KR20050099535A - Coloring resin composition, color filter, and liquid-crystal display - Google Patents

Abstract

A coloring resin composition which has satisfactory transparency, is less apt to leave a coloring resin composition residue remaining undissolved in the nonimage areas on a substrate, and has excellent adhesion to the substrate. It is inhibited from generating foreign matters such as dried agglomerates in application by die coating and is capable of evenly forming color pixels with a high density. The coloring resin composition comprises a colorant, a solvent, a dispersant, and a binder resin, and is characterized in that the binder resin comprises a nitrogen-free binder resin having a structure formed by causing the epoxy group of an epoxidized unsaturated compound (b) to add to each of carboxy groups of a carboxylated resin (a) and the dispersant comprises a nitrogenous dispersant, the proportion of the nitrogenous dispersant to the colorant being 0.01 to 0.5 by weight.

Description

Colored resin composition, color filter and liquid crystal display device {COLORING RESIN COMPOSITION, COLOR FILTER, AND LIQUID-CRYSTAL DISPLAY}

The present invention relates to a colored resin composition, a method of manufacturing the same, a color filter, and a liquid crystal display device. More specifically, the coloring which is excellent in transmittance | permeability, has high pattern adhesiveness at the time of image development, little residual to a non-image part after image development, and suppresses generation | occurrence | production of the dry aggregated mass at the tip of a die lip at the time of application | coating by a diecoat. A resin composition, a color filter in which a pixel is formed using this colored resin composition, and a liquid crystal display device provided with this color filter.

Background Art Conventionally, pigment dispersion, dyeing, electrodeposition, and printing methods are known as methods for producing color filters used in liquid crystal displays and the like. Especially, the pigment dispersion method which has the outstanding characteristic on average is the most widely employ | adopted from a viewpoint of spectral characteristics, durability, a pattern shape, and precision.

Pigment dispersion method is normally performed in the following procedures. First, a black matrix is formed on a transparent support such as a glass substrate by a metal light shielding film such as chromium or chromium oxide, and then, for example, a colored resin composition in which red pigment is dispersed (hereinafter, these compositions are referred to as "color resist"). When applied to the entire surface by a spin coat method or the like and exposed after exposure using a mask, a red pixel is obtained. Three colors of pixels are formed by applying, exposing and developing the blue and green pixels in the same order. Since the black matrix portion is concave between the pixels, a protective film is often formed by covering the surface with a transparent resin such as an epoxy resin or an acrylic resin for smoothing, but a protective film may not be formed. A transparent conductive film such as an ITO (indium tin oxide) film is formed on the protective film by a method such as sputtering or vacuum deposition (on the pixel and the black matrix when the protective layer is not formed).

In recent years, the above-mentioned pigment dispersion method is often adopted even when forming a black matrix. Specifically, a color filter is manufactured by apply | coating, exposing, and developing the coloring resin composition (henceforth this composition may be described as "black resist") which disperse | distributed black pigment.

Recently, the trend of technological innovation is rapid, and high permeability and high concentration are required for color filters. In order to form a high permeable color filter, it is necessary to increase the dispersion degree of a color material, and for this reason, the nitrogen atom containing dispersant excellent in dispersibility became widely used. In order to form a highly permeable and high concentration color filter, it is necessary to raise the color material concentration in the colored resin composition to be used, and also to increase the content concentration of the nitrogen atom-containing dispersant at the same time. However, only by using these dispersants, sufficient liquid stability is not obtained, and there is a problem that yellowing occurs in the heating step in manufacturing the color filter, thereby lowering the transmittance of the pixel. On the other hand, normally, a colored resin composition is manufactured by the process of mixing and disperse | distributing a coloring material and a dispersing agent, and preparing a colored resin composition, and the process of mixing a solvent, binder resin, etc. with this colored resin composition, but the binder mixed with a colored resin composition As resin, it is known to use resin which consists of a structure which adds the epoxy part of an epoxy-group-containing unsaturated compound to the carboxyl group part of resin which has a carboxyl group (for example, see WO96-23237). However, in this photosensitive resin composition, the said problem was not fully solved.

In addition, in the liquid crystal display device, the demand for high-speed response for moving picture display has increased, and the cell gap between the color filter and the opposing substrate tends to be narrowed, that is, the amount of liquid crystal per area of the cell has decreased.

In the case where the nitrogen atom-containing dispersant is contained in the colored resin composition in a large amount, elution occurs into the liquid crystal through the ITO film or the like after the liquid crystal cell formation, or a problem of lowering the voltage holding ratio of the liquid crystal occurs. In addition, when the high-speed response proceeds, the amount of liquid crystal per cell area decreases as described above, so that the voltage holding ratio further decreases. When the voltage holding ratio of the liquid crystal is lowered, it is said to cause display defects such as display unevenness and partial deterioration (see, for example, Japanese Patent Application Laid-Open No. 2000-292920 and Japanese Patent Application Laid-Open No. 2000-311228), in particular, high permeability, high concentration, This is a major problem in high-speed liquid crystal display devices.

In order to solve the problem of display nonuniformity, the method of using the dispersing agent which has a decomposition temperature which is -20 degreeC or more higher than the temperature in the colored layer formation process is proposed as a dispersing agent contained in a colored resin composition. Here, the decomposition temperature is defined as the heating temperature when the amount of extraction of organic impurities when the colored layer is extracted with liquid crystal when the colored resin composition containing the dispersant is heat treated to form 100 ppm ( See, for example, Japanese Patent Laid-Open No. 2000-171784).

However, in the case where a nitrogen atom-containing dispersant is used, the voltage holding ratio decreases and the problem of display unevenness sometimes increases in this method.

Moreover, in order to form a high concentration color filter, it was necessary to raise the color material density | concentration in the colored resin composition to be used. On the other hand, as a result of relatively reduced components contributing to image forming properties such as photosensitivity and solubility, the original image forming performance is lost, and undissolved matters of the colored resin composition tend to remain in the non-image portion after development. If the undissolved product of the colored resin composition remains in the non-pixel portion on the substrate, the resulting color filter causes a decrease in transmittance, contrast and the like, and in the case of remaining in the pattern edge portion, peeling of the ITO film or deterioration of the sealing property in the liquid crystal celization step It was supposed to affect the post-process, such as causing.

In order to solve such a subject, the method of adding the organic carboxylic acid compound of molecular weight 1000 or less to a colored resin composition is proposed (for example, refer Unexamined-Japanese-Patent No. 3293171). Using this method, the effect of reducing the residual amount of undissolved matters on the non-pixel portion after development was recognized for some colored resin compositions formed by dispersing a pigment with a binder polymer.

On the other hand, various new technologies have also been developed for the manufacturing method of the color filter. In the pixel formation process, for example, about the application | coating process of a resist, the resist was dripped at the center part of a board | substrate, and it was the mainstream until it uniformized by the spin coat method so far. However, in recent years, the coating technique by the die coating method has been developed and partially put into practical use in view of the increase in the amount of resist used as the substrate is enlarged and the limitation of the spin coater on the device (such as the ability of the motor).

However, the technique of applying the resist by the die coating method is conventionally used, for example, in the manufacture of floppy disks (registered trademarks) and the like. Usually, when continuous application of a coating liquid such as a resist onto a medium such as a polymer film is performed. It is preferably employed.

On the other hand, in the case of sheet coating such as a color filter, the method of applying the resist is intermittent coating, and the tip of the die lip is repeatedly wetted and dried. When the color resist or black resist which disperse | distributed the pigment of high concentration dries at the tip of a die lip, a pigment density increases rapidly, and agglomeration of a pigment may generate | occur | produce. These flocculated agglomerates adhere to the die lip tip and, when the resist is ejected again, are peeled off the lip tip and moved onto the substrate, and remain on the substrate until the end without being easily removed in a subsequent process. Such agglomerated mass becomes a pixel defect of a color filter, and causes a quality defect. This poor phenomenon is one of the phenomena to be avoided because the yield of the product is lowered.

<Start of invention>

MEANS TO SOLVE THE PROBLEM The present inventors used the thing which the nitrogen atom in a nitrogen atom containing dispersant has a bad influence on voltage retention, and when a nitrogen-containing functional group part is easy to decompose | disassemble and volatilize by heating, voltage retention improves rather, Therefore, the total nitrogen amount after heating as a nitrogen atom containing dispersant It was found that it is preferable to use a thing with a low residual ratio of. However, in a nitrogen atom-containing dispersant having a low residual ratio of the total amount of nitrogen after heating, even if the voltage retention is improved, the transmittance and developability may be insufficient, and depending on the application, it is preferable to use a dispersant having a high total nitrogen residual ratio. As a result, overall performance may be improved.

Further, as described in Japanese Patent No. 3293171, addition of the organic carboxylic acid compound also lowers the adhesion of the image portion as well as the non-image portion, resulting in a narrowing of the development margin, resulting in peeling of the pixel and defects of white exposure. It was found to be easy to occur. That is, it became very difficult to satisfy both the reduction of the residual amount of an unsealed product and the adhesiveness of an image, and when it was going to maintain high quality, it was the situation that the yield must be reduced.

As the performance required for the colored resin composition, not only the above-described developing characteristics but also excellent coating properties matched with the new coating method represented by recent die coats, in particular, the inhibiting ability of the dry aggregated mass have begun to be demanded.

This invention is made | formed in view of the subject mentioned above, and the objective is as follows.

(1) Even when a nitrogen atom-containing dispersant having a high residual ratio of total nitrogen after heating is used, the voltage retention of the liquid crystal decreases due to a material in direct and indirect contact with the liquid crystal layer while satisfying the requirement of high permeability and high concentration, and poor display. To provide the colored resin composition which suppressed.

(2) When apply | coating on a board | substrate, the undissolved matter of a colored resin composition remain | survives in the non-image part on a board | substrate, it is excellent in adhesiveness with a board | substrate, and foreign substances, such as a dry aggregated mass at the time of application | coating by a diecoat, etc. It provides the colored resin composition which can form the high concentration color pixel in which generation | occurrence | production of the suppression was suppressed uniformly.

(3) It provides a high quality color filter in which the undissolved matter of a colored resin composition does not remain in the non-pixel part on a board | substrate, and the foreign material etc. resulting from dry aggregation remain.

(4) To provide a high quality liquid crystal display device using the color filter substrate.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, as a result, it contains the binder resin which has a specific structure, and makes the weight ratio of the nitrogen atom containing dispersant with respect to a coloring material into a specific range, and the residual ratio of the total amount of nitrogen after heating is Even when a high nitrogen atom-containing dispersant is used, it has been found that voltage drop can be prevented and high transmittance and developability can be achieved.

In addition, by using a binder resin having a specific structure in combination with a dispersant having a specific structure, undissolved matter does not remain on the non-image portion on the substrate, and excellent adhesion to the substrate, and dry coagulation at the time of application by die coating The present inventors have found that a colored resin composition capable of uniformly forming a high concentration of colored pixels in which the occurrence of foreign matter such as lumps is suppressed has been found to complete the present invention.

In addition, by using the resin of the specific structure which was conventionally used as binder resin at the time of preparing a colored resin composition as a dispersing agent at the time of preparing a colored resin composition, liquid stability of a colored resin composition became high enough, and was produced using this. The photosensitive coloring resin composition gave the result which was excellent in developability, scumming, thermal stability, and liquid stability, and it discovered that the permeability of the formed pixel becomes further high and reached this invention.

That is, the gist of the present invention contains a nitrogen atom-free binder resin and a nitrogen atom-containing dispersant having a structure formed by adding an epoxy group of an epoxy group-containing unsaturated compound (b) to a carboxyl group of a resin (a) having a carboxyl group as a binder resin. Moreover, the weight ratio of the nitrogen atom containing dispersant with respect to a coloring material is 0.01-0.5, The colored resin composition characterized by the above-mentioned.

Moreover, another summary of this invention is a colored resin composition containing a color material, a solvent, a dispersing agent, and binder resin,

Binder resin copolymerizes 5 to 90 mol% of (A) epoxy containing (meth) acrylate, and 10-95 mol% of other radically polymerizable compounds which can be copolymerized with (B) (A) component, and is contained in the obtained copolymer Resin obtained by adding (C) unsaturated monobasic acid to 10-100 mol% of the prepared epoxy group, and then adding (D) polybasic acid anhydride to 10-100 mol% of hydroxyl groups produced when said (C) component is added. The dispersing agent is an AB block copolymer comprising (E) a urethane-based dispersant, (F) a graft copolymer containing a nitrogen atom, (G) an A block having a quaternary ammonium salt in the side chain and a B block having no quaternary ammonium salt. And / or one or more of the BAB block copolymers.

Another aspect of the present invention is a colored resin composition containing a colorant, a solvent, and a binder resin, which is coated with the colored resin composition having a film thickness of x = 0.60 in a CIE color system and calcined at 230 ° C. for 30 minutes. The Y value in the following colorimetric system is in the range represented by either of the following formulas (1) and (2),

Y≥200y-41.4 (y <0.34) (1)

Y≥100y-7.4 (y≥0.34) (2)

(Wherein Y and y represent reflectance and chromaticity in the CIE color system, respectively.)

When the pattern was formed using the colored resin composition, the minimum pattern width remaining as a linear image was 10 µm or less,

In addition, 1 kgf / cm 2 of non-pixel portion (on base glass) having an area of 10 cm 2 was fabricated using 1 cm × 1 cm of cotton composed of polyester long fibers of 3 μm or less on average, impregnated with 0.1 cc / cm 2 of ethanol. It is in the red colored resin composition characterized by the spectral reflectance of 500 nm of the pigment adhesion part when it washes by the pressure of.

Moreover, another summary of this invention is a colored resin composition containing a color material, a solvent, and binder resin,

The colored resin composition is applied to a film thickness such that the chromaticity in the CIE color system is y = 0.55, and the Y value in the color system after firing at 230 ° C. for 30 minutes is within a range represented by the following formula,

Y≥240x-7.1

(Wherein Y and x represent reflectance and chromaticity in the CIE color system, respectively.)

When the pattern was formed using the colored resin composition, the minimum pattern width remaining as a linear image was 10 µm or less,

In addition, 1 kgf / cm 2 of non-pixel portion (on base glass) having an area of 10 cm 2 was fabricated using 1 cm × 1 cm of cotton composed of polyester long fibers of 3 μm or less on average, impregnated with 0.1 cc / cm 2 of ethanol. It is in the green colored resin composition characterized by the spectral reflectance of 450 nm of the pigment adhesion part when it washes by the pressure of 95% or more.

Moreover, another summary of this invention is a colored resin composition containing a color material, a solvent, and binder resin,

The colored resin composition was applied at a film thickness such that the chromaticity in the CIE color system became y = 0.14, and after baking at 230 ° C. for 30 minutes, the Y value in the color system was in a range represented by the following formula,

Y≥20x + 16.2

(Wherein Y and x represent reflectance and chromaticity in the CIE color system, respectively.)

When the pattern was formed using the colored resin composition, the minimum pattern width remaining as a linear image was 10 µm or less,

In addition, 1 kgf / cm 2 of non-pixel portion (on base glass) having an area of 10 cm 2 was fabricated using 1 cm × 1 cm of cotton composed of polyester long fibers of 3 μm or less on average, impregnated with 0.1 cc / cm 2 of ethanol. The 550 nm spectral reflectance of a pigment adhesion part is 95% or more when it wash | cleans by the pressure of the blue coloring resin composition characterized by the above-mentioned.

Another aspect of the present invention is a color filter comprising a substrate and a pixel formed on the substrate, wherein a part or all of the pixels are formed using the colored resin composition.

This invention shows the effect enumerated below.

1. When the colored resin composition which concerns on this invention apply | coats this on a board | substrate, undissolved matter does not remain in the non-pixel part on a board | substrate, it is excellent also in adhesiveness with a board | substrate, and can form a high density color pixel uniformly. have. Moreover, even when it is apply | coated by the die-coat method, generation | occurrence | production of foreign substances, such as a dry flocculation mass, is few. In addition, since the transmittance of the formed pixels is high and the influence on the voltage holding ratio of the liquid crystal is very small, display defects such as display unevenness and partial degradation are unlikely to occur.

2. In the color filter which concerns on this invention, the undissolved matter of a colored resin composition does not remain in the non-pixel part on a board | substrate. Moreover, since the transmittance of the formed pixel is very high and the influence on the voltage holding ratio of a liquid crystal is very small, display defects, such as display nonuniformity and partial deterioration, hardly arise, and are very high quality.

3. In the liquid crystal display device according to the present invention, undissolved matters of the colored resin composition do not remain in the non-pixel portion on the substrate, and because of the high permeability of the formed pixels, and the voltage holding ratio of the liquid crystal is less likely to be uneven. It uses very high quality color filter which is hard to occur and is very high quality.

(The best mode for carrying out the invention)

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

[1] Constituents of the colored resin composition (resist)

The colored resin composition (resist) which concerns on this invention makes a coloring material, a solvent, a dispersing agent, and binder resin an essential component, and if necessary, other additives other than the said component may be mix | blended.

Hereinafter, each component is demonstrated.

[1-1] Color materials:

A color material means the material which colors the colored resin composition which concerns on this invention. Although a pigment or dye can be used as a coloring material, A pigment is preferable from a viewpoint of heat resistance, light resistance, etc.

As the pigment, pigments of various colors such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, and brown pigments can be used. Examples of the structure include organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indansrene and perylene. In addition, various inorganic pigments can also be used. Hereinafter, the specific example of the pigment which can be used is shown by a pigment number. The following "C. I. Pigment Red 2 ”and the like mean a color index (C.I.).

In red pigment, CI 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 Can be.

Among them, CI Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, and more preferably CI Pigment Red 177, 209, 224, 254 to be.

As blue pigment, CI 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 Can be mentioned.

Among them, C. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C. I. Pigment Blue 15: 6.

As green pigment, CI pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 Can be. Among these, C. I. pigment green 7, 36 is preferable.

As yellow pigment, CI 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 them, C. I. pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and more preferably C. I. pigment yellow 83, 138, 139, 150, 180.

In orange pigment, CI 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 them, C. I. pigment oranges 38, 71 are preferable.

As purple pigment, CI 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 them, C. I. pigment violet 19, 23 is preferable, and C. I. pigment violet 23 is more preferable.

Examples of other pigments include barium sulfate, lead sulfate, titanium oxide, yellow lead, bengal, chromium oxide, and the like.

Said various pigment can also use multiple types together. For example, a green pigment and a yellow pigment may be used together as a pigment for color adjustment, or a blue pigment and a purple pigment may be used together. Moreover, the average particle diameter of these pigments is 1 micrometer or less normally, Preferably it is 0.5 micrometer or less, More preferably, it is 0.25 micrometer or less.

Examples of the dye that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like. .

As an azo dye, CI acid yellow 11, CI acid orange 7, CI acid red 37, CI acid red 180, CI acid blue 29, CI direct red 28, CI direct red 83, CI direct yellow 12, CI, for example Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI disperse blue 165, CI basic blue 41, CI basic red 18, CI modern red 7, CI modern yellow 5, CI modern black 7, etc. are mentioned.

As an anthraquinone type dye, for example, CI bat blue 4, CI acid blue 40, CI acid green 25, CI reactive blue 19, CI reactive blue 49, CI disperse red 60, CI disperse blue 56, CI Disperse Blue 60 etc. are mentioned.

In addition to the above, as a phthalocyanine dye, for example, CI pad blue 5 or the like, as a quinone imine dye, for example CI basic blue 3, CI basic blue 9 and the like as a quinoline dye, for example CI Solvent yellow 33, CI acid yellow 3, CI disperse yellow 64, etc. are mentioned as a nitro type dye, for example, CI acid yellow 1, CI acid orange 3, CI disperse yellow 42, etc.

Moreover, when forming the resin black matrix of a color filter using a coloring resin composition, a black color material can be used. The black color material may be a black color material alone, or may be a mixture of red, green, blue, and the like. Moreover, these color materials can be suitably selected from an inorganic or organic pigment or dye. In the case of inorganic and organic pigments, it is preferable to disperse | distribute to 1 micrometer or less normally, Preferably it is 0.5 micrometer or less as an average particle diameter.

As a black color material which can be used independently, carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, etc. are mentioned.

Among the black color materials, carbon black is preferable from the viewpoint of light blocking rate and image characteristics. Examples of the carbon blacks include the following carbon blacks.

In Mitsubishi Chemical Corporation product, it is 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, OIL31B and the like.

As a product made by Degussa, Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V , Printex G, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170, etc. Can be mentioned.

As a product of the cabot company production, Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL0, BLACK PEARLS480, PEARLS130, VULCAN XC72R, ELFTEX-8, etc. are mentioned.

As a product of the Colombian carbon company production, RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U , RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000 and the like.

In addition, it is particularly preferable to use resin-coated carbon black for the production of resin black matrices having high optical density and high surface resistivity.

