composition the polymkeric substance that is polymerized of monomer component:

[Chemical formula 1]

In the formula (1), R ^1aAnd R ^2aIndependent separately, it is 1～25 alkyl that the expression hydrogen atom maybe can have substituent carbonatoms;

[Chemical formula 2]

In the formula (2), R ^1bThe expression hydrogen atom maybe can have substituent alkyl, L ³The linking group or the Direct Bonding of expression divalent, X represent following formula (3) expression group or can substituted adamantyl;

[chemical formula 3]

In the formula (3), R ^2b, R ^3b, and R ^4bExpression hydrogen atom, hydroxyl, halogen atom, amino or organic group, L ¹And L ²The linking group of expression divalent, L ¹, L ²And L ³In also can interosculate more than 2 and form ring.

2. according to the described colorant dispersion liquid of claim 1, wherein, (B) content of dispersion agent is below the 95 weight % with respect to (A) colorant.

3. according to claim 1 or 2 described colorant dispersion liquids, wherein, (a) containing the graft copolymer of nitrogen-atoms and/or the content of acrylic block copolymer is below the 40 weight % with respect to (A) colorant.

4. according to each described colorant dispersion liquid in the claim 1～3, wherein, the content of the polymkeric substance that (b) obtains as monomer component polymerization that must composition with the compound of above-mentioned general formula (1) and/or (2) expression is below the 55 weight % with respect to (A) colorant.

5. a colored resin composition wherein uses any described colorant dispersion liquid in the claim 1～4.

6. colored resin composition, said composition contains (A) colorant, (B) dispersion agent and (C) solvent, wherein, (B) dispersion agent contains at least: (a) contain the graft copolymer of nitrogen-atoms and/or acrylic block copolymer and (b) with the compound of following general formula (1) and/or (2) expression serve as must composition the polymkeric substance that is polymerized of monomer component:

[Chemical formula 1]

In the formula (1), R ^1aAnd R ^2aIndependent separately, it is 1～25 alkyl that the expression hydrogen atom maybe can have substituent carbonatoms;

[Chemical formula 2]

In the formula (2), R ^1bThe expression hydrogen atom maybe can have substituent alkyl, L ³The linking group or the Direct Bonding of expression divalent, X represent following formula (3) expression group or can substituted adamantyl;

[chemical formula 3]

In the formula (3), R ^2b, R ^3b, and R ^4bExpression hydrogen atom, hydroxyl, halogen atom, amino or organic group, L ¹And L ²The linking group of expression divalent, L ¹, L ²And L ³In also can interosculate more than 2 and form ring.

7. a colour filter wherein uses claim 5 or 6 described colored resin compositions.

8. a liquid crystal indicator wherein uses the described colour filter of claim 7.