JP2019113614A - Photosensitive coloring composition for color filter, and color filter - Google Patents

Abstract

To provide a photosensitive coloring composition for color filters, which allows for forming good pattern shapes and a coating film with superior developability and water stain resistance, and to provide a method of producing a color filter with filter segments formed using the same.SOLUTION: The above challenge is cleared by a photosensitive coloring composition for color filters, containing a colorant (A), a photopolymerizable compound (B), a photopolymerization initiator (C), β-hydroxyalkylamide (D), and a carboxyl group-containing oxetane compound (E).SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive coloring composition for color filters used in the manufacture of color filters used in color liquid crystal display devices, color organic EL display devices, color image pickup tube devices and the like, and filters formed using the same. The present invention relates to a color filter having a segment.

At present, as a method for producing a color filter, a method called a pigment dispersion method in which a pigment excellent in light resistance and heat resistance is used as a colorant is in the mainstream.
In the case of the pigment dispersion method, a photosensitive coloring composition (pigment resist) in which a pigment is dispersed in a photosensitive resin solution is applied to a transparent substrate such as glass, and the solvent is removed by drying. Then, the unexposed area is removed in the development step to form a first color pattern, and if necessary, a treatment such as heating is applied, and then the same operation is sequentially repeated for all filter colors to produce a color filter. can do.

In recent years, color liquid crystal display devices have formed a large market as liquid crystal color televisions, notebook computers for car navigation and liquid crystal display devices integrated type, and monitors and televisions for desktop personal computers utilizing the features of energy saving and space saving. It is beginning to spread as well. Attention is focused on as a display device to replace conventional CRTs, but at present the color reproduction characteristics of liquid crystal display devices are inferior to that of CRTs.
Therefore, in a color filter in which filter segments of respective colors are arranged, a demand for high color reproducibility is increasing.

  Also, in order to improve the contrast, a black matrix is generally disposed between the filter segments of each color of the color filter, but in recent years, the forming material of this black matrix has environmental problems, low reflection, and low cost. From the point of view, a resin black matrix in which a light shielding pigment is dispersed in a resin is noted instead of the metal chromium black matrix. However, the resin black matrix has a problem that the light shielding property (optical density) is lower than that of the metal chromium black matrix.

  In order to improve the color reproduction characteristics of the color filter and the light shielding property of the black matrix, it is necessary to increase the content of the pigment in the photosensitive coloring composition or to increase the film thickness. However, in the method of increasing the content of the pigment, problems such as deterioration in sensitivity, developability and resolution occur. In the method of increasing the film thickness, the exposure light does not reach the bottom of the film, and problems such as poor pattern shape and deterioration of chemical resistance, solvent resistance and heat resistance due to insufficient sensitivity in the coating film occur. Do. In order to solve such problems, it is necessary to increase the sensitivity of the photosensitive coloring composition and to impart curability. With respect to the improvement in sensitivity, the resin may be provided with a reactive double bond, a photopolymerization initiator, or the like. Selection or increase of the photosensitive agent, (3) selection or increase of the monomer, and the like are carried out, and as an example thereof, Patent Document 1 can be mentioned. With regard to imparting curability, Patent Document 2 and Patent Document 3 propose selection or increase of a curing agent, addition of a thermal crosslinking group to a dispersant, and the like. However, there is a limit to the application of double bond of resin, selection of photo polymerization initiator, sensitizer and monomer, introduction of curable component, and selection of curing agent, and there is a limit to shape rectangularity by heat flow, developability Problems such as defects and poor water stain resistance remain.

JP, 2002-167404, A JP, 2012-198527, A JP, 2009-155406, A

  The object of the present invention is to provide a photosensitive coloring composition for color filters which is excellent in heat flowability (pattern shape, linearity), developability and water stain resistance, and a color filter using the same. is there.

  As a result of intensive studies to solve the above problems, the present inventors have found that when a β-hydroxyalkylamide and a carboxyl group-containing oxetane compound are used as a photosensitive coloring composition for a color filter, It has been found that the formation of a pattern shape having good properties, the developability and the resistance to water stain are excellent, and the present invention has been made.

  <1> Color filter photosensitive material containing a colorant (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a β-hydroxyalkylamide (D), and a carboxyl group-containing oxetane compound (E) Coloring composition.

  The photosensitive coloring composition for said color filters whose weight average molecular weight (Mw) of a <2> carboxyl group containing oxetane compound (E) is 5,000-20,000.

The photosensitive coloring composition for said color filters whose <3> (beta) -hydroxy alkylamide (D) is a compound represented by following General formula (1).
General formula (1)

[In general formula (1), X is an n-valent group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom, n is an integer of 2 to 6, and R ¹ and Each R ² independently represents a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by the general formula (2), or a group represented by the general formula (3) At least one of R ¹ and R ² which is a group and is bonded to one or more nitrogen atoms is a group represented by the general formula (2), and at least one is a general formula (3) Is a group represented by

General formula (2)

General formula (3)

[In general formulas (2) and (3), R ^{3 to} R ⁶ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxyl group, and R ⁷ may react with a hydroxyl group Represents a residue of a compound having a functional group. ]

  The said photosensitive coloring composition for color filters whose content of <4> (beta) -hydroxy alkylamide (D) is 1-20 mass parts with respect to the total solid amount in the photosensitive coloring composition for color filters.