As a colorant which can be mixed to prepare a black colorant, Victoria Pure Blue (42595), Oramine O (41000), Catyron Brilliant Flavin (Basic 13), Ledin 6GCP (45160), Ledin B (45170) , Supranin OK70: 100 (50240), Eriograsin X (42080), No.120 / Rionol Yellow (21090), Rionol Yellow GRO (21090), Simulator Fast Yellow 8GF (21105), Benzidine Yellow 4T- 564D (21095), Simula Fast Red 4015 (12355), Lionol Red 7B4401 (15850), Fasten Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Leonogen red GD (Pigment Red 168), Leonol Green 2YS (Pigment Green 36), etc. are mentioned. The numbers in parentheses refer to the color index (C. I.).

In addition, when it shows with the CI number about the pigment which can be mixed, for example, CI yellow pigment 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, CI orange pigment 36, 43, 51, 55, 59, 61, CI red pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, CI Violet Pigment 19, 23, 29, 30, 37, 40, 50, CI Blue Pigment 15, 15: 1, 15: 4, 22, 60, 64, CI Green Pigment 7, CI Brown Pigment 23, 25, 26, etc. are mentioned.

The ratio of the color material to the total solids in the colored resin composition is usually 1% by weight or more, preferably 10% by weight or more, and usually 70% by weight or less, preferably 60% by weight or less. If the ratio of the colorant is too small, the film thickness against the color concentration becomes too large, which adversely affects the gap control during liquid crystal cell formation. On the other hand, when there are too many ratios of a color material, sufficient image formability may not be obtained. In addition, in this invention, "all solid content" means all components other than the solvent component mentioned later.

[1-2] Solvent:

In the colored resin composition of this invention, a solvent has a function which melt | dissolves or disperse | distributes components other than the above mix | blended if necessary other than a coloring material, a dispersing agent, and binder resin, and adjusts a viscosity.

Examples of the solvent include diisopropyl ether, mineral spirits, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, Valsol # 2, Afco # 18 Solvent, Diisobutylene, Amyl Acetate, Butyl Acetate, Afcosiner, Butyl Ether, Diisobutyl Ketone, Methylcyclohexene, Methylnonyl Ketone, Propyl Ether, Dodecane, Socal Solvent No .1 and No.2, amyl formate, dihexyl ether, diisopropyl ketone, sorbetso # 150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl Benzoate, amyl chloride, ethylene glycol diethyl ether, ethyl orthoformate, methoxymethylpentanone, methylbutyl ketone, methylhexyl ketone, methyl isobutylate, benzonitrile, ethyl propionate, methyl cellosolve acetate, Methyl iso Milk ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methyl amyl ketone, methyl isopropyl ketone, propyl pro Cypionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, 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, 3-ethoxypropionic acid Methyl, 3-methoxypropionate, 3-methoxyethylpropionate, 3-methoxypropylpropionate, 3-methoxypropionate, diglyme, ethyleneglycol acetate, ethylcarbitol, butylcarbitol, ethyleneglycol monobutylether , Propylene glycol -t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate and the like. These solvents may be used individually by 1 type, or may be used in combination of 2 or more type.

Although content of the solvent in the whole colored resin composition of this invention does not have a restriction | limiting in particular, The upper limit is 99 weight% or less normally. When the solvent exceeds 99% by weight, the colorant, the dispersant, etc. are too small to be suitable for forming a coating film. In addition, the minimum of solvent content is 75 weight% or more normally, Preferably it is 80 weight% or more, More preferably, it is 82 weight% or more in order to consider the viscosity etc. suitable for application | coating.

[1-3] Dispersant:

The dispersant in the present invention is a nitrogen atom-containing dispersant, and the residual ratio of the total amount of nitrogen when heated at 230 ° C. for 30 minutes (weight ratio of total amount of nitrogen after heating to total amount of nitrogen before heating) is usually 95% by weight or less, preferably Is a dispersant of up to 90% by weight, more preferably up to 80% by weight. In addition, the residual ratio (weight ratio of weight after heating to weight before heating) of the nitrogen atom-containing dispersant when heated at 230 ° C. for 30 minutes is preferably 95% by weight or less, and more preferably 90% by weight or less.

In the present invention, before heating at 230 ° C. for 30 minutes, drying is carried out under reduced pressure under conditions of 10 mmHg at 48 ° C. for 48 hours at 60 ° C., and the solvent component is dried to make this before heating. Then, it puts in heating furnaces, such as a circulating hot stove, and heats 230 degreeC 30 minutes. The nitrogen content before and after heating is usually measured using an elemental analyzer such as a CHN system, and the weight is usually measured by precision balance.

As the nitrogen atom-containing dispersant, a surfactant, a polymer dispersant or the like is usually used, but a polymer dispersant is particularly suitable. The polymer dispersant may be any one of a urethane-based dispersant, a graft copolymer containing a nitrogen atom, an AB block copolymer composed of an A block having a quaternary ammonium salt in the side chain and a B block having no quaternary ammonium salt, and / or a BAB block copolymer. It is preferable to contain one or more. In this invention, by using these dispersing agents and the specific binder resin mentioned later in combination, the high adhesiveness at the time of image development of the coating film and board | substrate formed with a coloring composition and suppressing the remainder of undissolved matter can be achieved, maintaining dispersion stability. .

Moreover, a dispersing agent may be used independently and may mix 2 or more types of dispersing agents. In the case of mixing two or more nitrogen atom-containing dispersants, the residual ratio is defined as the residual ratio in the total of the respective nitrogen atom-containing dispersants combined at each mixing ratio.

As a form of the nitrogen atom in a nitrogen atom containing dispersing agent, an amino group, a quaternary ammonium salt, etc. are preferable. This is because these functional groups usually have basicity and are easy to coordinate with acidic groups such as pigments and pigment derivatives, and consequently contribute to dispersion stabilization. The amine number of a dispersing agent is 2-100 KOHmg / g normally, Preferably it is 3-80KOHmg / g. If the amine value is too low, basicity is insufficient and dispersion stability is insufficient. If the amine value is too high, the voltage holding ratio of the liquid crystal is lowered, and as a result, it is not easy to cause display defects.

The weight ratio of the nitrogen atom-containing dispersant to the colorant is usually 0.01 or more and 0.5 or less. Preferably it is 0.02 or more, Preferably it is 0.3 or less, More preferably, it is 0.2 or less. Too high a ratio of dispersant may adversely affect the voltage holding ratio, and may cause display defects such as display unevenness and partial burn in. On the other hand, when the ratio of the dispersant is too small, dispersibility may not be sufficiently expressed, resulting in high transmittance and high viscosity stability. Cannot be achieved.

Next, a preferable dispersing agent is demonstrated in detail.

[1-3-1] urethane-based dispersant

Examples of the urethane-based dispersant include (1) a polyisocyanate compound, (2) a compound having one or two hydroxyl groups in the same molecule, and (3) a dispersion resin obtained by reacting a compound having active hydrogen and a trivalent amino group in the same molecule. It is preferable.

(1) polyisocyanate compound

Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tolidine di Aliphatic diisocyanates such as aromatic diisocyanates such as isocyanates, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4'-methylene Aromatic rings, such as alicyclic diisocyanate, such as bis (cyclohexyl isocyanate) and (omega), (omega)-diisocyanate dimethyl cyclohexane, xylylene diisocyanate, (alpha), (alpha), (alpha)-tetramethyl xylylene diisocyanate, Aliphatic diisocyanate having, lysine ester triisocyanate, 1,6,11-undecane Tree such as triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate Isocyanate, these trimers, water adduct, these polyol adduct, etc. are mentioned.

Preferable polyisocyanates are trimers of organic diisocyanates, most preferred are trimers of tolylene diisocyanate and trimers of isophorone diisocyanate, and these may be used alone or in combination.

As a method for producing a trimer of isocyanate, the polyisocyanates may be prepared by using a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, and the like. The method of obtaining the desired isocyanurate group-containing polyisocyanate is carried out by removing the unreacted polyisocyanate by solvent extraction and thin film distillation after terminating the trimerization by adding the catalyst poison.

(2) Compound having one or two hydroxyl groups in the same molecule

Examples of the compound having one or two hydroxyl groups in the same molecule include polyether glycols, polyester glycols, polycarbonate glycols, polyolefin glycols, and the like, in which a single terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms. And mixtures of two or more of these.

As polyether glycol, polyether diol, polyether ester diol, and these two or more types of mixtures are mentioned. As polyetherdiol, what is obtained by individual or copolymerization of alkylene oxide, for example, polyethyleneglycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, And mixtures of two or more thereof. Polyetherester diols are those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or by reacting alkylene oxides with polyester glycols, for example poly (polyoxytetra). Methylene) adipate, and the like. Most preferred as the polyether glycol are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which the single terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentylglycol, 2-methyl -1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexane Diol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexane Aliphatic glycols such as diol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, xylylene glycol, bis Aromatic glycols such as hydroxyethoxybenzene, N-meth Obtained by polycondensing N-alkyldialkanolamines such as diethanolamine), for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate and the like, or the diols Or polylactone diol or polylactone monool obtained by using a monohydric alcohol having 1 to 25 carbon atoms as an initiator, for example, polycaprolactone glycol, polymethylvalerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol are polycaprolactone glycol or polycaprolactone containing an alcohol having 1 to 25 carbon atoms as an initiator, and more specifically, a compound obtained by ring-opening addition of ε-caprolactone to monool.

Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, and the like.

Examples of the polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, and the like.

Among the compounds having one or two hydroxyl groups in the same molecule, polyether glycol and polyester glycol are particularly preferable.

The number average molecular weight of the compound which has one or two hydroxyl groups in the same molecule is 300-10,000 normally, Preferably it is 500-6,000, More preferably, it is 1,000-4,000.

(3) Compound having active hydrogen and tertiary amino group in the same molecule

Examples of the hydrogen atom directly bonded to active hydrogen, that is, an oxygen atom, a nitrogen atom or a sulfur atom, include hydrogen atoms in functional groups such as hydroxyl groups, amino groups and thiol groups, and among them, hydrogen atoms of amino groups, particularly primary amino groups, are preferable. .

Although tertiary amino group is not specifically limited, For example, the dialkylamino group which has a C1-C4 alkyl group, such as methyl, ethyl, isopropyl, n-butyl, or this dialkylamino group connects, and forms the heterocyclic structure, Group, more specifically, imidazole ring or triazole ring.

Exemplary compounds having active hydrogen and tertiary amino groups in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, and N, N-dipropyl. -1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N-dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1,4-butanediamine etc. are mentioned.

In addition, the tertiary amino group is a nitrogen-containing hetero ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, N-containing hetero 5-membered ring such as benzoxazole ring, benzothiazole ring, benzothiadiazol ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring, etc. And nitrogen-containing hetero six-membered ring. Preferred as these nitrogen-containing heterocycles are imidazole rings or triazole rings.

Specific examples of the compounds having these imidazole rings and primary amino groups include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole, and the like. have. Specific examples of the compound having a triazole ring and a primary amino group include 3-amino-1,2,4-triazole and 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1. , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5- Amino-1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4- Triazoles are preferred.

As for the preferable compounding ratio of a dispersion resin raw material, the compound which has one or two hydroxyl groups in the same molecule with respect to 100 weight part of polyisocyanate compounds is normally 10-200 weight part, Preferably it is 20-190 weight part, More preferably, The compound having 30 to 180 parts by weight and active hydrogen and tertiary amino group in the same molecule is usually 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight.

The polystyrene reduced weight average molecular weight measured by GPC of the urethane-based dispersion resin of the present invention is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. Dispersibility and dispersion stability are inferior in molecular weight 1,000 or less, solubility falls in 200,000 or more, inferior in dispersibility, and control of reaction becomes difficult.

The urethane-based dispersion resin of the present invention is produced according to a known method for producing polyurethane resin. As a solvent at the time of manufacture, Ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone, esters, such as ethyl acetate, butyl acetate, and a cellosolve, benzene Hydrocarbons such as toluene, xylene, hexane, some alcohols such as diacetone alcohol, isopropanol, second butanol, and third butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, Aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide are used.

As a catalyst at the time of manufacture, a normal urethanation reaction catalyst is used. For example, tin type, such as dibutyl tin dilaurate, dioctyl tin dilaurate, dibutyl tin dioctoate, and stanac octoate, iron type, such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine Tertiary amines, such as these, etc. are mentioned.

The amount of introduction of the compound having active hydrogen and tertiary amino groups in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g by the amine value of the dispersion resin after the reaction. More preferably, it is the range of 5-95 mgKOH / g. If the amine value is less than or equal to the above range, the dispersibility tends to be lowered, and if it exceeds the above range, developability tends to decrease. Moreover, when an isocyanate group remains in dispersion resin in the above reaction, when an isocyanate group is further crushed with an alcohol or an amino compound, since time-lapse stability of a dispersion resin becomes high, it is preferable.

Content of the said dispersing agent with respect to a coloring material component in a coloring composition is 10-300 weight% normally, Preferably it is 20-100 weight%, Especially preferably, it is 30-80 weight%. Too small a dispersant component may cause insufficient adsorption to the colorant and prevent agglomeration, and may lead to high viscosity or gelation. On the contrary, too large a film thickness becomes too thick. Neither is preferable because a defect may appear.

[1-3-2] graft copolymers containing nitrogen atoms

As a graft copolymer containing a nitrogen atom, it is preferable to have a repeating unit containing a nitrogen atom in a principal chain. Especially, it is preferable to have a repeating unit represented by Formula (I) or / and a repeating unit represented by Formula (II).

(In formula, R <_1> represents a C1-C5 alkylene group and A represents a hydrogen atom or any of following formula (III)-(V).)

In said formula (I), R <_1> represents linear or branched C1-C5 alkylene groups, such as methylene, ethylene, and propylene, Preferably it is C2-C3, More preferably, it is an ethylene group. A represents a hydrogen atom or any of the following formulas (III) to (V), but is preferably formula (III).

R ₁ In the formula (Ⅱ), A has the same meaning as R _1, A in formula (Ⅰ).

W ₁ of the formula (Ⅲ) represents an alkylene group of a linear or branched chain having 2 to 10 carbon atoms ground, particularly butylene, pentylene, and the like, is preferably an alkylene group having a carbon number of 4-7, such as hexylene. p represents the integer of 1-20, Preferably it is an integer of 5-10.

Y <_1> shows a bivalent coupling group in said Formula (IV), Especially, a C1-C4 alkylene group, such as ethylene and a propylene, and a C1-C4 alkyleneoxy group, such as ethyleneoxy and propyleneoxy, are preferable. W <_2> represents linear or branched C2-C10 alkylene groups, such as ethylene, propylene, and butylene, Especially, C2-C3 alkylene groups, such as ethylene and propylene, are preferable. Y ₂ represents a hydrogen atom or —CO—R ₂ (R ₂ represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, etc., and among these, 2 to 5 carbon atoms such as ethyl, propyl, butyl, and pentyl) Is preferably an alkyl group). q represents the integer of 1-20, Preferably it is an integer of 5-10.

The formula (Ⅴ) of the W ₃ represents a hydroxyalkyl group of 1 to 50 carbon atoms having 1 to 5 alkyl group or a hydroxyl group of 1 to 50 carbon atoms, particularly an alkyl group having a carbon number of 10 to 20 such as stearyl, monohydroxy The C10-C20 hydroxyalkyl group which has 1-2 hydroxyl groups, such as stearyl, is preferable.

It is preferable that the content rate of the repeating unit represented by Formula (I) or (II) in the graft copolymer of this invention is high, Usually, it is 50 mol% or more, Preferably it is 70 mol% or more. Although it may have both the repeating unit represented by Formula (I) and the repeating unit represented by Formula (II), and there is no restriction | limiting in particular in the content rate, Preferably it contains many repeating units of Formula (I) It is preferable. The total number of repeating units represented by formula (I) or formula (II) is usually 1 to 100, preferably 10 to 70, and more preferably 20 to 50. Moreover, you may contain repeating units other than Formula (I) and Formula (II), and an alkylene group, an alkyleneoxy group, etc. can be illustrated as another repeating unit, for example. The graft copolymers of the present invention, that the terminal is a -NH ₂ and -R ₁ -NH ₂ (R ₁ has the same meaning as R ₁₎ are preferred.

Moreover, if the graft copolymer of this invention is linear, the main chain may be branched.

As a weight average molecular weight measured by GPC of the said dispersing agent, 3000-100000 are preferable and 5000-50000 are especially preferable. If the weight average molecular weight is less than 3000, the aggregation of the colorant cannot be prevented, and the viscosity may be high or gelated. If the weight average molecular weight is more than 100000, the viscosity itself is high and the solubility in organic solvents is not preferable.

Content of the said dispersing agent with respect to the color material component in a coloring composition is 10-300 weight% normally, Preferably it is 20-100 weight%, Especially preferably, it is 30-80 weight%. If the dispersant component is too small, the adsorption to the colorant is insufficient to prevent aggregation, and if it is too high, the viscosity may be increased or gelled. On the contrary, if the dispersant component is too large, the film thickness becomes thick. Since defects may occur, neither is preferable.

The synthesis | combining method of the said dispersing agent can employ | adopt a well-known method, For example, the method of Unexamined-Japanese-Patent No. 63-30057 can be used.

[1-3-3] A-B block copolymer and / or B-A-B block copolymer consisting of an A block having a quaternary ammonium salt in the side chain and a B block having no quaternary ammonium salt

A block in a block copolymer of the dispersing agent is a quaternary ammonium salt group, preferably ^{_{-N + R 1a R 2a R 3a}} · Y - ( However, R _1a, R _2a and R _3a are each independently a hydrogen atom or Or a cyclic or chain hydrocarbon group which may be substituted, or two or more of R _1a , R _2a, and R _8a may be bonded to each other to form a cyclic structure Y ⁻ represents a large anion; It has a quaternary ammonium base group represented by). This quaternary ammonium base may be directly bonded to the main chain, or may be bonded to the main chain via a divalent linking group.

-N ⁺ R _1a R _2a R _3a Examples of the cyclic structure formed by bonding two or more of R _1a , R _2a, and R _3a to each other include, for example, a 5 to 7 membered nitrogen-containing heterocyclic monocyclic ring, or a condensed ring formed by condensing two of them. Can be. The nitrogen-containing heterocycle preferably has no aromaticity, and more preferably a saturated ring. Specifically, the following are mentioned, for example.

(In the formula, R represents any one of R _1a to R _3a .)

These cyclic structures may further have a substituent.

-N ⁺ R _1a R _2a R _3a to the desired than in R _1a ~R _3a is a phenyl group which may have a substituent or an alkyl group of 1 to 3 carbon atoms which may have a substituent.

It is preferable that A block contains the partial structure represented by following General formula (I) especially.

(In Formula (1), R _1a , R _2a, and R _3a each independently represent a hydrogen atom or a cyclic or chain hydrocarbon group which may be substituted. Or 2 of R _1a , R _2a , and R _3a) Two or more may combine with each other to form a cyclic structure, R _4a represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y ⁻ represents a large anion.)

Wherein in the general formula (1), roneun divalent linking group X, for example having 1 to 10 carbon atoms alkylene group, arylene group, -CONH-R _5a a -, -COO-R _6a - (However, R _5a and R _6a is And a direct bond, an alkylene group having 1 to 10 carbon atoms or an ether group having 1 to 10 carbon atoms (-R _7a -OR _8a- : R _7a and R _8a each independently represents an alkylene group). It is -COO-R _6a - a.

In addition, examples of the large anion Y ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .

Two or more types of partial structures containing the above-mentioned specific quaternary ammonium base may be contained in one A block. In that case, 2 or more types of quaternary ammonium base containing partial structures may be contained in either aspect of random copolymerization or block copolymerization in the A block. Moreover, the partial structure which does not contain the quaternary ammonium base may be contained in A block, and the partial structure derived from the (meth) acrylic acid ester monomer mentioned later as an example of this partial structure is mentioned.

The content in the A block of the partial structure containing no such quaternary ammonium base is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, but such a quaternary ammonium base-free partial structure is contained in the A block. Most preferably not included.

On the other hand, as a B block which comprises the block copolymer of a dispersing agent, For example, Styrene-type monomers, such as styrene and (alpha) -methylstyrene; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (Meth) acrylic acid ester monomers, such as (meth) acrylate, glycidyl ethyl acrylate, and N, N-dimethylaminoethyl (meth) acrylate; (Meth) acrylate type monomers, such as (meth) acrylic acid chloride; (Meth) acrylamide monomers such as (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, and N, N-dimethylaminoethylacrylamide; Vinyl acetate; Acrylonitrile; Allyl glycidyl ether, crotonic acid glycidyl ether; The polymer structure which copolymerized comonomers, such as N-methacryloyl morpholine, is mentioned.

It is preferable that B block is a partial structure derived from the (meth) acrylic acid ester system monomer represented especially with following General formula (II). In addition, in this specification, "(meth) acryl", "(meth) acrylate", etc. shall mean "acryl or methacryl", "acrylate or methacrylate", etc., for example, "(meth) Acrylic acid "shall mean" acrylic acid or methacrylic acid. "

(In formula (II), R _9a represents a hydrogen atom or a methyl group. R _10a represents a cyclic or chain alkyl group which may have a substituent, an allyl group which may have a substituent, or an aralkyl group which may have a substituent. Is displayed.)

2 or more types of partial structures derived from the said (meth) acrylic acid ester system monomer may be contained in one B block. Of course, the B block may further include partial structures other than these. When the partial structure derived from 2 or more types of monomer exists in the B block which does not contain a quaternary ammonium base, each partial structure may be contained in either aspect of random copolymerization or block copolymerization in the B block. When it contains partial structure other than the partial structure derived from the said (meth) acrylic acid ester monomer in a B block, content in B blocks of partial structures other than the (meth) acrylic acid ester monomer becomes like this. Preferably it is 0-50 weight %, More preferably, it is 0-20 weight%, It is most preferable that partial structures other than this (meth) acrylic acid ester monomer are not contained in B block.

Although the dispersing agent used by this invention is an A-B block or B-A-B block copolymer type high molecular compound which consists of such A block and B block, such a block copolymer is prepared by the living polymerization method shown below, for example.

Living polymerization methods include anionic living polymerization, cationic living polymerization, and radical living polymerization. In the anion living polymerization method, the polymerization active species is an anion, and is represented by the following scheme, for example.

In radical living polymerization, the polymerization active species is a radical, and is shown by the following scheme, for example.

Moreover, when synthesize | combining the dispersing agent used by this invention, Unexamined-Japanese-Patent No. 9-62002, R. 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), Ute Koichi, Hatada Koichi, Polymer Processing, 36, 366 (1987), Higashimura Toshinobu, Sawamoto Teruo, Polymer Proceedings, 46, 189 (1989) , M. Kuroki, T. Aida, J. Am. Chem. Known methods described in Sic, 109, 4737 (1987), Ada Takuzo, Inoue Yohei, Organic Synthetic Chemistry, 43, 300 (1985), D. Y Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987), and the like. Can be adopted.

Whether the dispersant used in the present invention is an AB block copolymer or a BAB block copolymer, the A block / B block ratio (weight ratio) constituting the copolymer is usually 1/99 or more, particularly 5/95 or more, and usually 80 It is preferable that it is / 20 or less, especially the range of 60/40 or less. Outside this range, it may not be possible to have good heat resistance and dispersibility.

In addition, the amount of the quaternary ammonium base in 1 g of the A-B block copolymer and the B-A-B block copolymer used in the present invention is preferably 0.1 to 10 mmol, and may not have good heat resistance and dispersibility outside this range.

Moreover, although the amino group which generate | occur | produced in the manufacturing process is contained in this block copolymer normally, the amine titer is about 1-100 mg-KOH / g. The amine number is a value expressed in mg number of KOH by neutralizing and titrating a basic amino group with an acid and corresponding to the acid value.

The acid value of this block copolymer also varies depending on the presence or absence of the acid group on which the acid value is based, but is generally low. The acid value is usually 10 mg-KOH / g or less, and its molecular weight is usually 1000 in terms of polystyrene. As mentioned above, the range of 100,000 or less is preferable. If the molecular weight of the block copolymer is less than 1000, the dispersion stability will be lowered, and if it exceeds 100,000, the developability and resolution will tend to be lowered. It is essential to be a graft copolymer containing nitrogen atoms. In this invention, by using this specific dispersing agent and specific binder resin mentioned later in combination, high adhesiveness at the time of image development of the coating film and board | substrate formed with a colored resin composition, and suppression of remainder of undissolved matter can be achieved, maintaining dispersion stability. .

Moreover, it is preferable that the dispersing agent in this invention contains a phosphate ester type dispersing agent in addition to the said block copolymer. Thereby, the solubility at the time of image development becomes favorable.

The phosphate ester may be either a primary to tertiary ester, but a primary ester is preferred from the viewpoint of dispersibility. As a structure of the part couple | bonded with phosphoric acid, the structure which has a hydroxyl group at the terminal represented by polyethers, such as polyester, such as polycaprolactone, and polyethyleneglycol, is mentioned, for example. These may be copolymers of polyester and a polyether. Moreover, you may have a double bond, such as (meth) acrylate, at the one end of a polyester chain and / or a polyether chain, and may form a copolymer with another radically polymerizable compound.

Specifically, the phosphate ester preferably has a partial structure represented by the following structural formula (3).

As a synthesis method of such a phosphate ester, it can manufacture by the method of Unexamined-Japanese-Patent No. 50-22536 and 58-128393, for example.

The molecular weight Mw of the said phosphate ester type dispersing agent is 200 or more normally and 5000 or less normally, Preferably it is the range of 1000 or less. Since it is originally added for the purpose of providing developing solubility, it is not preferable to make it too high molecular weight.

The content of the phosphate ester dispersant is usually 5 parts by weight or more, preferably 10 parts by weight or more, and usually 100 parts by weight or less, preferably 80 parts by weight or less, based on 100 parts by weight of the block copolymer. When the ratio of phosphate ester is too small, there exists a possibility that sufficient image development solubility may not be expressed. On the other hand, even if there are too many ratios of a phosphate ester, an effect is saturated and there exists a possibility that a dispersibility may fall on the contrary.

[1-4] Binder Resin

The colored resin composition which concerns on this invention is used suitably as a coating liquid at the time of apply | coating to a transparent substrate and manufacturing a color filter substrate. Below, the case where it uses as curable coloring resin composition for color filters is demonstrated as an example.

The binder resin in this invention contains any of the following resins.

[1-4-1]

In this invention, resin which has a structure which adds the epoxy part of an epoxy group containing unsaturated compound (b) to the carboxyl group part of resin (a) which has a carboxyl group can be used individually or in combination.

Although it does not specifically limit as resin (a) which has a carboxyl group, Usually, it is obtained by superposing | polymerizing the polymerizable monomer which has a carboxyl group. Examples of the polymerizable monomer having a carboxyl group include (meth) acrylic acid, (anhydride) maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, and 2-acryloyloxyethyl. Adipic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acrylo Yloxypropyl succinic acid, 2- (meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acrylic Royloxypropylmaleic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth In addition to acryloyloxybutyl phthalic acid and 2- (meth) acryloyloxybutyl maleic acid, (meth) acrylic acid has (epsilon) -caprolactone, (beta) -propiolactone, (gamma) -part Acids (anhydrides) such as (anhydride) succinic acid, (anhydride) phthalic acid and (maleic anhydride) were added to hydroxyalkyl (meth) acrylate and to monomers to which lactones such as lactone and 6-valerolactone were added. A monomer etc. are mentioned.

In these, Preferably it is (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid, More preferably, it is (meth) acrylic acid. You may use these multiple types.

Moreover, resin (a) which has a carboxyl group may copolymerize the other polymerizable monomer which does not have a carboxyl group to the polymerizable monomer which has the said carboxyl group. Although it does not specifically limit as another polymerizable monomer, Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl ( Meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl ( Meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, styrene and derivatives thereof, α- Methyl styrene, polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene It may be a recall macromonomer, macromonomer, such as polycaprolactone macromonomer or the like.

Among the above, Preferably, styrene, methyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and hydroxide Oxypropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate. You may use together multiple types.

In addition, in this specification, "(meth) acryl-", "(meth) acrylate", etc. shall mean "acryl- or methacryl-", "acrylate or methacrylate", etc., for example, (Meth) acrylic acid "shall mean" acrylic acid or methacrylic acid. "

It is preferable that resin (a) which has a carboxyl group has a hydroxyl group further from the dispersibility of a pigment. In particular, hydroxyalkyl (meth) acrylates, such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate, and glycerol mono (meth) acryl Copolymers containing a rate as a copolymerization component are preferred.

Specifically, hydroxyl groups, such as methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, and cyclohexyl maleimide, are included. Polymerizable monomer which does not contain, and hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate, and (meth A copolymer with acrylic acid etc. are mentioned.

In addition, as a specific example of preferable resin, methyl (meth) acrylate, benzyl (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylic acid ester / (meth) acrylic acid copolymers such as methacrylate, styrene / (meth) acrylic acid copolymer, styrene / α-methylstyrene / (meth) acrylic acid copolymer, cyclohexyl maleimide / (meth) acrylic acid And copolymers.

The acid value of "resin (a) which has a carboxyl group" in this invention is 30-500KOHmg / g normally, Preferably it is 40-350KOHmg / g, More preferably, it is 50-300KOHmg / g. In addition, the introduction ratio of the "resin having a carboxyl group" to the carboxyl group when adding a compound having an ethylenically unsaturated group and an epoxy group is usually 10 mol% or more, preferably 30 mol% or more, and usually 90 mol% or less, preferably 80 mol% or less. to be. If the introduction ratio is too small, sufficient dispersion performance tends not to be obtained because the side chains having ethylenically unsaturated double bonds cannot be sufficiently introduced. On the contrary, too much tends to deteriorate the solubility of the colored resin composition.

Moreover, the weight average molecular weight of polystyrene conversion measured by GPC of resin (a) which has a carboxyl group in this invention is 2000 or more normally, Preferably it is 3000 or more, More preferably, it is 4000 or more, Usually it is 100000 or less, Preferably it is 80000 Hereinafter, More preferably, it is 50000 or less. When the weight average molecular weight is too small, liquid stability is inferior, and when too large, the solubility of a colored resin composition tends to deteriorate.

An epoxy group containing unsaturated compound (b) means the compound which has an ethylenically unsaturated group and an epoxy group in 1 molecule.

As an epoxy group containing unsaturated compound (b), for example, glycidyl (meth) acrylate, allyl glycidyl ether, (alpha)-ethyl acrylate glycidyl, crotonyl glycidyl ether, (iso) crotonic acid glycidyl Although acyclic epoxy group containing unsaturated compounds, such as ether and 4-hydroxybutyl (meth) acrylate glycidyl ether, are mentioned, An alicyclic epoxy group containing unsaturated compound is preferable at the point of heat resistance and dispersibility.

Here, as an alicyclic epoxy group containing unsaturated compound, the alicyclic epoxy group is, for example, a 2,3-epoxycyclopentyl group, a 3,4-epoxycyclohexyl group, and 7,8-epoxy [tricyclo [5.2.1.0 ] Decyl-2-yl] group etc. are mentioned. Moreover, what is derived from a (meth) acryloyl group as an ethylenically unsaturated bond is preferable. As a preferable alicyclic epoxy group containing ethylenically unsaturated compound, For example, (3, 4- epoxycyclohexyl) methyl (meth) acrylate, the compound represented by the following general formula (1)-(15), etc. are mentioned specifically, Can be mentioned.

(Wherein R _1b represents a hydrogen atom or a methyl group)

(Wherein R _1b represents a hydrogen atom or a methyl group, and R _2b represents an alkylene group having 1 to 10 carbon atoms.)

(Wherein R _1b represents a hydrogen atom or a methyl group, and R _2b represents an alkylene group having 1 to 10 carbon atoms.)

(Wherein R _1b is a hydrogen atom or a methyl group, R _2b is an alkylene group of 1 to 10 carbon atoms, R _3b is a hydrocarbon group of 1 to 10 carbon atoms, k represents 0 or an integer of 1 to 10).

(Wherein R _1b represents a hydrogen atom or a methyl group, and R _2b represents an alkylene group having 1 to 10 carbon atoms.)

(In formula, R <_1b> respectively independently represents a hydrogen atom or a methyl group, and R <_2b> represents a C1-C10 alkylene group.)

(In formula, R <_1b> respectively independently represents a hydrogen atom or a methyl group, and R <_2b> represents a C1-C10 alkylene group.)

(Wherein R _1b represents a hydrogen atom or a methyl group, and R _2b represents an alkylene group having 1 to 10 carbon atoms.)

(Wherein R _1b represents a hydrogen atom or a methyl group, and R _2b represents an alkylene group having 1 to 10 carbon atoms.)

(Wherein R _1b represents a hydrogen atom or a methyl group, and R _2b represents an alkylene group having 1 to 10 carbon atoms.)

(Wherein R _1b represents a hydrogen atom or a methyl group, and R _2b represents an alkylene group having 1 to 10 carbon atoms.)

(Wherein R _1b represents a hydrogen atom or a methyl group)

(Wherein R _1b represents a hydrogen atom or a methyl group)

(Wherein R _1b represents a hydrogen atom or a methyl group, and R _2b represents an alkylene group having 1 to 10 carbon atoms.)

(Wherein R _1b represents a hydrogen atom or a methyl group)

In General Formulas (1) to (15), examples of R _2b include a methylene group, an ethylene group, a propylene group, a butylene group, and the like, but are preferably a methylene group, an ethylene group, or a propylene group. In said general formula (1)-(15), general formula (3) is preferable.

Among the above compounds, 3,4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable. These epoxy group containing unsaturated compounds can be used together 2 or more types.

In the present invention, a resin having a structure in which an epoxy group of an epoxy group-containing unsaturated compound (b) is added to a carboxyl group of a resin (a) having a carboxyl group must necessarily be produced by reacting an epoxy group-containing unsaturated compound with a resin having a carboxyl group. It is not necessary to have the above structure as a result.

As a method of making an epoxy group containing unsaturated compound (b) react with the carboxyl group of resin (a) which has a carboxyl group, a well-known method can be used.

For example, tertiary amines, such as triethylamine and benzylmethylamine, dodecyl trimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetra, are used for resin (a) which has a carboxyl group, and epoxy group containing unsaturated compound (b). In the presence of a catalyst such as a quaternary ammonium salt such as butylammonium chloride or benzyltriethylammonium chloride, pyridine or triphenylphosphine, and reacting for several hours to several tens of hours in an organic solvent at a reaction temperature of 50 to 150 An epoxy compound can be introduce | transduced into a carboxyl group.

The acid value of binder resin manufactured as mentioned above is 10-200 KOHmg / g normally, Preferably it is 20-150, More preferably, it is 30-150. The polystyrene reduced weight average molecular weight (Mw) measured by GPC is usually 2000 or more, preferably 4000 or more, more preferably 5000 or more, usually 120000 or less, preferably 90000 or less, more preferably 50000 or less, particularly preferably Preferably less than 30000. When the weight average molecular weight is too small, liquid stability is inferior, and when too large, the solubility of a colored resin composition tends to deteriorate. As a ratio in the total solid of the colored resin composition of the said binder resin, it is 10-80 weight% normally, Preferably it is 20-70 weight%. Moreover, as a ratio with respect to a color material, it is 20-300 weight% normally, Preferably it is 30-200 weight%, More preferably, it is 40-100 weight%.

[1-4-2]

In this invention, the nitrogen atom-free binder resin of that excepting the above can be used individually or in combination. As a particularly preferable structure of the binder resin, 5 to 90 mol% of (A) epoxy group-containing (meth) acrylate and (B) 10 to 95 mol% of other radically polymerizable compounds copolymerizable with the (A) component. It is a copolymer, (C) unsaturated monobasic acid is added to 10-100 mol% of the epoxy group of the said (A) component, and it is (D) to 10-100 mol% of the hydroxyl group produced by addition of the said (C) component. It is resin obtained by adding polybasic acid anhydride. Hereinafter, this binder resin is demonstrated.

<(A) epoxy group-containing (meth) acrylate>

As an epoxy group containing (meth) acrylate, For example, glycidyl (meth) acrylate, 3, 4- epoxy butyl (meth) acrylate, (3, 4- epoxycyclohexyl) methyl (meth) acrylate, Although 4-hydroxybutyl (meth) acrylate glycidyl ether can be illustrated, glycidyl (meth) acrylate is especially preferable.

(A) Content in the copolymerization monomer of an epoxy group containing (meth) acrylate is 5 mol% or more normally, Preferably it is 20 mol% or more, More preferably, it is 30 mol% or more, and also usually 90 mol% or less, Preferably it is 80 It is the range of mol% or less, More preferably, it is 70 mol% or less. If too large, other components may decrease, and heat resistance or strength may decrease. If too small, the addition amount of the polymerizable component and the alkali-soluble component is insufficient, which is not preferable.

<(B) Another radically polymerizable compound copolymerizable with component (A)>

As (B) component, it is preferable to contain the mono (meth) acrylate which has a structure represented by following formula (VI).

In said general formula (VI), R <_3> -R <_8> respectively independently represents a hydrogen atom or C1-C3 alkyl groups, such as a methyl group, an ethyl group, and a propyl group. R ₉ and R ₁₀ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group. Alternatively, R ₉ and R ₁₀ may be linked to each other to form a ring. The ring formed by connecting R ₉ and R ₁₀ is preferably an aliphatic hydrocarbon ring. The aliphatic hydrocarbon ring may be either saturated or unsaturated and its carbon number is preferably 5 or 6.

Among the said general formula (VI), Especially preferably, it is a mono (meth) acrylate which has a structure represented by following formula (VIII), (VIII) or (VIII).

As mono (meth) acrylate which has a structure of said general formula (VI), a well-known thing can be used, For example, what is represented by the following structural formula (i) is mentioned.

(In formula (VIII), R ₁₁ represents a hydrogen atom or a methyl group, and R ₁₂ represents a group represented by the formula (VI).)

The content in the copolymerization monomer of the mono (meth) acrylate having the structure of the general formula (VI) is usually 10 mol% or more, preferably 15 mol% or more, and usually 90 mol% or less, preferably 70 mol% or less More preferably, it is 50 mol% or less of range. By having these structures, heat resistance and strength can be increased.

Although it does not specifically limit as another (B) component, As the specific example, (alpha)-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivative of styrene and styrene; Dienes such as butadiene, 2,3-dimethylbutadiene, isoprene and chloroprene; Methyl (meth) acrylate, ethyl (meth) acrylate, (n) propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, (meth ) Tert-butyl acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, isoboronyl (meth) acrylate, (meth) Adamantyl acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninil (meth) acrylate, (meth) acrylate Piperonyl acrylate, Salicylic (meth) acrylate, Furyl (meth) acrylate, Purpu (meth) acrylate Tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, credil (meth) acrylate, (meth) acrylic acid-1,1,1-trifluoro Ethyl, Perfluoroethyl (meth) acrylate, Perfluoro-n-propyl (meth) acrylate, Perfluoro-iso-propyl (meth) acrylate, Triphenylmethyl (meth) acrylate, Cumyl (meth) acrylate, ( (Meth) acrylic acid esters such as 3- (N, N-dimethylamino) propyl, (meth) acrylic acid-2-hydroxyethyl and (meth) acrylic acid-2-hydroxypropyl; (Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N-di (meth) acrylic acid amides such as -iso-propylamide and anthracenylamide (meth) acrylate; Vinyl compounds such as (meth) acrylic acid acrylate, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, and vinyl acetate; Unsaturated dicarboxylic acid diesters such as diethyl citrate, diethyl maleate, diethyl fumarate and diethyl itaconic acid; Monomaleimide, such as N-phenylmaleimide, N-cyclohexyl maleimide, N-lauryl maleimide, and N- (4-hydroxyphenyl) maleimide; N- (meth) acryloyl phthalimide etc. are mentioned. In order to provide further excellent heat resistance and strength, it is effective to use at least one selected from styrene, benzyl (meth) acrylate and monomaleimide as the component (B).

The content of the component (B) in the copolymerization monomer is usually 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more, and usually 95 mol% or less, preferably 80 mol% or less, more preferably It is preferably in the range of 70 mol% or less. If the content of the component (B) is too large, the amount of the polymerizable component and the alkali-soluble component is insufficient because the component (A) is reduced. On the contrary, if the content of the component (B) is too small, the heat resistance and the strength decrease, which is not preferable.

<(C) unsaturated monobasic acid>

(C) unsaturated monobasic acid is added to 10-100 mol% of the epoxy groups contained in the copolymer of the said (A) component and (B) component.

As a component (C), a well-known thing can be used and unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned, A specific example is acrylic acid, methacrylic acid, crotonic acid, o-, m-, p And monocarboxylic acids such as α-haloalkyl, alkoxyl, halogen, nitro and cyano substituents of -vinylbenzoic acid and (meth) acrylic acid. Especially, acrylic acid or methacrylic acid is preferable.

The addition rate of the component (C) is usually 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more, relative to the epoxy group contained in the copolymer of the component (A) and the component (B). Usually, it is 100 mol% or less. When too small, the bad influence by a residual epoxy group, such as aging stability, is feared.

<(D) polybasic acid anhydride>

(D) polybasic acid anhydride is added to 10-100 mol% of the hydroxyl groups produced when (C) component is added to the epoxy group of the copolymer of (A) component and (B) component.

(D) The polybasic acid anhydride is used to make the binder resin of the present invention alkali-soluble, and known ones can be used, but examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydro phthalic anhydride and hexa Dibasic acid anhydrides such as hydrophthalic anhydride and chloric anhydride; And polybasic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride and biphenyltetracarboxylic anhydride. Especially, tetrahydro phthalic anhydride or succinic anhydride is preferable.

The addition rate of the polybasic acid anhydride is usually 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more, and usually 100 mol% or less of the entire hydroxyl group generated when the component (C) is added to the epoxy group. Preferably it is 90 mol% or less, More preferably, it is added to 80 mol% or less. If the addition rate is too large, the residual film ratio may decrease during development, and if too small, the solubility is insufficient.