  The photosensitive coloring composition for said color filters in which a <5> coloring agent (A) contains a green pigment.

  The color filter which comprises the filter segment formed with the said photosensitive coloring composition for color filters on a <6> base material.

  According to the present invention, the photosensitive coloring composition for color filters is excellent in heat flow properties and linear by containing the β-hydroxyalkylamide (D) and the compound (E) having a carboxylic acid-containing oxetane group. It is possible to provide a photosensitive coloring composition for a color filter which can form a good pattern shape and can form a coating film excellent in water stain resistance and developability. In addition, the above can provide a high quality color filter.

  Both the β-hydroxyalkylamide and the carboxyl group-containing oxetane compound of the present invention are known as materials that cure at low temperature bake. In each use alone, the heat crosslinking component in the coating film is insufficient, and the linearity of the pattern shape due to the heat flow at the time of high temperature baking occurs. However, by using in combination, cross-linking can be performed stepwise by high-temperature baking from a low temperature of a pattern shape utilizing different reaction temperatures, and the effect of suppressing the heat flow at the time of coating film baking can be obtained. In addition, the increase in the molecular weight of the coating film due to the reaction between the acid group in the carboxyl group-containing oxetane compound and the β-hydroxyalkylamide also contributes to further suppression of the heat flow of the coating film at the time of baking. Thereby, the colored composition of the present invention can obtain a good pattern shape of linearity even at high temperature baking.

  Further, by using the above-mentioned β-hydroxyalkylamide and the carboxyl group-containing oxetane compound in combination, the developability is specifically improved, and the effect of reducing the water stain of the pattern coating film generated at the time of development can be obtained. Therefore, the coloring composition of the present invention can also obtain good developability and water stain resistance.

The photosensitive coloring composition for color filters of the present invention comprises a colorant (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a β-hydroxyalkylamide (D), and a carboxyl group-containing oxetane compound. It is characterized by containing (E).
Hereinafter, the present invention will be described in detail. In the present application, “(meth) acryloyl”, “(meth) acrylic”, “(meth) acrylic acid”, “(meth) acrylate” or “(meth) acrylamide” are particularly described. Unless there is any, respectively, "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide" It shall represent. In addition, “CI” listed in the present specification means a color index (CI).

<Photosensitive coloring composition for color filter>
<Colorant (A)>
The photosensitive coloring composition for color filters of the present invention contains a colorant (A).
As the colorant, conventionally known dyes such as pigments or dyes can be used, and these pigments and dyes can be used alone or in combination of two or more kinds in any ratio as needed. In addition, a pigment and a dye can be used in combination to adjust the chromaticity, brightness, and contrast ratio.

  The pigment is excellent in the heat resistance and coloring power of the color filter, and organic or inorganic pigments can be used singly or in combination of two or more. The pigment is preferably a pigment having high color developability and high heat resistance, particularly a pigment having high heat decomposition resistance, and usually an organic pigment is used.

  The dye is excellent in increasing the lightness and increasing the contrast of the color filter, and any dye generally used can be used without limitation. As the dye, any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, architectural dyes, sulfur dyes and the like can be used. In addition, these may be in the form of derivatives or laked lakes of dyes.

  Furthermore, acid dyes having an acidic group such as sulfonic acid and carboxylic acid, and in the case of direct dyes, inorganic salts of acid dyes, acid dyes and quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, Or a salt forming compound with a nitrogen-containing compound such as a primary amine compound, or using as a salt forming compound by using a resin component having these functional groups as a salt forming compound, or using it as a sulfone amide compound In order to be excellent in resistance, it is possible to make a coloring composition excellent in fastness, which is preferable. Further, a salt forming compound of an acid dye and a compound having an onium base is also preferable because it is excellent in fastness, and more preferably, the compound having an onium base is a resin having a cationic group in a side chain.

  In the case of the form of a basic dye, it can be used by using an organic acid or perchloric acid or a metal salt thereof to form a salt. The salt forming compound of the basic dye is preferable because it is excellent in resistance and compatibility with the pigment, and the basic dye and the organic sulfonic acid, organic sulfuric acid, fluorine group-containing phosphorus anion compound which is a counter component which works as a counter ion It is more preferable to use a salt forming compound obtained by forming a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugated base of an organic acid having a halogenated hydrocarbon group, or an acid dye. It is a thing.

  The content of the colorant in the photosensitive coloring composition for color filters of the present invention is preferably 5 to 85% by mass, and more preferably 7% of the total solid content of the photosensitive coloring composition. It is -80 mass%. If the amount is less than 5% by mass, the film thickness with respect to the color density becomes too large, which may adversely affect the gap control and the like in forming a liquid crystal cell. If it is more than 85% by mass, the monomer and the photopolymerization initiator can not be sufficiently contained, and the desired sensitivity may not be obtained.