<Method of manufacturing binder resin>

The well-known solution polymerization method is applied to copolymerization reaction of (A) component and (B) component. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and an organic solvent which is usually used can be used. For example, Ethylene glycol monoalkyl ether acetates, such as ethyl acetate, isopropyl acetate, a cellosolve acetate, and a butyl cellosolve acetate; Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; Propylene glycol monoalkyl ether acetates; Acetate esters such as dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol and butyl carbitol; Triethylene glycol dialkyl ethers; Propylene glycol dialkyl ethers; Dipropylene glycol dialkyl ethers; Ethers such as 1,4-dioxane and tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Hydrocarbons such as benzene, toluene, xylene, octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; Lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate; Dimethyl formamide, N-methylpyrrolidone, etc. are mentioned. These solvents may use individually or in combination of 2 or more types.

The amount of the solvent used is usually 30 parts by weight or more, preferably 50 parts by weight or more, and usually 1000 parts by weight or less, preferably 800 parts by weight or less with respect to 100 parts by weight of the binder resin. Outside this range, control of the molecular weight becomes difficult.

The radical polymerization initiator used in the present invention is not particularly limited as long as the radical polymerization initiator can be initiated, and an organic peroxide catalyst or an azo compound that is usually used can be used. For example, as the specific example, it is classified into well-known ketone peroxide, peroxy ketal, hydroperoxide, diallyl peroxide, diacyl peroxide, peroxy ester, peroxy dicarbonate, and also azo compound Valid.

As a specific example, for example, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxy benzoate, t-hexyl peroxy benzoate, t-butylper Oxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl -2,5-bis (t-butylperoxy) hexyl-3,3-isopropylhydroperoxide, t-butylhydroperoxide, dicumylperoxide, dicumylhydroperoxide, acetylperoxide, bis (4- t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t -Butyl peroxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexyl peroxy) 3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azobiscarboxyl Mead etc. can be used. Depending on the polymerization temperature, an appropriate half-life radical polymerization initiator is selected.

The amount of the radical polymerization initiator to be used is usually 0.5 parts by weight or more, preferably 1 parts by weight or more, and usually 20 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of the total monomer used in the copolymerization reaction. to be.

In the polymerization method, the monomer used for the copolymerization reaction and the radical polymerization initiator may be dissolved in a solvent, heated up while stirring, and the polymerization reaction may be carried out, or the monomer to which the radical polymerization initiator is added may be added dropwise to the solvent heated up and stirred. Moreover, you may add the monomer dropwise in the middle of adding and heating a radical polymerization initiator in a solvent. Although reaction conditions can be changed freely according to the target molecular weight, as reaction temperature, it is the range of 70 degreeC or more normally, Preferably it is 80 degreeC or more, and usually 150 degreeC or less, Preferably it is 130 degreeC or less. The reaction time is usually 2 hours or more, preferably 3 hours or more, and usually 20 hours or less, preferably 10 hours or less.

A well-known method can be used as a method of adding (C) unsaturated monobasic acid to the said copolymer, and then adding (D) polybasic acid anhydride.

In the present invention, in order to further improve the photosensitivity, after addition of the polybasic acid anhydride (D), a glycidyl ether compound having a glycidyl (meth) acrylate or a polymerizable unsaturated group is added to a part of the resulting carboxyl group or developed. In order to improve the properties, a glycidyl ether compound having no polymerizable unsaturated group may be added to part of the resulting carboxyl group after addition of the polybasic acid anhydride. Moreover, you may use both together. As a specific example of the glycidyl ether compound which does not have a polymerizable unsaturated group, the glycidyl ether compound which has a phenyl group and an alkyl group (made by Nagase Chemical Co., Ltd., brand name: Denacol EX-111, Denacol EX-121, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192).

As a weight average molecular weight (Mw) measured by GPC (Gel Permeation Chromatograhy: gel permeation chromatography) of the binder resin of this invention, it is 2000 or more normally, Preferably it is 3000 or more, More preferably, it is 5000 or more, Usually it is 100000 or less Preferably it is 50000 or less, More preferably, it is 10000 or less, Especially preferably, it is the range of 8000 or less. If the weight average molecular weight is less than 2000, the heat resistance and the film strength are inferior, while if the weight average molecular weight is more than 100000, the solubility in the developer is insufficient. In die-coating, it is preferable that it is 10000 or less in order to prevent dry cohesion at the tip of a die lip at the time of coating. Moreover, as for molecular weight distribution (Mw / Mn), 2-5 are preferable.

These binder resins are contained in the range of 10 weight% or more normally, Preferably it is 20 weight% or more, and also 80 weight% or less normally, Preferably it is 70 weight% or less in the total solid of the coloring resin composition of this invention. Moreover, as a ratio with respect to a coloring material, it is 20 weight% or more normally, Preferably it is 30 weight% or more, More preferably, it is 50 weight% or more, Moreover, 500 weight% or less normally, Preferably it is 300 weight% or less, More preferably, It is the range of 200 weight% or less.

And about these resin structures, for example, Unexamined-Japanese-Patent No. 8-297366 and 2001-89533 are described, and although it is already well-known, it mixes with the dispersing agent which has a specific structure as mentioned above. Only by the desired effect.

[1-5] Organic carboxylic acid, organic carboxylic anhydride

The coloring composition of this invention may contain the organic carboxylic acid and / or organic carboxylic anhydride of molecular weight 1000 or less. It is preferable that these are contained when a dispersing agent is a urethane type dispersing agent.

As an organic carboxylic acid compound, an aliphatic carboxylic acid or an aromatic carboxylic acid is mentioned specifically ,. As aliphatic carboxylic acid, monocarboxylic acid, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, capronic acid, glycolic acid, acrylic acid, methacrylic acid, oxalic acid, maronic acid, succinic acid, glutamic acid, ah Tree such as dicarboxylic acid such as dific acid, pimeric acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, tricarbaric acid and aconitic acid Carboxylic acid, and the like. Moreover, as an aromatic carboxylic acid, the carboxylic acid which the carboxyl group couple | bonded through the carbon bond from the carboxylic acid and phenyl group which the carboxyl group directly bonded to phenyl groups, such as benzoic acid and phthalic acid, is mentioned. Among these, especially those having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500, specifically maleic acid, succinic acid and itaconic acid are preferable.

Examples of the organic carboxylic anhydride include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specific examples include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, and anhydride. Aliphatic carboxyl such as maleic acid, itaconic anhydride, glutaric anhydride, 1,2-cyclohexenedicarboxylic acid anhydride, n-octadecylsuccinic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride Acid anhydrides. As aromatic carboxylic anhydride, phthalic anhydride, trimellitic anhydride, a pyromellitic anhydride, naphthalic anhydride etc. are mentioned. Among these, those having a molecular weight of 600 or less, in particular, having a molecular weight of 50 to 500, specifically maleic anhydride, succinic anhydride, and itaconic anhydride are preferable.

The addition amount of these organic carboxylic acid and / or organic carboxylic anhydride is 0.01-10 weight% normally in total solid, Preferably it is 0.03-5 weight%, More preferably, it is the range of 0.05-3 weight%.

By adding these organic carboxylic acids and / or organic carboxylic anhydrides having a molecular weight of 1,000 or less, it is possible to further reduce the residuals of undissolved substances in the coloring composition while maintaining high pattern adhesion. Japanese Patent No. 3293171 proposes a method of adding an organic carboxylic acid compound having a molecular weight of 1000 or less to a coloring composition. As described above, in this method, the adhesion of the image portion is lowered, and as a result, the development margin is narrowed and the pixel is reduced. Peeling and a white exposure defect tend to generate | occur | produce. However, in the combination with the dispersing agent and binder resin of this invention, even if organic carboxylic acid and / or organic carboxylic anhydride are added, this phenomenon does not occur and only the effect which reduces the remainder of an undissolved thing is expressed.

[1-5] Photopolymerizable Monomer

The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but an addition polymerizable compound having one or more ethylenic double bonds (hereinafter referred to as an "ethylenic compound") is preferable. An ethylenic compound is a compound which has an ethylenic double bond which add-polymerizes and hardens | cures by the effect | action of the photoinitiation system mentioned later, when the coloring resin composition of this invention is irradiated with actinic light. In addition, the monomer in this invention means the concept corresponding to a so-called high polymer substance, and means the concept which also contains a dimer, a trimer, and an oligomer in addition to the monomer of consultation.

As an ethylenic compound, For example, unsaturated carboxylic acid, ester of it and a monohydroxy compound, ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, unsaturated Ester obtained by esterification of polyhydric hydroxy compounds, such as carboxylic acid, polyhydric carboxylic acid, and the above-mentioned aliphatic polyhydroxy compound, aromatic polyhydroxy compound, a polyisocyanate compound, and (meth) acryloyl containing hydroxy Ethylenic compound etc. which have a urethane skeleton which made the compound react are mentioned.

As ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, penta And acrylic acid esters such as erythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and glycerol acrylate. Moreover, the methacrylic acid ester which changed the acrylic acid part of these acrylates into the methacrylic acid part, the itaconic acid ester which changed into the itaconic acid part, the crotonic acid ester which changed into the crotonic acid part, or the maleic acid ester which changed into the maleic acid part etc. are mentioned. have.

As ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate, etc. are mentioned.

The ester obtained by esterification of an unsaturated carboxylic acid, a polyhydric carboxylic acid, and a polyhydric hydroxy compound is not necessarily a single substance, but may be a mixture. Representative examples include condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, of acrylic acid, adipic acid, butanediol and glycerin And condensates.

As an ethylenic compound which has a urethane skeleton which made the polyisocyanate compound and the (meth) acryloyl-group containing hydroxy compound react, Aliphatic diisocyanate, such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; Alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; Aromatic diisocyanates, such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl The reactant of (meth) acryloyl-group containing hydroxy compounds, such as propane and 3-hydroxy (1,1,1- trimethacryloyloxymethyl) propane, is mentioned.

In addition, examples of the ethylenic compound used in the present invention include acrylamides such as ethylenebisacrylamide; Allyl esters such as diallyl phthalate; Vinyl group containing compounds, such as divinyl phthalate, etc. are also useful.

The blending ratio of these ethylenic compounds is usually at least 0% by weight, preferably at least 5% by weight, more preferably at least 10% by weight, and usually at most 80% by weight, preferably in the total solids of the colored resin composition of the present invention. It is 70 weight% or less, More preferably, it is 50 weight% or less, Especially preferably, it is 40 weight% or less. The proportion to the colorant is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, particularly preferably 20% by weight or more, and usually 200% by weight or less, preferably 100% by weight. % Or less, More preferably, it is 80 weight% or less.

[1-6] photopolymerization initiator system

When the colored resin composition which concerns on this invention contains the ethylenic compound of a monomer component, the photoinitiator type component which has a function which absorbs light directly or photosensitizes, and produces | generates a polymerization active radical by causing a decomposition reaction or a hydrogen drawing reaction. It is preferable to mix | blend. In addition, in this invention, a photoinitiator type component means the mixture in which additives, such as a photoinitiator, an accelerator, and a dye, are used together.

As a photoinitiator which comprises a photoinitiator type component, For example, the metallocene compound containing the titanocene compound of each Unexamined-Japanese-Patent No. 59-152396, Unexamined-Japanese-Patent No. 61-151197, Hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, and N-phenyl as disclosed in JP-A-58-403023, JP-A-45-37377, JP-A-10-39503 Radical activators such as N-aryl-α-amino acids such as glycine, N-aryl-α-amino acid salts and N-aryl-α-amino acid esters, and "fine chemicals" (March 1, 1991, March 1, vol. 20, No. 4), dialkyl acetophenone series, benzoin, chioxanthone derivatives, etc. described in pages 16 to 26, Japanese Unexamined Patent Publication No. Hei 4-221958, Japanese Unexamined Patent Publication No. 4-219756 Titanocene and xanthene pigments, α-aminoalkylphenone compounds, The system which combined the ethylenic saturated double bond containing compound which can add-polymerize which has an amino group or a urethane group, etc. are mentioned.

Specific examples of the polymerization initiator that can be used in the present invention are listed below.

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloro Halomethylated triazine derivatives such as rhomethyl) -s-triazine;

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, 2-trichloromethyl-5 Halomethylated oxadiazole derivatives such as 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, (4'- Imidazole derivatives such as methoxyphenyl) -4,5-diphenylimidazole dimer;

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

Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone;

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

2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, α-hydroxy-2-methylphenylpropaneone, 1-hydroxy-1-methyl Ethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 '-(methylthio) phenyl) -2-morpholino-1- Acetophenone derivatives such as propane, 1,1,1-trichloromethyl- (p-butylphenyl) ketone;

Thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-di Thioxanthone derivatives such as isopropyl thioxanthone;

benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate; Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine; Phenazine derivatives such as 9,10-dimethylbenzphenazine;

Anthrone derivatives such as benzanthrone;

Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoro Phenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6 -Trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti-2,4-di-fluoro Phenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2 Titanocene, such as, 6-di-fluorophenyl-1-yl and di-cyclopentadienyl-Ti-2,6-di-fluoro-3- (phyl-1-yl) -phenyl-1-yl derivative;

2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone- 1,4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2 Α-aminoalkylphenones such as, 5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin and 4- (diethylamino) chalcone compound.

As an accelerator which comprises a photoinitiator type component, For example, N, N- dialkylamino benzoic acid alkyl esters, such as N, N- dimethylamino benzoic acid ethyl ester, 2-mercapto benzothiazole, and 2-mercapto benzoxa Mercapto compounds having heterocycles such as sol and 2-mercaptobenzoimidazole, aliphatic polyfunctional mercapto compounds and the like. Two or more types of mixtures may be sufficient as a photoinitiator and an accelerator, respectively.

The blending ratio of the photopolymerization initiator-based component is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 0.7% by weight or more, and usually 30% by weight or less in the total solids of the colored resin composition of the present invention. Preferably it is 20 weight% or less, More preferably, it is 10 weight% or less. If the blending ratio is significantly low, it may cause a decrease in sensitivity to the exposure light. On the contrary, if the blending rate is significantly high, the solubility of the unexposed portion in the developing solution may be lowered to induce developing defects. Moreover, although these may mix and use multiple types of photoinitiators and accelerators, respectively, As a preferable combination of a photoinitiator and an accelerator, the combination of an imidazole derivative, the (alpha)-aminoalkyl phenone type compound, and the mercapto compound which has a heterocycle is mentioned. Can be.

The photoinitiator type component can mix | blend the sensitizing dye according to the wavelength of an image exposure light source as needed for the purpose of improving a sensitivity. As these sensitizing dyes, the xanthene dyes described in Japanese Unexamined Patent Publications Nos. 4-221958 and 4-219756, and the heterocycles described in Japanese Unexamined Patent Publications No. 3-239703 and 5-289335, respectively. Having coumarin pigment, 3- Ketokumarin compound of Unexamined-Japanese-Patent No. 3-239703, 5-289335, Pyromethene pigment of Unexamined-Japanese-Patent No. 6-19240, and other Unexamined-Japanese-Patent No. SO 47-2528, WO 54-155292, JP 45-37377, JP 48-84183, 52-112681, 58-15503, 60-88005, 59-56403, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 57-168088, Japanese Patent Laid-Open No. 5-107761, Japanese Patent Laid-Open No. 5-210240, Japanese Patent Laid-Open No. The pigment | dye which has the dialkylamino benzene skeleton described in each publication 4-288818, etc. are mentioned.

Preferred of these sensitizing dyes are amino group-containing sensitizing dyes, more preferably compounds having an amino group and a phenyl group in the same molecule. Especially preferred are 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, Benzophenone compounds such as 3,3'-diaminobenzophenone and 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzooxazole, 2- (p-dimethylaminophenyl) benzo [4,5] benzoxazole, 2- (p -Dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-di Ethylaminophenyl) 1,3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) P-dialkylaminophenyl group-containing compounds such as quinoline, (p-dimethylaminophenyl) pyrimidine and (p-diethylaminophenyl) pyrimidine. Most preferred of these are 4,4'-dialkylaminobenzophenones.

The blending ratio of the sensitizing dye in the colored resin composition according to the present invention is usually 0% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% by weight or more, and usually 20% by weight in the total solids of the colored resin composition. The amount is preferably 15% by weight or less, more preferably 10% by weight or less.

[1-7] Other Solids

As above-mentioned, solid content other than the said component can be mix | blended with the colored resin composition which concerns on this invention as needed. As these components, a dispersing aid, a surfactant, a thermal polymerization inhibitor, a plasticizer, a storage stabilizer, a surface protector, an adhesion promoter, a developer, and the like can be added. As a dispersion adjuvant, a pigment derivative is mentioned, for example.

As the pigment derivative, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indansrene, perylene, perinone, diketopyro And derivatives such as ropyrrole pigments and dioxazine pigments. As the substituent of the pigment derivative, sulfonic acid group, sulfonamide group and quaternary salts thereof, phthalimide methyl group, dialkylaminoalkyl group, hydroxyl group, carboxyl group, amide group and the like are directly added to the pigment skeleton or through an alkyl group, an aryl group, a heterocyclic group or the like. The thing which couple | bonded is mentioned, Preferably a sulfonamide group, its quaternary salt, and a sulfonic acid group are mentioned, More preferably, it is a sulfonic acid group. In addition, these substituents may be substituted by two or more in one pigment skeleton, and the mixture of the compound from which a substituent differs may be sufficient. Specific examples of the pigment derivative include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, and sulfonic acid of diketopyrrolopyrrole pigments. Derivatives, sulfonic acid derivatives of dioxazine pigments, and the like.

Moreover, you may add a pigment derivative etc. as a dispersing adjuvant in order to improve pigment dispersibility and dispersion stability. As the pigment derivative, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindolin, dioxazine, anthraquinone, indansrene, perylene, and perinone And derivatives such as diketopyrrolopyrrole pigments and dioxazine pigments. As the substituent of the pigment derivative, sulfonic acid group, sulfonamide group and quaternary salts thereof, phthalimide methyl group, dialkylaminoalkyl group, hydroxyl group, carboxyl group, amide group and the like are directly added to the pigment skeleton or through an alkyl group, an aryl group, a heterocyclic group or the like. The bonded thing is mentioned, Preferably a sulfonamide group, its quaternary salt, and a sulfonic acid group are mentioned, More preferably, it is a sulfonic acid group. In addition, these substituents may be substituted by two or more in one pigment skeleton, and the mixture of the compound from which a substituent differs may be sufficient. Specific examples of the pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of isoindolin pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, And sulfonic acid derivatives of diketopyrrolopyrrole pigments, and sulfonic acid derivatives of dioxazine pigments. Among them, sulfonic acid derivative of Pigment Yellow 138, sulfonic acid derivative of Pigment Yellow 139, sulfonic acid derivative of Pigment Red 254, sulfonic acid derivative of Pigment Red 255, sulfonic acid derivative of Pigment Red 264, Pigment Red 272 Sulfonic acid derivatives, sulfonic acid derivatives of Pigment Red 209, sulfonic acid derivatives of Pigment Orange 71, sulfonic acid derivatives of Pigment Violet 23, more preferably sulfonic acid derivatives of Pigment Yellow 138, and sulfonic acid derivatives of Pigment Red 254. The addition amount of the pigment derivative is usually 0.1% by weight or more, and usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less. If the amount is small, the effect is not exerted. On the contrary, if the amount is too large, dispersibility and dispersion stability deteriorate.

As surfactant, various things, such as anionic, cationic, nonionic, and amphoteric surfactant, can be used, but it is preferable to use nonionic surfactant from the point which is unlikely to adversely affect various characteristics. The concentration range of the surfactant is usually 0.001% by weight or more, preferably 0.005% by weight or more, more preferably 0.01% by weight or more, most preferably 0.03% by weight or more, and usually 10% by weight based on the total amount of the composition. Below, preferably 1% by weight or less, more preferably 0.5% by weight or less, and most preferably 0.3% by weight or less are used.

Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like. It is preferable that the compounding quantity of a thermal polymerization inhibitor is the range of 0 weight% or more and 3 weight% or less with respect to the total solid of a composition.

As the plasticizer, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricredyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerine and the like are used. It is preferable that the compounding quantity of these plasticizers is the range of 10 weight% or less normally with respect to the total solid of a composition.

[2] properties of colored resin composition (resist)

The colored resin composition (resist) which concerns on this invention has the characteristic that it is excellent in permeability, is excellent in image development adhesiveness, and there are few undissolved residues by using especially the specific binder resin and dispersing agent mentioned above. More importantly, they may have characteristics of low viscosity change rate, good re-dissolution property and high voltage holding ratio. Hereinafter, each characteristic is demonstrated.

[2-1] Permeability

Regarding the transmittance, the reflectance of each pixel of red, green, and blue is evaluated from the measured values measured by the following method. It demonstrates concretely below.

A colored resin composition to be applied is applied onto a glass substrate (ANA 100 manufactured by Asahi Glass Co., Ltd.) having a width of 5 cm by the spin coating method, heated at 80 ° C. for 3 minutes on a hot plate, and the entire surface is 100 mJ /. After exposing to 2 cm <2>, it spray-developed for 30 second by 0.3 MPa water pressure at 23 degreeC 0.1weight% sodium carbonate aqueous solution, and baked at 230 degreeC 30 minutes in a hot-air circulation path after that. The coating thickness of the colored resin composition after baking was adjusted so that x = 0.60 for red, y = 0.55 for green, and y = 0.14 for blue (all C light sources) in color coordinates indicated by a CIE color system.

For measurement of chromaticity, a spectrophotometer "U-3500" manufactured by Hitachi, Ltd. is used.

The red colored resin composition of this invention exists in the range whose Y value in a CIE color system is represented by either of the following formulas.

Y≥200y-41.4 (y <0.34)

Y≥100y-7.4 (y≥0.34)

More preferably, it exists in the range represented by either of the following formulas.

Y≥200y-40.9 (y <0.34)

Y≥100y-6.9 (y≥0.34)

Moreover, the green coloring resin composition of this invention exists in the range in which the Y value in a CIE color system is represented by a following formula.

Y≥240x-7.1

Also preferably, it is in a range represented by the following formula.

Y≥240x-6.6

Moreover, the blue coloring resin composition of this invention exists in the range whose Y value in a CIE color system is represented by a following formula.

Y≥20x + 16.2

Also preferably, it is in a range represented by the following formula.

Y≥20x + 16.4

By using the colored resin composition excellent in the transmittance of this invention, since the transmittance | permeability of a color filter becomes high and also the brightness of a liquid crystal display device becomes high, there exists an advantage that an image becomes clear.

[2-2] Development Adhesiveness

About developing adhesiveness, it evaluates by the minimum pattern width measured by the following method. It demonstrates concretely below.

The colored resin composition to be applied is coated on a glass substrate to have a dry film thickness of 1.3 μm, dried at 60 ° C. for 1 minute, and then dried at 110 ° C. for 2 minutes, and a test mask having linear openings having a line width of 1 μm is used. After exposing to a gap of 150 μm at an exposure dose of 300 mJ / cm 2, the solution was developed with a 0.1 wt% aqueous solution of sodium carbonate at a solution temperature of 23 ° C. at a liquid pressure of 0.2 kg / cm 2 for 60 seconds. Subsequently, when the pattern was formed by spray washing with a water pressure of 3 kg / cm 2 for 30 seconds, the minimum pattern width remaining as a linear image was measured.

The minimum pattern width of the colored resin composition of this invention is 10 micrometers or less, Preferably it is 8 micrometers or less.

By using the colored resin composition excellent in image development adhesiveness of this invention, a high quality color filter can be formed without a white exposure defect.

[2-3] Beauty Seafood Residues

The unsealed seafood residue is evaluated by the spectral reflectance measured by the following method. It demonstrates concretely below.

About the color filter obtained by the colored resin composition made into the object, the cloth (for example, Toray Co., Ltd. make) which consists of polyester long fiber of an average 3 micrometers or less of 30x100 mm part of a non-pixel part (on base glass) Toraysee MK clean cloth) was wiped at a pressure of 1 kgf / ㎠. The said cloth is fixed to the front-end | tip of the each material made from 1 cm x 1 cm of resin, and what used the eyedropper impregnated with 0.1 cc of ethanol is used. Spectral reflectance is measured on the conditions which used the integrating sphere by the Shimadzu Corporation spectrophotometer UV3100S for 1 cm x 1 cm part of the wiped cloth. Table 5 shows spectral reflectances of λ = 500 nm (corresponding to red residue), 450 nm (corresponding to green residue), and 550 nm (corresponding to blue residue).

In the present invention, the spectral reflectance of 500 nm in red, 450 nm in green, and 550 nm in blue is 95% or more, preferably 97% or more, in the above evaluation method.

By using the colored resin composition with few undissolved residues of the present invention, it is possible to form a high-quality color filter that does not have a decrease in transmittance, contrast, or the like, and that the peeling of the ITO film and the deterioration of the sealability in the liquid crystal cell forming step do not occur. .

[2-4] Viscosity Change Rate

The viscosity change rate is evaluated by the following method. It demonstrates concretely below.

Viscosity (20 rpm) immediately after preparing the colored resin composition of interest, and after leaving it to stand in a thermostat at 23 degreeC for 7 days is measured using the E-type viscosity meter "RE-80L" by Toki Kogyo.

In the colored resin composition of this invention, the viscosity change after 7 days is 10% or less with respect to initial stage viscosity, Preferably it is 5% or less, More preferably, it is 3% or less.

The colored resin composition having a low viscosity change rate of the present invention has an advantage of being able to be used under the same process conditions for a long time because of its excellent storage stability.

[2-5] Redissolution

Re-dissolution is evaluated by the following method. It demonstrates concretely below.

Each colored resin composition was applied to a glass substrate having a width of 50 mm by a spin coat method at a dry film thickness of 2.5 μm, dried in a natural air for 60 minutes, and then for 3 minutes to 6.25 g of a solvent for forming the colored composition. It is immersed and redispersed, particle size distribution is measured by Nikkiso micro track UPA 10 minutes after the start of immersion, and volume average particle diameter mv is computed.

As for the colored resin composition of this invention, the volume average particle diameter mv in a redispersion liquid is 200 nm or less normally, Preferably it is 150 nm or less.

Since the colored resin composition of the present invention having a good redissolution property is difficult to form dry cohesive foreign substances at the tip of the die lip even when applied by the die coating method, foreign matter defects can be suppressed and a high quality color filter can be formed at high yield. have.

[2-6] Voltage maintenance rate

The voltage retention is evaluated by the following method. It demonstrates concretely below.

An electrode substrate A having an ITO film formed on an entire surface of an alkali-free glass substrate (AN-100 manufactured by Asahi Glass Co., Ltd.) having a width of 2.5 cm and a central portion of one glass substrate having a width of 2.5 cm An electrode substrate B having a 1 cm wide ITO film formed by a 2 mm wide extraction electrode was prepared. After applying the alignment film agent (Sun Ever 7474) manufactured by Nissan Chemical Co., Ltd. on the electrode substrates A and B by spin coating method, the resultant was dried at 110 ° C. for 1 minute on a hot plate, and then 200 ° C. 1 in a hot air circulation path. Heating is performed for a time to form a coating film having a film thickness of 70 nm.

After coating the coloring composition of each Example on the electrode substrate A which apply | coated the orientation film agent by the spin coat method, heating 80 degreeC 3 minutes on a hotplate, exposing the whole surface to 100mJ / cm <2>, 0.1 degreeC sodium carbonate of 23 degreeC Spray development is carried out for 30 seconds by the water pressure of 0.3 MPa with aqueous solution, and it bakes 230 degreeC 30 minutes in a hot-air circulation furnace. Application | coating conditions are adjusted so that the film thickness of the coloring composition after baking may be set to 1.7 micrometers. On the outer periphery of the electrode substrate B to which the alignment film was applied, an epoxy resin-based sealing agent containing silica beads having a diameter of 5 μm was applied using a dispenser, and then the outer edge portion was 3 mm on the surface where the coloring composition of the electrode substrate A was applied. It heats 180 degreeC for 2 hours in a hot-air circulation path in the state which arrange | positioned so as to oppose and was compressed. The liquid crystal (MLC-6846-000 by Merck Japan Co., Ltd.) is inject | poured into the empty cell obtained in this way, the peripheral part is sealed with a UV hardening type sealing compound, and the liquid crystal cell for voltage retention measurements is completed. After the liquid crystal cell was annealed (heated at 105 ° C. for 2.5 hours in a hot air circulation path), a pulse voltage was applied to electrode substrates A and B under conditions of an applied voltage of 5 V and a pulse frequency of 60 Hz to measure the voltage retention.

In the present invention, the voltage holding ratio is usually 80% or more, preferably 90% or more.

The color filter formed by the colored resin composition with the high voltage holding ratio of the present invention does not produce poor display when attached to a liquid crystal display device and is of high quality.

[3] Preparation of colored resin composition (coating solution for color filter)

Next, the method of preparing the colored resin composition which concerns on this invention is demonstrated.

First, a colorant, a solvent, and a dispersing agent are weighed each predetermined amount, and a colorant is disperse | distributed in a dispersion processing process, and it manufactures as a liquid colored resin composition (ink liquid). In this dispersion treatment process, a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer and the like can be used. Since the color material becomes fine particles by performing this dispersion process, the coating characteristic of a colored resin composition improves and the transmittance | permeability of the color filter substrate of a product improves.

When disperse | distributing a color material, it is preferable to use together binder resin, a dispersion aid, etc. suitably. As binder resin used when disperse | distributing a color material, it is especially preferable to use resin which has a structure which adds the epoxy part of an epoxy-group containing unsaturated compound to the carboxyl group part of resin which has a carboxyl group. In addition, when performing a dispersion process using a sand grinder, it is preferable to use glass beads or zirconia beads of 0.1 to several mm in diameter. The temperature at the time of the dispersion treatment is usually set at 0 ° C or higher, preferably at room temperature or higher, and usually at 100 ° C or lower, preferably at 80 ° C or lower. Since the appropriate time varies depending on the composition of the ink phase liquid (the colorant, the solvent, the dispersant having a nitrogen-containing functional group), the size of the sand grinder, and the like, it is necessary to adjust the dispersion time appropriately.

A solvent, a binder resin, and optionally a photopolymerizable monomer, a photopolymerization initiator-based component, a component other than the above, and the like are mixed with the ink liquid obtained by the dispersion treatment to obtain a uniform dispersion solution. As binder resin mixed with an ink liquid, it is preferable that it is alkali-soluble resin, The nitrogen which has a structure which adds the epoxy part of an epoxy-group-containing unsaturated compound (b) to the carboxyl group part of resin (a) which has a carboxyl group mentioned above. Copolymer of atom-free binder resin, (A) epoxy group containing 5-90 mol% of (meth) acrylate, and (B) 10-95 mol% of other radically polymerizable compounds which can be copolymerized with said (A) component. (C) unsaturated monobasic acid is added to 10-100 mol% of the epoxy group of the said (A) component, and (D) polybasic acid anhydride is added to 10-100 mol% of the hydroxyl group produced by addition of the said (C) component. It is this added photosensitive resin, The resin etc. whose weight average molecular weight Mw is 2000-10000 are especially preferable. Moreover, the said resin may be used together with other resin.

It is preferable that 60 weight% or more of the resin component in a photosensitive coloring resin composition (it defines with "resin" in this case as weight average molecular weight in GPC being 1000 or more) is alkali-soluble resin. If alkali-soluble resin is less than 60 weight%, solubility may be insufficient.

And the content rate of the nitrogen atom-free binder resin which has a structure which adds the epoxy part of an epoxy group containing unsaturated compound to the carboxyl group part of resin which has a carboxyl group mentioned above among alkali-soluble resin components is preferable, and is 30 weight% or more normally Preferably it is 50 weight% or more, More preferably, it is 80 weight% or more. When it is less than 30 weight%, the photopolymerizable effect derived from the unsaturated bond in the said resin cannot be exhibited, and a sensitivity may fall.

The compounding ratio of resin in the photosensitive coloring resin composition is 5 to 60 weight% normally in the total solid in the photosensitive coloring resin composition, Preferably it is 10 to 50 weight%.

Moreover, since fine dust may mix in each process of a dispersion process and mixing, it is preferable to filter the obtained ink liquid with a filter etc.

[4] color filter substrate manufacturing

Next, the color filter concerning this invention is demonstrated.

The color filter which concerns on this invention was formed using the colored resin composition mentioned above on the board | substrate, It is characterized by the above-mentioned.

[4-1] Transparent Substrates (Supports)

As the transparent substrate of the color filter, the material is not particularly limited as long as it is transparent and has a suitable strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, thermoplastic resin sheet of polysulfone, epoxy resin, and unsaturated. Thermosetting resin sheets, such as polyester resin and poly (meth) acrylic-type resin, or various glass, etc. are mentioned. Especially, glass and heat resistant resin are preferable from a heat resistant viewpoint.

The transparent substrate and the black matrix forming substrate may be subjected to corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as a silane coupling agent or urethane resin, and the like, in order to improve surface properties such as adhesiveness. The thickness of the transparent substrate is usually in the range of 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. In addition, when performing the thin film formation process of various resins, the film thickness is 0.01 micrometer or more normally, Preferably it is 0.05 micrometer or more, and also usually 10 micrometers or less, Preferably it is the range of 5 micrometers or less.

[4-2] Black Matrix

The color filter according to the present invention can be produced by forming a black matrix on the above-mentioned transparent substrate and further forming red, green, and blue pixel images. The said colored resin composition is used as a coating liquid for resist formation of 1 or more types of these black, red, green, and blue. On the base glass surface on the transparent substrate for the black resist, on the resin black matrix formation surface formed on the transparent substrate for the red, green, and blue, or on the metal black matrix formation surface formed using chromium compound or other light shielding metal material. Each process, such as application | coating, heat drying, image exposure, image development, and thermosetting, is performed on it, and the pixel image of each color is formed.

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

These metal light shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film form by a positive photoresist, an etching solution obtained by mixing dicerium ammonium nitrate with perchloric acid and / or nitric acid is used for chromium. Other materials are etched using an etchant according to the material, and finally, the black matrix can be formed by peeling the positive photoresist with a dedicated release agent.

In this case, first, a thin film of these metals or metal-metal oxides is formed on the transparent substrate by vapor deposition or sputtering. Next, after forming the coating film of a colored resin composition on this thin film, a coating film is exposed and developed using the photomask which has a repeating pattern, such as a stripe, a mosaic, and a triangle, and a resist image is formed. Thereafter, the coating film can be etched to form a black matrix.

When using the colored resin composition for black matrices, a black matrix is formed using the colored resin composition containing a black color material. For example, black by black color materials alone or plural, such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, or a mixture of red, green, blue, etc. suitably selected from inorganic or organic pigments and dyes. Using the colored resin composition containing a color material, a black matrix can be formed in the same manner as the method for forming the following red, green, and blue pixel images.

[4-3] pixel formation

After coating and drying a colored resin composition containing a coloring material of one of red, green, and blue on the transparent substrate on which the black matrix is formed, the photomask is overlaid on the coating film and image exposure, development, As needed, a pixel image is formed by thermosetting or photocuring, and a colored layer is created. By performing this operation with respect to the colored resin composition of red, green, and blue three colors, a color filter image can be formed, respectively.

Coating of the colored resin composition for color filters can be performed by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Among them, the die coating method is preferable from a comprehensive viewpoint, such that the amount of coating liquid used is drastically reduced, and there is no influence of mist or the like adhered when the spin coating method is used.

If the thickness of the coating film is too large, the pattern development becomes difficult and the gap adjustment in the liquid crystal cell forming step may be difficult. On the other hand, if the coating film is too small, it is difficult to increase the pigment concentration, and the desired color expression may not be possible. The thickness of the coating film is usually 0.2 µm or more, preferably 0.5 µm or more, more preferably 0.8 µm or more, and usually 20 µm or less, preferably 10 µm or less, more preferably 5 µm or less in terms of the film thickness after drying. Range.

[4-4] Drying of Coating Film

It is preferable to use the drying method using a hotplate, an IR oven, and a convection oven for drying of the coating film after apply | coating a coloring resin composition to a board | substrate. Usually, after drying preliminarily, it is heated again and dried. The conditions of predrying can be suitably selected according to the kind of the said solvent component, the performance of the dryer to be used, and the like. The drying temperature and drying time are selected according to the type of solvent component, the performance of the dryer used, and the like, but specifically, the drying temperature is usually 40 ° C or higher, preferably 50 ° C or higher, and usually 80 ° C or lower, preferably 70 It is the range of ° C or less, and the drying time is usually 15 seconds or more, preferably 30 seconds or more, and usually 5 minutes or less, preferably 3 minutes or less.

The temperature condition of the reheat drying is preferably a temperature higher than the predrying temperature, specifically, 50 ° C or higher, preferably 70 ° C or higher, and usually 200 ° C or lower, preferably 160 ° C or lower, particularly preferably 130 ° C. It is the following range. Moreover, although drying time changes also with heating temperature, it is preferable to set it as the range of normally 10 second or more, especially 15 second or more, and usually 10 minutes or less, especially 5 minutes. The higher the drying temperature, the better the adhesion to the transparent substrate. However, if the drying temperature is too high, the binder resin may be decomposed and thermal polymerization may occur. Moreover, in the drying process of this coating film, you may use the pressure reduction drying method which dries in a pressure reduction chamber, without raising a temperature.

[4-5] Exposure Process

Image exposure is performed by superimposing a negative matrix pattern on the coating film of a colored resin composition, and irradiating a light source of an ultraviolet-ray or visible light through this mask pattern. At this time, you may expose after forming an oxygen barrier layer, such as a polyvinyl alcohol layer, on a photopolymerizable layer in order to prevent the sensitivity fall of the photopolymerizable layer by oxygen as needed. The light source used for the image exposure is not particularly limited. Examples of the light source include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, fluorescent lamps, and argon ion lasers, YAG lasers, Laser light sources, such as an excimer laser, a nitrogen laser, a helium cadmium laser, and a semiconductor laser, etc. are mentioned. An optical filter can also be used when irradiating light of a specific wavelength.

[4-6] Development Process

The color filter according to the present invention is subjected to image exposure using the light source for the coating film using the colored resin composition according to the present invention, and then developed using an aqueous solution containing an organic solvent or a surfactant and an alkaline compound. It can manufacture by forming an image on a board | substrate. This aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

As an alkaline compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate Inorganic alkaline compounds such as sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine, mono-di- or triethylamine, mono- Or organic alkaline compounds such as dipropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. 2 or more types of mixtures may be sufficient as these alkaline compounds.

As surfactant, For example, Nonionic surfactant, alkyl, such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, monoglyceride alkyl ester, etc. Anionic surfactants, such as benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfate, alkyl sulfonate, and sulfosuccinic acid ester salt, amphoteric surfactant, such as alkylbetaines and amino acids, are mentioned.

As an organic solvent, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, etc. are mentioned, for example. The organic solvent may be used alone or in combination with an aqueous solution.

There is no restriction | limiting in particular in the conditions of image development processing, The image development temperature is 10 degreeC or more normally, Especially 15 degreeC or more, Furthermore, 20 degreeC or more, Moreover, 50 degrees C or less normally, Especially 45 degrees C or less, Furthermore, the range of 40 degrees C or less is preferable. . As the developing method, any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like can be used.

Moreover, the color filter which concerns on this invention apply | coats to the board | substrate the curable coloring resin composition containing (1) solvent, a phthalocyanine-type pigment as a color material, and polyimide-type resin as a binder resin, in addition to the manufacturing method mentioned above, and performs a pixel by an etching method. It can also manufacture by the method of forming an image. (2) A method of forming a pixel image directly on a transparent substrate by using a colored resin composition containing a phthalocyanine-based pigment as a coloring ink, or (3) Electrodepositing a colored resin composition containing a phthalocyanine-based pigment. The method of using as a liquid, immersing a board | substrate in this electrodeposition liquid, and depositing a colored film on the ITO electrode which became a predetermined pattern, etc. are mentioned. And (4) a method in which a film coated with a colored resin composition containing a phthalocyanine-based pigment is adhered to a transparent substrate to be peeled off, image exposure and development are performed to form a pixel image, and (5) coloration containing a phthalocyanine-based pigment. The method of forming a pixel image with an inkjet printer using a resin composition as a coloring ink, etc. are mentioned. The manufacturing method of a color filter employ | adopts a suitable method according to the composition of the colored resin composition for color filters.

[4-7] Heat Curing Treatment

The color filter after development is subjected to a thermosetting process. The thermosetting treatment conditions at this time are usually 100 ° C or higher, preferably 150 ° C or higher, and usually 280 ° C or lower, preferably 250 ° C or lower, and the time is 5 minutes or more and 60 minutes or less. Is selected from the range of. Through these series of steps, formation of a patterned image of one color is completed. This process is repeated in sequence to pattern black, red, green, and blue to form a color filter. In addition, the order of patterning of four colors is not limited to the order mentioned above.

[4-8] Formation of Transparent Electrode

The color filter according to the present invention is used as a part of a component such as a color display or a liquid crystal display by forming a transparent electrode such as ITO on an image in this state. However, in order to increase surface smoothness and durability, Top coat layers, such as an amide and a polyimide, can also be formed. In some applications, such as a planar orientation driving method (IPS mode), a transparent electrode may not be formed.

[5] liquid crystal displays (panels)

Next, the manufacturing method of the liquid crystal display device (panel) which concerns on this invention is demonstrated. In the liquid crystal display device according to the present invention, after forming an alignment film on the color filter according to the present invention and spreading a spacer on the alignment film, the liquid crystal cell is attached to an opposing substrate to form a liquid crystal cell. This is completed by connecting to the counter electrode by injecting. As the alignment film, a resin film such as polyimide is suitable. The gravure printing method and / or the flexographic printing method are usually used for formation of the alignment film, and the thickness of the alignment film is several tens of nm. After hardening an oriented film by thermosetting, it is processed into the surface state which can surface-treat and adjust the inclination of a liquid crystal by ultraviolet irradiation or the process using the rubbing cloth.

As for the spacer, one having a size corresponding to a gap (gap) with the opposing substrate is used, and usually 2 to 8 µm is suitable. The photospacer PS of a transparent resin film can be formed on a color filter substrate by the photolithographic method, and this can be utilized instead of a spacer. An array substrate is usually used as the counter substrate, and a TFT (thin film transistor) substrate is particularly suitable.

The adhesion gap with the opposing substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 µm or more and 8 µm or less. After attaching with the counter substrate, portions other than the liquid crystal inlet are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating to seal around the liquid crystal cell.

The liquid crystal cell sealed in the periphery is cut in panel units, and then the pressure is reduced in the vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and the liquid crystal is injected into the liquid crystal cell. The pressure reduction degree in the liquid crystal cell is usually 1 × 10 ⁻² Pa or more, preferably 1 × 10 ⁻³ or more, and usually 1 × 10 ⁻⁷ Pa or less, preferably 1 × 10 ⁻⁶ Pa or less. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and a heating temperature is 30 degreeC or more normally, Preferably it is 50 degreeC or more, and it is 100 degrees C or less normally, Preferably it is the range of 90 degrees C or less. The heating and holding at the time of reduced pressure usually falls within a range of 10 minutes or more and 60 minutes or less, and is then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected is sealed by curing the UV curable resin with the liquid crystal inlet, thereby completing the liquid crystal display device (panel).

There is no restriction | limiting in particular in the kind of liquid crystal, It is a conventionally known liquid crystal, such as an aromatic type, an aliphatic type, and a polycyclic compound, Any of a lyotropic liquid crystal and a thermotropic liquid crystal may be used. There are known nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, and the like in thermotropic liquid crystals.

Next, although a manufacture example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded. In addition, in the following Example, "part" shows a "weight part."

<Examples 1-18 and Comparative Examples 1-13>

Synthesis Example 1 Synthesis of Binder Resin a

145 weight part of propylene glycol monomethyl ether acetates were stirred, replacing with nitrogen, and it heated up at 120 degreeC. 82 weight part of monoacrylates (Hitachi Chemical Co., Ltd. FA-513M) which has 20 weight part of styrene, 57 parts of glycidyl methacrylates, and a tricyclodecane skeleton are dripped here, and it continues at 120 degreeC for 2 hours. Stirred. Next, the inside of the reaction vessel was changed to air substitution, 0.7 parts by weight of trisdimethylaminomethylphenol and 0.12 parts by weight of hydroquinone were added to 27 parts by weight of acrylic acid, and the reaction was continued at 120 ° C for 6 hours. Then, 52 weight part of tetrahydro phthalic anhydride (THPA) and 0.7 weight part of triethylamines were added, and it was made to react at 120 degreeC for 3.5 hours. The weight average molecular weight Mw measured by GPC of the binder resin obtained in this way was about 15000.

Synthesis Example 2 Synthesis of Binder Resin b

145 weight part of propylene glycol monomethyl ether acetates were stirred, replacing with nitrogen, and it heated up at 120 degreeC. 10 weight part of styrene, 71 weight part of glycidyl methacrylates, and 82 weight part of monoacrylates (FA-513M by Hitachi Chemical Co., Ltd.) which have a tricyclodecane skeleton are dripped here, and it is further rested at 120 degreeC for 2 hours. Stirring was continued. Next, the inside of the reaction vessel was replaced with air substitution, 0.9 parts by weight of trisdimethylaminomethylphenol and 0.15 parts by weight of hydroquinone were added to 34 parts by weight of acrylic acid, and the reaction was continued at 120 ° C for 6 hours. Then, 65 weight part of tetrahydro phthalic anhydride (THPA) and 0.8 weight part of triethylamines were added, and it was made to react at 120 degreeC for 3.5 hours. The weight average molecular weight Mw measured by GPC of the binder resin obtained in this way was about 17000.

Synthesis Example 3 Synthesis of Binder Resin c

145 weight part of propylene glycol monomethyl ether acetates were stirred, replacing with nitrogen, and it heated up at 120 degreeC. Monoacrylate having 18 parts by weight of benzyl methacrylate, 10 parts by weight of methyl methacrylate, 71 parts by weight of glycidyl methacrylate and a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) 62 The weight part was dripped, and stirring was continued at 120 degreeC again for 2 hours. Next, the inside of the reaction vessel was replaced with air substitution, 0.9 parts by weight of trisdimethylaminomethylphenol and 0.15 parts by weight of hydroquinone were added to 34 parts by weight of acrylic acid, and the reaction was continued at 120 ° C for 6 hours. Then, 65 weight part of tetrahydro phthalic anhydride (THPA) and 0.8 weight part of triethylamines were added, and it was made to react at 120 degreeC for 3.5 hours. The weight average molecular weight Mw measured by GPC of the binder resin obtained in this way was about 13000.

Synthesis Example 4 Synthesis of Binder Resin d

145 weight part of propylene glycol monomethyl ether acetates were stirred, replacing with nitrogen, and it heated up at 120 degreeC. 30 weight part of styrene and 34 weight part of methacrylic acid were dripped here, and stirring was continued at 120 degreeC for 2 hours. Next, the inside of the reaction vessel was replaced with air substitution, 0.9 parts by weight of trisdimethylaminomethylphenol and 0.15 parts by weight of hydroquinone were added to 51 parts of (3,4-epoxycyclohexyl) methyl acrylate, and the reaction was continued at 120 ° C for 6 hours. I was. The weight average molecular weight Mw measured by GPC of the binder resin obtained in this way was about 18000.

Synthesis Example 5 Synthesis of Binder Resin e

145 weight part of propylene glycol monomethyl ether acetates were stirred, replacing with nitrogen, and it heated up at 120 degreeC. 53 weight part of benzyl methacrylate, 40 weight part of methyl methacrylates, and 26 weight part of methacrylic acid were dripped here, and stirring was continued at 120 degreeC for 2 hours. Next, the inside of the reaction vessel was replaced with air substitution, 0.9 parts by weight of trisdimethylaminomethylphenol and 0.15 parts by weight of hydroquinone were added to 40 parts by weight of (3,4-epoxycyclohexyl) methyl acrylate, and the reaction was continued at 120 ° C for 6 hours. I was. The weight average molecular weight Mw measured by GPC of the binder resin obtained in this way was about 16000.

Synthesis Example 6 Synthesis of Binder Resin a '

145 weight part of propylene glycol monomethyl ether acetates were stirred, replacing with nitrogen, and it heated up at 120 degreeC. 82 weight part of monoacrylates (Hitachi Chemical Co., Ltd. FA-513M) which has 20 weight part of styrene, 57 parts of glycidyl methacrylates, and a tricyclodecane skeleton are dripped here, and it continues at 140 degreeC for 2 hours. Stirred. Next, the inside of the reaction vessel was changed to air substitution, 0.7 parts by weight of trisdimethylaminomethylphenol and 0.12 parts by weight of hydroquinone were added to 27 parts by weight of acrylic acid, and the reaction was continued at 120 ° C for 6 hours. Then, 52 weight part of tetrahydro phthalic anhydride (THPA) and 0.7 weight part of triethylamines were added, and it reacted at 120 degreeC for 3.5 hours. When the weight average molecular weight Mw of the binder resin obtained in this way was measured by GPC, it was about 5000.

Synthesis Example 7 Synthesis of Binder Resin b '

145 weight part of propylene glycol monomethyl ether acetates were stirred, replacing with nitrogen, and it heated up at 120 degreeC. 10 weight part of styrene, 71 weight part of glycidyl methacrylates, and 82 weight part of monoacrylates (Hitachi Chemical Co., Ltd. FA-513M) which have a tricyclodecane skeleton are dripped here, and it is further again at 140 degreeC for 2 hours Stirring was continued. Next, the inside of the reaction vessel was replaced with air substitution, 0.9 parts by weight of trisdimethylaminomethylphenol and 0.15 parts by weight of hydroquinone were added to 34 parts by weight of acrylic acid, and the reaction was continued at 120 ° C for 6 hours. Then, 65 weight part of tetrahydro phthalic anhydride (THPA) and 0.8 weight part of triethylamines were added, and it was made to react at 120 degreeC for 3.5 hours. When the weight average molecular weight Mw of the binder resin obtained in this way was measured by GPC, it was about 6000.

Synthesis Example 8 Synthesis of Binder Resin c '

145 weight part of propylene glycol monomethyl ether acetates were stirred, replacing with nitrogen, and it heated up at 120 degreeC. 82 weight part of monoacrylates (Hitachi Chemical Co., Ltd. FA-513M) which has 20 weight part of styrene, 57 parts of glycidyl methacrylates, and a tricyclodecane skeleton are dripped here, and it continues at 120 degreeC for 2 hours. Stirred. Next, the inside of the reaction vessel was changed to air substitution, 0.7 parts by weight of trisdimethylaminomethylphenol and 0.12 parts by weight of hydroquinone were added to 27 parts by weight of acrylic acid, and the reaction was continued at 120 ° C for 6 hours. Then, 52 weight part of tetrahydro phthalic anhydride (THPA) and 0.7 weight part of triethylamines were added, and it reacted at 120 degreeC for 3.5 hours. When the weight average molecular weight Mw of the binder resin obtained in this way was measured by GPC, it was about 15000.

Synthesis Example 9 Synthesis of Binder Resin d '

145 weight part of propylene glycol monomethyl ether acetates were stirred, replacing with nitrogen, and it heated up at 120 degreeC. 10 weight part of styrene, 71 weight part of glycidyl methacrylates, and 82 weight part of monoacrylates (FA-513M by Hitachi Chemical Co., Ltd.) which have a tricyclodecane skeleton are dripped here, and it is further rested at 120 degreeC for 2 hours. Stirring was continued. Next, the inside of the reaction vessel was replaced with air substitution, 0.9 parts by weight of trisdimethylaminomethylphenol and 0.15 parts by weight of hydroquinone were added to 34 parts by weight of acrylic acid, and the reaction was continued at 120 ° C for 6 hours. Then, 65 weight part of tetrahydro phthalic anhydride (THPA) and 0.8 weight part of triethylamines were added, and it was made to react at 120 degreeC for 3.5 hours. When the weight average molecular weight Mw of the binder resin thus obtained was measured by GPC, it was about 17000.

Synthesis Example 10 Synthesis of Binder Resin e '

145 weight part of propylene glycol monomethyl ether acetates were stirred, replacing with nitrogen, and it heated up at 120 degreeC. 30 weight part of styrene and 34 weight part of methacrylic acid were dripped here, and it stirred at 140 degreeC again for 2 hours. Next, the inside of the reaction vessel was replaced with air substitution, 0.9 parts by weight of trisdimethylaminomethylphenol and 0.15 parts by weight of hydroquinone were added to 51 parts of (3,4-epoxycyclohexyl) methyl acrylate, and the reaction was continued at 120 ° C for 6 hours. I was. When the weight average molecular weight Mw of the binder resin thus obtained was measured by GPC, it was about 8000.

Synthesis Example 11 Synthesis of Binder Resin f '

145 weight part of propylene glycol monomethyl ether acetates were stirred, replacing with nitrogen, and it heated up at 120 degreeC. 53 weight part of benzyl methacrylate, 40 weight part of methyl methacrylates, and 26 weight part of methacrylic acid were dripped here, and it stirred at 140 degreeC again for 2 hours. Next, the inside of the reaction vessel was replaced with air substitution, 0.9 parts by weight of trisdimethylaminomethylphenol and 0.15 parts by weight of hydroquinone were added to 40 parts by weight of (3,4-epoxycyclohexyl) methyl acrylate, and the reaction was continued at 120 ° C for 6 hours. I was. When the weight average molecular weight Mw of the binder resin thus obtained was measured by GPC, it was about 8000.

Synthesis Example 12 Synthesis of Polycaprolactone

5 weight part of lauryl alcohol, 95 weight part of caprolactone, and 0.003 weight part of dibutyl tin dilaurate were mixed, and it heated to 160 degreeC within 1 hour. The addition reaction was terminated as soon as 99% solids content was obtained.

Synthesis Example 13 Synthesis of Polycaprolactone

The reaction was carried out under the same conditions as in Synthesis Example 12 except that the lauryl alcohol of Synthesis Example 12 was changed to methanol.

Synthesis Example 14 Synthesis of Urethane-Based Dispersion Resin

32 weight part of tolylene diisocyanate (the Mitsubishi Chemical Corporation make Mytec GP750A, resin solid content 50wt%, 2,4 bodies: 2,6 body = 8: 2 mixture, butyl acetate solution) and a catalyst 0.01 part by weight of tindilaurate was diluted with 47 parts by weight of PGMEA (propylene glycol monomethyl ether acetate). Under stirring, a mixture of 14.4 parts by weight of polycaprolactone having an average molecular weight of 2,000 with a lauryl alkoxy group (obtained in Synthesis Example 12) and 9.6 parts by weight of polyoxytetramethylene glycol having an average molecular weight of 1,000 was added dropwise thereto. Reaction was carried out for 3 hours. Next, 1 part by weight of N, N-dimethyl-1,3-propanediamine was added and reacted again at 40 ° C for 1 hour. The amine titer of the solution containing the dispersion resin thus obtained was found to be 32 mgKOH / g by neutralization titration. The resin content was determined by a dry-up method (heated at 150 ° C. for 30 minutes with a hot plate, and the solvent was removed to calculate the resin concentration based on the weight change). The resin content was 40 wt%.

Synthesis Example 15 Synthesis of Urethane-Based Dispersion Resin

Synthesis example except for changing polycaprolactone having an average molecular weight of 2,000 with one end of lauryl alkoxy group to polycaprolactone having an average molecular weight of 2,000 with one end of methoxy group (obtained in Synthesis Example 13). In the same manner as in 14, a dispersion resin having the following structure was obtained. The acid value of this resin was 32 mgKOH / g and the resin content was 40 wt%.

Synthesis Example 16 Synthesis of Urethane-Based Dispersion Resin

N, N was replaced with polycaprolactone having an average molecular weight of 2,000 having one end of lauryl alkoxy group in Synthesis Example 14 and having an average molecular weight of 2,000 having one methoxy group (obtained in Synthesis Example 13). A dispersion resin was obtained in the same manner as in Synthesis example 14 except that -dimethyl-1,3propanediamine was changed to 3-amino-1,2,4-triazole. The acid value of this resin was 32 mgKOH / g and the resin content was 40 wt%.

The structural formulas of the urethane-based dispersants prepared in Synthesis Examples 14 to 16 are shown below.

In the structural formula, each R independently represents any one of the groups shown in Table 1.

Table 1

Synthesis Example 17 Synthesis of Dispersant A '

50 parts by weight of polyethyleneimine having a molecular weight of about 5000 and 40 parts by weight of n = 5 polycaprolactone were mixed with 300 parts by weight of propylene glycol monomethyl ether acetate, and the mixture was stirred at 150 ° C. for 3 hours under nitrogen atmosphere. Thus, the weight average molecular weight Mw measured by GPC of the synthesize | combining dispersing agent was about 9000.

Synthesis Example 18 Synthesis of Dispersant B '

50 parts by weight of polyethyleneimine having a molecular weight of about 5000, 40 parts by weight of polycaprolactone of n = 5 and 6 parts by weight of stearic acid were mixed with 300 parts by weight of propylene glycol monomethyl ether acetate, and the mixture was stirred at 150 ° C. for 3 hours. . Thus, the weight average molecular weight Mw measured by GPC of the synthesize | combining dispersing agent was about 9300.

Synthesis Example 19 Synthesis of Dispersant C '

50 parts by weight of polyethyleneimine having a molecular weight of about 10000, 40 parts by weight of polycaprolactone of n = 5 and 6 parts by weight of stearic acid were mixed with 450 parts by weight of propylene glycol monomethyl ether acetate, and the mixture was stirred at 150 ° C. for 3 hours. . Thus, the weight average molecular weight Mw measured by GPC of the synthesize | combining dispersing agent was about 19000.

<Preparation of Red Pigment Dispersion>

10.00 parts by weight of CI Pigment Red 177 as a colorant, 33.75 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 6.25 parts by weight of the dispersant described in Table 1 as a dispersant, and 180 parts by weight of zirconia beads having a diameter of 0.5 mm in a stainless steel container And disperse | distributed for 6 hours with the paint shaker, the red pigment dispersion liquid was prepared.

<Preparation of Blue Pigment Dispersion>

CI pigment blue 15: 6 10.00 parts by weight as a colorant, 33.75 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 6.25 parts by weight of the dispersant described in Table 1 as a dispersant, and 180 parts by weight of zirconia beads having a diameter of 0.5 mm in a stainless steel container. It was filled and dispersed for 6 hours with a paint shaker to prepare a blue pigment dispersion.

<Preparation of Green Pigment Dispersion>

10.00 parts by weight of CI Pigment Green 36 as a colorant, 33.75 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 6.25 parts by weight of the dispersant shown in Tables 2 to 4 as a dispersant, and 180 parts by weight of zirconia beads having a diameter of 0.5 mm. Was charged and dispersed for 6 hours with a paint shaker to prepare a green pigment dispersion.

TABLE 2

A Dispersant synthesized in Synthesis Example-3 B Dispersant synthesized in Synthesis Example-4 C Dispersant synthesized in Synthesis Example-5 D Vicchemy Disperbyk-2000 (modified acrylic block copolymer) E Kusumoto Chemicals Disperon DA-325 (amine salt of polyether phosphate ester)

TABLE 3

Table 4

<Preparation of coloring composition>

Based on the composition shown to Tables 5-9, the other component was mixed with the said pigment dispersion liquid, and the curable resin composition of Examples 1-18 and Comparative Examples 1-13 was prepared.

And 0.33 weight part of succinic acid was added as an organic carboxylic acid component in addition to the component of Table 5 and Table 6 only for the comparative example 9.

Table 5

Type of ingredient The details of the ingredient Compounding amount (part by weight) Color The pigment dispersion 10.0 menstruum Pigment Dispersion + Propylene Glycol Monomethyl Ether Acetate 127.0 Dispersant The pigment dispersion 6.25 Binder resin Structure shown in the following table 6.5 Organic carboxylic acid, organic carboxylic anhydride Compounds listed in the table below Listed in the table below Photopolymerizable monomer 1 Ethylenic compound (a) 3.25 Photopolymerizable monomer 2 Ethylenic compound (b) 3.25 Photopolymerization initiator system component 1 2-mercaptobenzothiazole 0.83 Photopolymerization initiator system component 2 methyl p-dimethylaminobenzoate 0.83 Photopolymerization Initiator Component 3 Michalers Ketone 0.83

[Note] (1) The ethylenic compound (a) is a compound represented by the following structural formula [IV].

(2) The ethylenic compound (b) is trimethylolpropane triacrylate.

Table 6

Dispersant Binder resin Organic carboxylic acid, organic carboxylic anhydride Kinds Addition amount (part by weight) Example-1 A a Succinic anhydride 0.35 Example-2 B a Succinic anhydride 0.35 Example-3 C a Succinic anhydride 0.35 Example-4 A b Maleic anhydride 0.35 Example-5 C b Maleic anhydride 0.35 Example-6 A c Maleic anhydride 0.35 Comparative Example-1 C d Succinic anhydride 0.35 Comparative Example-2 C e Succinic anhydride 0.35 Comparative Example-3 D b Succinic anhydride 0.35 Comparative Example-4 E b none 0 Comparative Example-5 D e none 0

TABLE 7

Binder Resin (A) Raw material monomer of (B) copolymer (mol%) (C) component (addition rate ^{1 )} ) (D) component (addition rate ²⁾ ) (A) component (B) component Glycidyl methacrylate Tricyclodecanylacrylate Styrene Benzyl methacrylate Methyl methacrylate Methacrylic acid Acrylic acid Tetrahydrophthalic acid a 40 40 20 0 0 0 88 86 b 50 40 10 0 0 0 90 82 c 50 30 0 10 10 0 90 82 d 0 0 60 0 0 40 ³⁾ 0 0 e 0 0 0 30 30 40 ⁴⁾ 0 0

1) Addition rate (mol%) of (C) component with respect to the epoxy group contained in (A) (B) copolymer

2) Addition rate (mol%) of (D) component with respect to the hydroxyl group produced when added to (C) component.

3) Add (3,4-epoxycyclohexyl) methylacrylate to 70 mol% of methacrylic acid.

4) (3,4-epoxycyclohexyl) methylacrylate is added to 55 mol% of methacrylic acid

Table 8

Binder Resin Weight average molecular weight (Mw) (A) Raw material monomer of (B) copolymer (mol%) (C) component (addition rate ^{1 )} ) (D) Component (addition rate ^{2 )} ) (A) component (B) component Glycidyl methacrylate Tricyclodecanylacrylate Styrene Benzyl methacrylate Methyl methacrylate Methacrylic acid Acrylic acid Tetrahydrophthalic acid a ' 5000 40 40 20 0 0 0 88 86 b ' 6000 50 40 10 0 0 0 90 82 c ' 15000 40 40 20 0 0 0 88 86 d ' 17000 50 40 10 0 0 0 90 82 e ' 8000 0 0 60 0 0 40 ³⁾ 0 0 f ' 8000 0 0 0 30 30 40 ⁴⁾ 0 0

1) Addition rate (mol%) of (C) component with respect to the epoxy group contained in (A) (B) copolymer

2) Addition rate (mol%) of (D) component with respect to the hydroxyl group produced when added to (C) component.

3) Add (3,4-epoxycyclohexyl) methylacrylate to 70 mol% of methacrylic acid.

4) (3,4-epoxycyclohexyl) methylacrylate is added to 55 mol% of methacrylic acid

Table 9

Dispersant Binder resin Example-1 A a Example-2 B a Example-3 C a Example-4 A b Example-5 C b Example-6 A c Example-7 A ' a Example-8 B ' a Example-9 C ' a Example-10 A ' b Example-11 B ' b Example-12 A ' c Example-13 A " a ' Example-14 A " b ' Example-15 A "+ B" (weight ratio 2: 1) a ' Example-16 A "+ B" (weight ratio 2: 1) b ' Example-17 A "+ B" (weight ratio 2: 1) c ' Example-18 A "+ B" (weight ratio 2: 1) d ' Comparative Example-1 C d Comparative Example-2 C e Comparative Example-3 D b Comparative Example-4 E b Comparative Example-5 D e Comparative Example-6 A ' d Comparative Example-7 A ' e Comparative Example-8 D ' b Comparative Example-9 A ' d Comparative Example-10 A "+ B" (weight ratio 2: 1) e ' Comparative Example-11 A "+ B" (weight ratio 2: 1) f ' Comparative Example-12 C " a ' Comparative Example-13 C " b '

<Examples 19-27 and Comparative Examples 14, 15>

Synthesis Example 20 Synthesis of Binder Resin (a ")

35 parts of propylene glycol monomethyl ether acetate, 8.8 parts of 1-methoxy-2-propanol, and 1.5 parts of azo polymerization initiator (V-59, manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a reaction vessel and placed under a nitrogen atmosphere. It heated up at ° C, 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 were dripped for 2 hours, and also it stirred for 4 hours, and obtained the polymerization reaction liquid. .

25.5 parts of propylene glycol monomethyl ether acetate, 0.05 part of p-methoxyphenol, and 0.3 part of triphenylphosphines were added to the polymerization reaction solution and dissolved therein, followed by dropwise addition of 17.5 parts of (3,4-epoxycyclohexyl) methyl acrylate. The mixture was reacted at 85 ° C. for 24 hours to obtain a resin solution having an ethylenically unsaturated group in the side chain (hereinafter referred to as binder resin (a ″).) The polymerization average molecular weight of the obtained binder resin (a ″) by GPC was determined in terms of polystyrene. The titer was neutralized with 18000 and KOH, and the acid value was 50. The introduction ratio into the carboxylic acid by (3,4-epoxycyclohexyl) methyl acrylate was 66% from the acid value before and after the reaction.

Synthesis Example 21 Synthesis of Binder Resin (b ")

35 parts of propylene glycol monomethyl ether acetate, 8.8 parts of 1-methoxy-2-propanol, and 1.5 parts of azo polymerization initiator (V-59, manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a reaction vessel and placed under a nitrogen atmosphere. It heated up at ° C, and 10.5 parts of benzyl methacrylate, 7.5 parts of methyl methacrylate, and 11.9 parts of methacrylic acid were dripped for 2 hours, and also it stirred for 4 hours, and obtained the polymerization reaction liquid (henceforth binder resin (b ")). The polymerization average molecular weight by GPC of the obtained binder resin (b ") carried out the neutralization titration by 12000 and KOH in polystyrene conversion, and the acid value was 120.

Synthesis Example 22 Synthesis of Binder Resin (c ")

First, 145 parts of propylene glycol monomethyl ether acetates were stirred while nitrogen-substituted, and it heated up at 120 degreeC. 20 parts of styrene, 57 parts of glycidyl methacrylates, and 82 parts of monoacrylates ("FA-513M" by Hitachi Chemical Co., Ltd.) which have a tricyclodecane skeleton were dripped here, and it stirred at 120 degreeC again for 2 hours. .

Subsequently, the inside of the reaction container was air-substituted, 27.0 parts of acrylic acid, 0.7 parts of trisdimethylaminomethylphenol and 0.12 parts of hydroquinone were added, and the reaction was continued at 120 ° C for 6 hours. Then, 52.0 parts of tetrahydro phthalic anhydride (THPA) and 0.7 parts of triethylamine were added, and it reacted at 120 degreeC for 3.5 hours, and obtained the polymerization reaction liquid (henceforth binder resin (c ").) The obtained binder resin ( The polymerization average molecular weight by GPC of c ") was about 15000 in polyethylene conversion.

The kind of dispersing agent used by the following various examples is as showing in following Table 10. In addition, the heating nitrogen loss measurement and the heating loss measurement of a dispersing agent were performed by the following method, and the result is shown in Table 10.

<Measurement of heating nitrogen loss of dispersant>

About 50-100 mg of a dispersing agent is weighed into a 50 ml beaker, it is made to dry under reduced pressure for 48 hours on 60 degreeC and 10 mmHg conditions. Let this be a sample before heating. The dried dispersant is heated in a hot air circulation furnace at 230 ° C. for 30 minutes. This is taken as a sample after heating. The dispersant before and after heating is elementally analyzed by the PE2400 Series CHNS / O Analyzer manufactured by PERKIN ELMER to measure the total amount of nitrogen. The amount of nitrogen is a ratio in the total amount, and the absolute amount is calculated by multiplying the weight before and after the heating measured by the following method.

<Measurement of heating loss of dispersant>

The weight of the dispersant before and after heating obtained by the above method is measured by precision balance.

Table 10

Dispersant Total nitrogen weight Before heating (wt%) After heating (wt%) Residual rate (%) Before heating (wt%) After heating (wt%) Residual rate (%) Geneca manufactured by SOLSPERSE 34750 4.50 4.35 97 0.0752 0.0705 94 Big Chemi Co., Ltd.DispersBYK-161 8.10 7.25 90 0.0618 0.0566 92 Big Chemi Co., Ltd.DispersBYK-2001 3.04 1.53 50 0.1044 0.0711 68

<Preparation of Pigment Dispersion>

CI pigment green (CIPG) 36 and CI pigment yellow (CIP Y) 138 as the colorant, propylene glycol monomethyl ether acetate (PGMEA) as the solvent, the dispersant described in Table 10, the binder resin (a) and (b) described above ) Was mixed at the weight ratios shown in Tables 11 and 12. Here, zirconia beads (0.5 mm diameter), which is three times the total weight thereof, were mixed, filled into a stainless steel container, and dispersed for 6 hours with a paint shaker to prepare a green pigment dispersion.

Table 11

Table 12

<Preparation of colored resin composition>

The other component was mixed with each said pigment dispersion liquid, and the coloring resin composition which has a solid content ratio of Table 13 was prepared. The colored resin composition was prepared by diluting the whole with propylene glycol monomethyl ether acetate so that the total solid content concentration might be 20 weight%.

Table 13

Type of ingredient The details of the ingredient Solid content ratio (%) Pigment dispersion The pigment dispersion 53.0 Binder resin Binder Resin (c ") 23.5 Photopolymerizable monomer 1 Ethylenic compound (d ") 7.8 Photopolymerizable monomer 2 Ethylenic compound (e ") 3.9 Photopolymerization initiator system component 1 2-mercaptobenzothiazole 3.9 Photopolymerization initiator system component 2 methyl p-dimethylaminobenzoate 3.9 Photopolymerization Initiator Component 3 Michalers Ketone 3.9

The ethylenic compound (d ") in Table 13 is a compound represented by the following general formula (7), and ethylenic compound (e") is trimethylol propane triacrylate.

<Production of color filter>

After forming a metal chromium by sputtering on a glass substrate (370 mm long, 470 mm wide, 0.7 mm thick) made by Asahigarasu Corporation, and forming a matrix pattern with a positive photoresist, the solution is made of ammonium diacetate. The chromium film was etched using an etchant mixed with perchloric acid. Finally, the positive photoresist was stripped with a 5% aqueous sodium hydroxide solution to form a black matrix.

The colored resin composition containing a red color material was apply | coated using the die coater on the glass substrate with black matrix obtained in this way. As the die coater, a stainless steel die coater having a width of 360 mm was used, and the lip spacing was 200 μm and the gap with the glass substrate surface was 100 μm. When apply | coating, the discharge amount of the coating liquid which shows an ink image was adjusted so that it might be set to 1.3 micrometers in dry film thickness. Then, it dried for 1 minute at 60 degreeC, and heat-dried for 2 minutes at 110 degreeC. Subsequently, the exposure process was performed with the exposure amount of 300 mJ / cm <2> by the 2 kW high pressure mercury lamp using the negative photomask which repeats with the pitch of 30 micrometers in width, 330 micrometers in length, and 110 micrometers in width. Thereafter, development was carried out, and development was carried out at a developer temperature of 23 ° C. using a 0.1% by weight aqueous sodium carbonate solution. Subsequently, the spray was washed with water at a pressure of 3 kg / cm 2 for 30 seconds to form a red pixel. Then, the thermosetting process was performed at the temperature of 230 degreeC for 7 minutes.

Subsequently, the colored resin compositions containing the blue and green pigments were respectively applied in the same order as described above, pre-dried, heated, exposed, developed, washed, and thermally cured to form each color pattern sequentially. A color filter was obtained.

Thus, 100 sheets of color filters were produced using the curable resin compositions of Examples 1 to 30 and Comparative Examples 1 to 19.

In addition, in Examples 19 to 30 and Comparative Examples 14 to 17, only a green colored resin composition was used, and in Example 31 and Comparative Examples 18 and 19, only a blue colored resin composition was used to produce a single color filter, which will be described later. Provided for evaluation.

<Evaluation of White Exposure Defects in Color Filters>

The presence or absence of white exposure defect generation was measured about the obtained color filter, and the white exposure defect generation rate is shown in Table 14. In Table 14, red, blue, and green mean that white exposure exists on pixels of each color. In addition, the white exposure defect defines the white exposure that the square root of [(long diameter) ² + (short diameter) ² ] is 40 micrometers or more, and the longevity of the color filter by which the white exposure defect was recognized in any one color is the total manufacturing lifetime. The value divided by 100 sheets was defined as the incidence of white exposure defects. The evaluation results are shown in Table 14.

<Evaluation of Beauty Products (Residues) in Non-Pixel Filters>

The obtained color filter was operated by reciprocating the 30 × 100 mm portion of the non-pixel portion (on the base glass) with Toraysee MK clean cloth manufactured by Toray 10 times with ethanol. Toraysee MK clean cloth was fixed to the tip of each material made of 1 cm × 1 cm of resin, and an impregnated 0.1 cc of ethanol was used using a dropper. When it was not recognized visually that a pigment adhered to Toraysee, it evaluated as "(circle)", and even if a small amount was recognized as "x". In addition, the spectroscopic reflectance was measured on the 1 cm x 1 cm part of the polished Toraysee by the Shimadzu Corporation spectrophotometer UV3100S on the conditions using an integrating sphere. Table 14 shows the spectral reflectances of λ = 500 nm (corresponding to red residue), 450 nm (corresponding to green residue), and 550 nm (corresponding to blue residue).

In addition, the boundary of the (circle) x evaluation evaluated visually was equivalent to 95% in the spectral reflectance.

Table 14

According to the said Table 14, in all the Examples, the occurrence rate of a white exposure defect is 0%, and the residue was not recognized by the naked eye and spectral reflectance. On the other hand, in Comparative Examples 1-13, 17, and 19, the white exposure defect was recognized or the residue by visual observation and spectral reflectance was recognized.

Although the white exposure defect and the residue were not all recognized in Comparative Examples 14-16 and 18, the permeability mentioned later deteriorated.

<Permeability Evaluation (Measurement of Chromaticity)>

The colored resin composition of each Example and a comparative example was apply | coated on the glass substrate (ANA100 made by Asahi Glass Co., Ltd.) by the spin coating method, and it heated at 80 degreeC 3 minutes on a hotplate, and made the whole surface After exposing to 100mJ / cm <2>, it spray-developed for 30 second by the water pressure of 0.3 Mpa by the 23 degreeC 0.1 weight% sodium carbonate aqueous solution. Then, it baked at 230 degreeC 30 minutes in a hot-air circulation furnace. The coating thickness of the colored resin composition after baking was adjusted so that x = 0.60 for red, y = 0.55 for green, and y = 0.14 for blue (all C light sources) in color coordinates represented by a CIE color system.

For measurement of chromaticity, a spectrophotometer "U-3500" manufactured by Hitachi, Ltd. was used.

The chromaticity of each colored resin composition is shown in Table 15.

Table 15

Table 15 (continued)

According to the said Table 15, all the red, green, and blue pixels of the Example existed in the range of the following formula.

Red Y≥200y-41.4 (y <0.34)

Y≥200y-41.4 (y≥0.34)

Green Y≥240x-7.1

Blue Y≥20x + 16.2

On the other hand, in Comparative Examples 12-17, the chromaticity of the green pixel and the chromaticity of the blue pixel of Comparative Examples 4, 12, 13, 18, and 19 did not fall within the above formulas, respectively.

<Evaluation of development adhesiveness>

The colored resin compositions of each of Examples and Comparative Examples were coated on a glass substrate to have a dry film thickness of 1.3 μm, dried at 60 ° C. for 1 minute, and then dried by heating at 110 ° C. for 2 minutes, and having linear openings having a line width of 1 μm. After exposure using a mask at an exposure dose of 300 mJ / cm 2 with a gap of 150 μm, the solution was developed for 60 seconds with a liquid pressure of 0.2 kg / cm 2 at a developer temperature of 23 ° C. with an aqueous solution of 0.1 wt% sodium carbonate. Subsequently, when the pattern was formed by spray washing with a water pressure of 3 kg / cm 2 for 30 seconds, the minimum pattern width remaining as a linear image was measured. The results are shown in Table 16.

Table 16

Table 16 (continued)

According to Table 16, in the examples, all of red, green, and blue had a minimum pattern width of 10 µm or less. On the other hand, in Comparative Examples 2, 5, 7, 9, and 11, it was found that the minimum pattern width exceeded 10 µm.

<Evaluation of Viscosity Change Rate>

Immediately after the colored resin composition was prepared, and the viscosity (20 rpm) after standing in a constant temperature bath at 23 ° C. for 7 days was measured using an E-type viscometer "RE-80L" manufactured by Toki Industries. The viscosity with respect to the colored resin composition of each Example and a comparative example and the viscosity change rate of 7 days are shown in Table 17.

Table 17

Table 17 (continued)

According to the said Table 17, all of the Examples were 10% or less of the viscosity change rate of red, green, and blue. On the other hand, the comparative examples 4, 12-16, and 18 were more than 10% of a viscosity change rate.

<Evaluation of Foreign Material Defects in Color Filters>

About the obtained color filter, the presence or absence of the foreign material defect generation was measured, and the foreign material defect generation rate is shown in Table 18. In Table 18, red, blue, and green color indicate that white exposure exists on pixels of each color. In addition, the foreign material defect is defined as the foreign material that the square root of [(long diameter) ² + (short diameter) ² ] is 100 µm or more, and the total number of color filters in which the foreign material defect is recognized in any one color is 100 sheets. The value divided by) was defined as the foreign matter defect occurrence rate. The evaluation results are shown in Table 18.

<Evaluation of Red Solubility (Measurement of Volume Average Particle Diameter mv)>

The colored resin composition of each Example and the comparative example was apply | coated to the glass substrate of 50 mm in width, respectively by the spin coat method at 2.5 micrometers of dry film thicknesses, and it dried in the natural air for 60 minutes. Then, it was immersed in 6.25 g of the solvent which forms the coloring composition for 3 minutes, and it was redispersed, 10 minutes after the start of immersion, particle size distribution was measured by Nikkiso micro track UPA, and the volume average particle diameter mv was computed. The results are shown in Table 18.

Moreover, the volume average particle diameter mv in re-dissolution was equivalent to 200 nm or less that the foreign material defect generation rate became 0%.

Table 18

Table 18 (continued)

According to the said Table 18, Examples 1-16 and 31 did not have the incidence of a foreign material defect, and found it excellent also for die-coat application.

<Measurement of voltage holding ratio>

An electrode substrate A having an ITO film formed on an entire surface of an alkali-free glass substrate (AN-100 manufactured by Asahi Glass Co., Ltd.) having a width of 2.5 cm and a central portion of one glass substrate having a width of 2.5 cm An electrode substrate B having a 1 cm wide ITO film formed by a 2 mm wide extraction electrode was prepared.

After applying the alignment film agent (Sun Ever 7474) manufactured by Nissan Chemical Co., Ltd. on the electrode substrates A and B by spin coating method, the resultant was dried at 110 ° C. for 1 minute on a hot plate, and then 200 ° C. 1 in a hot air circulation path. It heated for time and formed the coating film of film thickness 70nm.

After coating the coloring composition of each Example on the electrode substrate A which apply | coated the orientation film agent by the spin coat method, heating 80 degreeC 3 minutes on a hotplate, exposing the whole surface to 100mJ / cm <2>, 0.1 degreeC sodium carbonate of 23 degreeC Spray development was carried out with an aqueous solution at a pressure of 0.3 MPa for 30 seconds. Then, it baked at 230 degreeC 30 minutes in a hot-air circulation furnace. Application | coating conditions were adjusted so that the film thickness of the coloring composition after baking may be set to 1.7 micrometers.

On the outer periphery of the electrode substrate B to which the alignment film was applied, an epoxy resin-based sealing agent containing silica beads having a diameter of 5 μm was applied using a dispenser, and then the outer edge portion was 3 mm on the surface where the coloring composition of the electrode substrate A was applied. It heats 180 degreeC for 2 hours in a hot-air circulation path in the state which arrange | positioned so as to oppose and was compressed.

The liquid crystal (MLC-6846-000 by Merck Japan Corporation) was inject | poured into the empty cell obtained in this way, the peripheral part was sealed with UV curable sealing compound, and the liquid crystal cell for voltage retention measurements was completed.

The liquid crystal cell was annealed (heated at 105 ° C. for 2.5 hours in a hot air circulation path), and then a pulse voltage was applied to electrode substrates A and B under conditions of an applied voltage of 5 V and a pulse frequency of 60 Hz to measure voltage retention.

Table 19 shows the voltage retention of each coloring composition.

Table 19

Voltage retention rate (%) Example-19 94 Example-20 89 Example-21 95 Example-22 90 Example-23 97 Example-24 93 Example-25 60 Example-26 71 Example-27 72 Comparative Example-14 93 Comparative Example-15 93

According to the said Table 19, in Examples 19-24, it also turns out that it is excellent also in voltage retention.

<Examples 28-31 and Comparative Examples 16-19>

Synthesis Example 23 35 parts of propylene glycol monomethyl ether acetate, 8.8 parts of 1-methoxy-2-propanol, and 1.5 parts of V-59 (Azo polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a reaction vessel, followed by a nitrogen atmosphere. It heated up at 80 degreeC below, 9.5 parts of benzyl methacrylate, 6.5 parts of methyl methacrylates, 3.5 parts of 2-hydroxyethyl methacrylates, and 10.7 parts of methacrylic acid were dripped at 2 hours, and also it stirred for 4 hours, and the polymerization reaction liquid Got. 25.5 parts of propylene glycol monomethyl ether acetate were added to this polymerization reaction solution, 0.05 parts of p-methoxyphenol and 0.3 parts of triphenylphosphine were added and dissolved, and then 17.5 parts of (3,4-epoxycyclohexyl) methyl acrylate. The mixture was added dropwise and reacted at 85 ° C. for 24 hours to obtain a resin solution having an ethylenically unsaturated group in the side chain. The polymerization average molecular weight by GPC of the binder resin obtained in this way was 18000 in polystyrene conversion, and the neutralization titration by KOH was carried out, and the acid value was 50. The introduction ratio into the carboxylic acid by (3,4-epoxycyclohexyl) methyl acrylate was 66% from the acid value before and after the reaction.

<Example 28>

9.4 parts of Pigment Green 36 as pigments, 23.4 parts of the resin solution obtained in Synthesis Example 23 (9.4 parts as resin solids), and 42.4 parts of propylene glycol monomethyl ether acetate as a solvent were dispersed in a paint conditioner containing zirconia beads for 5 hours to obtain green ink. (Coloring resin composition) was obtained. It shows in Table 20 about the liquid property of this colored resin composition.

10.9 parts of green ink obtained in this way, 5.5 parts of resin solution obtained by mixing separately and preparing, 0.73 parts of dipentaerythritol hexaacrylate as a photopolymerizable monomer, 0.26 parts of biimidazole as a photoinitiator, a sensitizer 0.14 parts of 4,4'-bis (diethylamino) benzophenone (EABF) as an example, 0.05 parts of 2-mercaptobenzothiazole (2MBT) as a chain transfer agent, and 0.001 parts of fluorine-based surfactants (FC-430 manufactured by Sumitomo 3M). And the photosensitive resin composition which consists of 28.8 parts of propylene glycol monomethyl ether acetate as a solvent were added and mixed, and the green photosensitive colored resin composition was obtained.

The green photosensitive coloring composition was spin-coated on a glass substrate (AN635 manufactured by Asahi Glass Co., Ltd.), and dried by heating at 70 ° C. with a hot plate to obtain a photosensitive green layer having a thickness of 1.5 μm. Ultraviolet light of 200mJ / cm <2> was irradiated to this coating film using the ultrahigh pressure mercury lamp. Thereafter, a shower was developed for 120 seconds with an alkaline developer and washed with ultrapure water for 10 seconds to form a green pattern. When the pattern after image development was observed, the pattern with a good line shape and adhesiveness was obtained. Furthermore, scuming was visually observed by applying a halogen light to the developed unexposed part of the substrate. Table 20 shows the result as (circle) that there is no scuming at all, (triangle | delta) and the thing which looks white entirely as x as what was seen to be a little white. In addition, Table 21 shows the result of measuring the Y value in chromaticity (x, y) in a CIE colorimeter.

<Example 29>

9.4 parts of pigment green 36 as a pigment, 23.4 parts of the resin solution obtained in the synthesis example 23 (9.4 parts as resin solid content), 0.47 parts of the sulfonic acid derivatives of pigment yellow 138 as a dispersing aid, and 42.4 parts of propylene glycol monomethyl ether acetate as a solvent A green ink (colored resin composition) was obtained in the same manner as in Example 28 except for using. It shows in Table 1 about the liquid property of this colored resin composition. Using the obtained green ink, the photosensitive colored resin composition was formed by the method similar to the method of Example 28, and the green pattern was formed by the same method. When the pattern after image development was observed, the pattern with a good line shape and adhesiveness was obtained. Table 20 also shows the results of scumming of the substrate unexposed portion after development. In addition, the Y value of the obtained pixel is shown in Table 21.

<Example 30>

9.4 parts of Pigment Green 36 as pigments and 23.4 parts of the resin solution obtained in Synthesis Example 23 (9.4 parts as resin solids) were premixed with a homogenizer, and then the solvent was evaporated at 80 ° C. for 1 hour to color the kneading colored resin. A composition was obtained. The obtained colored resin composition was kneaded for 5 hours in a kneader to obtain a colored chip. Moreover, the temperature of kneader was controlled at 80 degreeC. After adding 42.4 parts of propylene glycol monomethyl ether acetate to 18.8 parts of obtained coloring chips and making it swell for 12 hours, it stirred for 3 hours using the homogenizer and created the mill face.

The mill face thus obtained was treated with a bead molar device for 10 minutes at residence time using 0.3 mm zirconia beads to create green ink.

It disperse | distributed for 5 hours with the paint conditioner containing zirconia beads, and obtained green ink (colored resin composition). It shows in Table 1 about the liquid property of this colored resin composition.

The photosensitive coloring resin composition was formed in the same method as the method of Example 28 using the green ink obtained in this way, and the green pattern was formed by the same method. When the pattern after image development was observed, the pattern with a good line shape and adhesiveness was obtained. Table 20 also shows the results for scumming of the substrate unexposed portion after development. In addition, the Y value of the obtained pixel is shown in Table 21.

Comparative Example 16

The colored resin composition was obtained by the same process as Example 28 except having used the benzyl methacrylate methacrylic acid copolymer (weight average molecular weight 15000, acid value 90) as resin. Table 20 shows the liquidity of the obtained colored resin composition. And although the photosensitive coloring resin composition was formed and developed by the same process as Example 28, the unexposed part did not melt even in 300s. Table 21 shows the Y value of the obtained pixel.

Comparative Example 17

A colored resin composition was obtained in the same manner as in Example 28 except that the commercially available urethane-based dispersant X was used. Table 20 shows the liquidity of the obtained colored resin composition. And a green pattern was formed in the same process as in Example 28. When the pattern after image development was observed, the pattern with a good line shape and adhesiveness was obtained. Table 20 shows the results for scumming of the substrate unexposed portion. In addition, the Y value of the obtained pixel is shown in Table 21.

Table 20

Suzy Liquid ^{* 1} Phenomenon residue Example 28 Synthesis Example 23 ○ ○ Example 29 Synthesis Example 23 ○ ○ Example 30 Synthesis Example 23 ○ ○ Comparative Example 16 Benzyl methacrylate methacrylic acid copolymer (polymerization average molecular weight 15000, acid value 90) × - Comparative Example 17 Urethane Dispersant X ○ ×

* 1 viscosity of the colored resin composition

○: low viscosity

△: slightly thickening

X: Thickening

Table 21

Suzy Y (when x = 0.234, y = 0.472) Example 28 Synthesis Example 23 56.9 Example 29 Synthesis Example 23 58.0 Example 30 Synthesis Example 23 57.0 Comparative Example 16 Benzyl methacrylate methacrylic acid copolymer (polymerization average molecular weight 15000, acid value 90) 55.3 Comparative Example 17 Urethane Dispersant X 56.1

<Example 31>

Pigment Blue 15: 6 as a pigment was dispersed in 9.4 parts, 23.4 parts of the resin solution obtained in Synthesis Example 23 (9.4 parts as a resin solid), and 42.4 parts of propylene glycol monomethyl ether acetate as a solvent in a paint conditioner containing zirconia beads for 10 hours. A blue ink (colored resin composition) was obtained. Table 22 shows the liquidity of the obtained colored resin composition.

In the same process as in Example 28, a blue pattern was formed. When the pattern after image development was observed, the pattern with a good line shape and adhesiveness was obtained. Moreover, the result regarding the scumming of the board | substrate unexposed part after image development is shown in Table 22. Table 23 shows the Y values of the obtained pixels.

Comparative Example 18

The colored resin composition was obtained by the same process as Example 28 except having used the benzyl methacrylate methacrylic acid copolymer (weight average molecular weight 14000, acid value 52) as resin. Table 22 shows the liquidity of the obtained colored resin composition. And although it developed in the same process as Example 28, the unexposed part did not melt even in 300s. Table 23 shows the Y value of the obtained pixel.

Comparative Example 19

A colored resin composition was obtained in the same manner as in Example 28 except that Commercial Polymer Dispersant Y was used as the resin. Table 22 shows the liquidity of the obtained colored resin composition. In the same process as in Example 28, a blue pattern was formed. When the pattern after image development was observed, the pattern with a good line shape and adhesiveness was obtained. Table 22 shows the results for scumming of the substrate unexposed portion. Table 23 also shows the Y values of the obtained pixels.

Table 22

Suzy Liquid ^{* 1} Phenomenon residue Example 31 Synthesis Example 23 ○ ○ Comparative Example 18 Benzyl methacrylate methacrylic acid copolymer (polymerization average molecular weight 14000, acid value 52) × - Comparative Example 19 Urethane Dispersant Y ○ ×

* 1 viscosity of the colored resin composition

○: low viscosity

△: slightly thickening

X: Thickening

Table 23

Suzy Y (when x = 0.134, y = 0.121) Example 31 Synthesis Example 23 15.1 Comparative Example 18 Benzyl methacrylate methacrylic acid copolymer (polymerization average molecular weight 14000, acid value 52) 14.7 Comparative Example 19 Urethane Dispersant Y 14.9

Also in Examples 28 to 31 and Comparative Examples 16 to 19, similarly to Examples 1 to 27 or Comparative Examples 1 to 15, permeability, development adhesiveness, white exposure defect, undissolved residue, viscosity change rate, redissolution, and voltage retention were evaluated respectively. It was. The results are shown in Tables 14 to 19.

From the above result, when comparing the result of Examples 1-31 (the colored resin composition concerning this invention) with the result of the comparative example 1-the comparative example 19, it turns out that it is as follows.

(1) The colored resin composition which concerns on this invention is high permeability and high concentration.

(2) The colored resin composition which concerns on this invention has little residual | surviving thing of an undissolved matter in the non-pixel part on a board | substrate after image development.

(3) The colored resin composition which concerns on this invention is excellent in the adhesiveness of the image at the time of image development, and generation | occurrence | production of a white exposure defect is suppressed.

(4) As for the colored resin composition which concerns on this invention, generation | occurrence | production of a foreign material defect is suppressed by the coating by the die-coat method.

(5) The colored resin composition which concerns on this invention has little viscosity change rate.

(6) The colored resin composition which concerns on this invention has very little influence on the voltage retention of a liquid crystal.

Although this invention was demonstrated in detail with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the meaning and range of this invention.

In addition, the present application is a Japanese patent application filed on July 18, 2002 (Japanese Patent Application No. 2002-210065), a Japanese patent application filed on February 7, 2003 (Japanese Patent Application No. 2003-30954), Japanese Patent Application Filed February 24, 2003 (Japanese Patent Application No. 2003-45364), Japanese Patent Application Filed February 25, 2003 (Japanese Patent Application No. 2003-47604), April 2003 Japanese Patent Application (Japanese Patent Application No. 2003-122854) filed on March 25, Japan Patent Application (Japanese Patent Application No. 2003-124291) filed on April 28, 2003 and Japanese Patent Application on October 27, 2003 It is based on the Japanese patent application (Japanese Patent Application No. 2003-366100), which is incorporated in its entirety by reference.

The present invention exhibits useful effects as follows, and its industrial use value is very large.

1. When apply | coating this on a board | substrate, the coloring resin composition which concerns on this invention does not remain undissolved thing in the non-pixel part on a board | substrate, and can form uniformly the high density color pixel excellent also in adhesiveness with a board | substrate. . In addition, even when the coating is performed by the die coating method, foreign matters such as dry flocculated agglomerates are less likely to occur. In addition, since the influence on the voltage holding ratio of the liquid crystal is very small, display defects such as display unevenness and partial degradation are unlikely to occur.

2. The color filter which concerns on this invention does not remain undissolved matter of a colored resin composition in the non-pixel part on a board | substrate. In addition, since the influence on the voltage holding ratio of the liquid crystal is very small, display defects such as display unevenness and partial deterioration are less likely to occur, and the quality is very high.

3. In the liquid crystal display device according to the present invention, an undissolved substance of the colored resin composition does not remain in the non-pixel portion on the substrate, and since the voltage holding ratio of the liquid crystal does not decrease well, a very high quality color filter in which display unevenness is unlikely to occur. Because it is used, it is very high quality.

Claims (34)

A colored resin composition containing a colorant, a solvent, a dispersant, and a binder resin, wherein the binder resin has a nitrogen atom-free binder having a structure in which an epoxy group of an epoxy group-containing unsaturated compound (b) is added to a carboxyl group of a resin (a) having a carboxyl group. Contains resin, The dispersant contains a nitrogen atom-containing dispersant, and the weight ratio of the nitrogen atom-containing dispersant to the colorant is 0.01 or more and 0.5 or less. The nitrogen atom-containing dispersant according to claim 1, wherein the nitrogen atom-containing dispersant comprises: (E) a urethane-based dispersant, (F) a graft copolymer containing a nitrogen atom, (G) an A block having a quaternary ammonium salt in the side chain and B having no quaternary ammonium salt The colored resin composition containing one or more of the AB block copolymer and / or BAB block copolymer which consists of a block. As a coloring resin composition containing a color material, a solvent, a dispersing agent, and binder resin, Binder resin copolymerizes 5 to 90 mol% of (A) epoxy containing (meth) acrylate, and 10-95 mol% of other radically polymerizable compounds which can be copolymerized with (B) (A) component, and is contained in the obtained copolymer Resin obtained by adding (C) unsaturated monobasic acid to 10-100 mol% of the prepared epoxy group, and then adding (D) polybasic acid anhydride to 10-100 mol% of hydroxyl groups produced when said (C) component is added. The dispersing agent is an AB block copolymer comprising (E) a urethane-based dispersant, (F) a graft copolymer containing a nitrogen atom, (G) an A block having a quaternary ammonium salt in the side chain and a B block having no quaternary ammonium salt. And / or one or more of the BAB block copolymers. The urethane-based dispersant according to claim 2 or 3, wherein (E) the urethane-based dispersant is (1) a polyisocyanate compound, (2) a compound having one or two hydroxyl groups in the same molecule, and (3) active hydrogen and 3 in the same molecule. It is a dispersion resin obtained by making the compound which has a primary amino group react. The colored resin composition characterized by the above-mentioned. (F) The graft copolymer containing a nitrogen atom has a repeating unit containing a nitrogen atom in the main chain of the graft copolymer, The coloring resin composition of Claim 2 or 3 characterized by the above-mentioned. The graft copolymer according to any one of claims 2, 3 and 5, wherein the graft copolymer containing a nitrogen atom is represented by a repeating unit represented by the following formula (I) or / and the following formula (II). It has a repeating unit displayed, The colored resin composition characterized by the above-mentioned. (In formula, R <_1> represents a C1-C5 alkylene group and A represents a hydrogen atom or any of following formula (III)-(V).) (In formula, R <_1> represents a C1-C5 alkylene group and A represents a hydrogen atom or any of following formula (III)-(V).) (W <_1> shows a C2-C10 alkylene group in a formula, and p shows the integer of 1-20.) (Wherein Y ₁ represents a divalent linking group, W ₂ represents the carbon number of 2~10 alkylene group, Y ₂ is a hydrogen atom or -CO-R ₂ (R ₂ represents an alkyl group having 1 to 10 carbon atoms), q represents the integer of 1-20.) (W <_3> shows a C1-C50 hydroxyalkyl group which has a C1-C50 alkyl group or 1-5 hydroxyl groups in a formula.) The A block of the AB block copolymer and / or BAB block copolymer of Claim 2 or 3 which consists of an A block which has a quaternary ammonium salt in a side chain, and a B block which does not have a quaternary ammonium salt, The colored resin composition characterized by including the partial structure represented by general formula (I). (In formula (I), R _1a , R _2a and R _3a each independently represent a hydrogen atom or a cyclic or chain hydrocarbon group which may be substituted. Or two or more of R _1a , R _2a and R _3a ). These may combine with each other and may form the cyclic structure. R _4a represents a hydrogen atom or a methyl group. X represents a divalent linking group, and Y ⁻ represents a large anion.) The colored resin composition of any one of Claims 2-7 which contains mono (meth) acrylate which has a structure represented by following General formula (VI) as (B) component of binder resin. . (In the general formula (VI), R ₃ to R ₈ each independently represent a hydrogen atom or an alkyl group having 1 to 3. R ₉ and R ₁₀ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Or R ₉ and R ₁₀ may be linked to each other to form a ring.) The colored resin composition according to any one of claims 2 to 8, further comprising a phosphate ester type dispersant as a dispersant. 10. The colored resin composition according to claim 9, wherein the phosphate ester type dispersant comprises a partial structure represented by the following General Formula (3). The colored resin composition according to any one of claims 3 to 10, which contains an organic carboxylic acid and / or an organic carboxylic anhydride having a molecular weight of 1,000 or less. The colored resin composition according to claim 1, wherein the resin (a) having a carboxyl group has a hydroxyl group. The colored resin composition according to any one of claims 1 to 12, which contains a photopolymerizable monomer. The colored resin composition as described in any one of Claims 1-13 containing a photoinitiation system component. The epoxy group of the epoxy group-containing unsaturated compound (b) is added to the carboxyl group of the resin (a) having a colorant, a solvent, a nitrogen atom-containing dispersant, and a carboxyl group. The colored resin composition obtained by mixing and disperse | distributing and disperse | distributing and nitrogen-containing binder resin which has a structure as needed. As a coloring resin composition containing a color material, a solvent, and binder resin, The colored resin composition is applied to a film thickness such that the chromaticity in the CIE color system is x = 0.60, and the Y value in the color system after firing at 230 ° C. for 30 minutes is represented by any one of the following formulas (1) and (2): In range, Y≥200y-41.4 (y <0.34) (1) Y≥100y-7.4 (y≥0.34) (2) (Wherein Y and y represent reflectance and chromaticity in the CIE color system, respectively.) When the pattern was formed using the colored resin composition, the minimum pattern width remaining as a linear image was 10 µm or less, In addition, 1 kgf / cm 2 of non-pixel portion (on base glass) having an area of 10 cm 2 was fabricated using 1 cm × 1 cm of cotton composed of polyester long fibers of 3 μm or less on average, impregnated with 0.1 cc / cm 2 of ethanol. The spectral reflectance of 500 nm of a pigment adhesion part is 95% or more when it wash | cleans by the pressure of the red colored resin composition. As a coloring resin composition containing a color material, a solvent, and binder resin, The colored resin composition is applied to a film thickness such that the chromaticity in the CIE color system is y = 0.55, and the Y value in the color system after firing at 230 ° C. for 30 minutes is within a range represented by the following formula, Y≥240x-7.1 (Wherein Y and x represent reflectance and chromaticity in the CIE color system, respectively.) When the pattern was formed using the colored resin composition, the minimum pattern width remaining as a linear image was 10 µm or less, In addition, 1 kgf / cm 2 of non-pixel portion (on base glass) having an area of 10 cm 2 was fabricated using 1 cm × 1 cm of cotton composed of polyester long fibers of 3 μm or less on average, impregnated with 0.1 cc / cm 2 of ethanol. The 450 nm spectral reflectance of a pigment adhesion part is 95% or more when it wash | cleans by the pressure of the green coloring resin composition characterized by the above-mentioned. As a coloring resin composition containing a color material, a solvent, and binder resin, The colored resin composition was applied at a film thickness such that the chromaticity in the CIE color system became y = 0.14, and after baking at 230 ° C. for 30 minutes, the Y value in the color system was in a range represented by the following formula, Y≥20x + 16.2 (Wherein Y and x represent reflectance and chromaticity in the CIE color system, respectively.) When the pattern was formed using the colored resin composition, the minimum pattern width remaining as a linear image was 10 µm or less, In addition, 1 kgf / cm 2 of non-pixel portion (on base glass) having an area of 10 cm 2 was fabricated using 1 cm × 1 cm of cotton composed of polyester long fibers of 3 μm or less on average, impregnated with 0.1 cc / cm 2 of ethanol. The 550 nm spectral reflectance of a pigment adhesion part is 95% or more when it wash | cleans by the pressure of the blue coloring resin composition. The colored resin composition according to any one of claims 16 to 18, wherein the rate of change of viscosity when stored at 23 ° C. for 7 days is 10% or less with respect to the initial viscosity. The colored resin composition as described in any one of Claims 16-19 containing a color material, a solvent, and binder resin, The dry film formed by this colored resin composition is immersed in the solvent which comprises this colored resin composition, and redispersed. When made, the volume average particle diameter (mv) in a redispersion liquid becomes 200 nm or less, The colored resin composition characterized by the above-mentioned. 21. The colored resin composition according to any one of claims 16 to 20, which comprises a color material, a solvent, and a binder resin, after annealing the coating film formed by the colored resin composition in contact with the liquid crystal. The voltage retention ratio at the time of applying a voltage to the said liquid crystal through a coloring resin layer is a coloring resin composition characterized by the above-mentioned. The radically polymerizable compound according to any one of claims 16 to 21, wherein the binder resin is copolymerizable with (A) epoxy-containing (meth) acrylate 5 to 90 mol% and (B) (A) component. 10-95 mol% is copolymerized, (C) unsaturated monobasic acid is added to 10-100 mol% of the epoxy group contained in the obtained copolymer, and then 10-10 of the hydroxyl group produced when the said (C) component is added. It is resin obtained by adding (D) polybasic acid anhydride to 100 mol%. The colored resin composition characterized by the above-mentioned. 23. The quaternary ammonium salt according to any one of claims 16 to 22, wherein the dispersant is (E) a urethane-based dispersant, (F) a graft copolymer containing a nitrogen atom, (G) an A block having a quaternary ammonium salt group in the side chain and a quaternary ammonium salt A colored resin composition comprising at least one of an AB block copolymer and / or a BAB block copolymer composed of a B block having no. It formed using the colored resin composition of any one of Claims 1-23, The color filter board | substrate characterized by the above-mentioned. It formed using the color filter substrate of Claim 24, The liquid crystal display device characterized by the above-mentioned. Resin (H) which consists of a structure which adds the epoxy group of an epoxy-group-containing unsaturated compound (b), and color material (I) by mixing and disperse | distributing a carboxyl group of resin (a) which has a carboxyl group to manufacture colored resin composition (J) The manufacturing method of the colored resin composition (M) containing the step and mixing the resin (K) and the solvent (L) with this colored resin composition (J). 27. The method for producing a colored resin composition according to claim 26, wherein the epoxy group-containing unsaturated compound (b) is an alicyclic epoxy compound. The method for producing a colored resin composition according to claim 26 or 27, wherein the resin (a) having a carboxyl group has a hydroxyl group. 29. The method for producing a colored resin composition according to any one of claims 26 to 28, comprising a pigment derivative as a dispersion aid. The colored resin composition represented by (J) used for the manufacturing method in any one of Claims 26-29. The colored resin composition represented by (M) manufactured by the manufacturing method of Claims 26-29. To the colored resin composition containing resin (H) which consists of adding the epoxy group of an epoxy-group-containing unsaturated compound (b), a coloring material (I), a photopolymerizable monomer, and a photoinitiator to the carboxyl group of resin (a) which has a carboxyl group. The colored resin composition as described above, wherein 60% by weight or more of the resin component is an alkali-soluble resin. The color filter substrate formed using the coloring resin composition of Claim 31 or 32. A liquid crystal display device comprising the color filter substrate according to claim 33.