  Specific examples of usable colorants are shown below, but the effect of the present invention is not limited thereto. Moreover, these coloring agents can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed. Below, the specific example of the coloring agent which can be used for the coloring composition for color filters is shown by a color index number.

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

As a red dye, C.I. I. Acid Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25: 1, 26, 26: 1, 26: 2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76: 1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131, 132, 133, 134, 135, 37, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 171, 172, 173, 175, 176, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388 and the like.
Also, C.I. I. Direct Red 1, 2, 2, 2, 4, 5, 6, 7, 8, 10, 10: 1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26: 1, 28, 29, 31, 31, 33, 33: 1, 34, 35, 36, 37, 42, 43, 43, 44, 46, 49, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67: 1, 68, 72, 72, 72, 72, 74, 75, 77, 78, 79, 81, 81: 1, 85, 86, 88, 89, 90, 97, 100, 101, 101: 1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 122: 1, 124, 125, 127, 127: 1, 127: 2, 128, 129, 130, 132, 134, 135, 136, 137, 1 8, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238 and the like can also be used.

[Green coloring agent]
As a green pigment, for example, C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63. It can be mentioned. Among these, from the viewpoint of obtaining high contrast ratio and high brightness, C.I. I. Pigment green 7, 36, 58, 62 or 63.

As a green dye, C.I. I. Acid green 2, 3, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 25: 1, 27, 34, 36, 37, 38, 40, 41, 42, 44, 54, 55, 59, 66, 69, 70, 71, 81, 84, 94, 95 and the like.
Also, C.I. I. Direct greens 11, 13, 14, 24, 30, 34, 38, 42, 49, 55, 56, 57, 60, 78, 79, 80, etc. can also be used.

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

As a blue dye, C.I. I. Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34 35, 37, 40, 41, 41: 41, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 62, 62: 1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 84, 85, 86, 88, 89, 90, 90: 1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 119, 120, 123, 124, 127, 127: 1, 128, 129, 135, 137, 138, 143, 145, 147, 50, 155, 159, 169, 174, 175, 176, 183, 198, 203, 204, 205, 206, 208, 213, 227, 230, 231, 232, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280 and the like.
Also, C.I. I. Direct Blue 1, 2, 3, 4, 6, 7, 8, 8: 1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21: 1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98: 1, 101, 106, 107, 108, 109, 111, 116, 122, 124, 128, 129, 130, 130: 1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158: 1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 21 , It can also be used like 215,225,226,229,230,231,242,243,244,253,254,260,263.

[Other coloring agents]
In addition to the red colorant, the green colorant and the blue colorant, other colorants may be used in combination for the purpose of adjusting the hue. As another coloring agent, for example, a yellow pigment or dye, an orange pigment or dye, or a purple pigment or dye can be used in combination.

  Examples of yellow pigments include C.I. I. Pigment yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 , 174, 175, 176, 180, 181, 182, 183, 185, 188, 189, 190, 191, 191, 191, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, 231 and the like. Among these, from the viewpoint of obtaining high contrast ratio and high brightness, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185, and more preferably C.I. I. Pigment yellow 83, 138, 139, 150, or 180.

As yellow dyes, C.I. I. Acid Yellow 2, 3, 4, 5, 6, 7, 8, 9, 9: 1, 10, 11, 11: 1, 12, 13, 14, 15, 16, 17, 17: 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199 and so on And the like.
Also, C.I. I. Direct yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 121 126, 127, 129, 132, 133, 134 and the like can also be used.

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

As the orange dye, C.I. I. Acid Orange 1, 1: 1, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 17, 18, 19, 20, 20: 1, 22, 23, 24, 24: 1, 25, 27, 28, 28: 1, 30, 31, 33, 35, 36, 37, 38, 41, 45, 49, 50, 51, 54, 55, 56, 59, 79, 83, 94, 95, 102, 106, 116, 117, 119, 128, 131, 132, 134, 136, 138 and the like.
Also, C.I. I. Direct Orange 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 17, 19, 20, 21, 24, 25, 26, 29, 29: 1, 30, 31, 32, 33, 43, 49, 51, 56, 59, 69, 72, 73, 74, 75, 76, 79, 80, 83, 84, 85, 87, 88, 90, 91, 92, 95, 96, 97, 98, 101, 102, 102: 1, 104, 108, 112, 114 and the like can also be used.

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

As a purple dye, C.I. I. Acid Violet 1, 2, 3, 4, 5, 5: 1, 6, 7, 7: 1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, etc. Can be mentioned.
Also, C.I. I. Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97 and the like can also be used.

When using as a red photosensitive coloring composition, in addition to a red coloring agent, it can use together and use a yellow coloring agent or an orange coloring agent.
Moreover, in order to achieve both solvent resistance and sensitivity, the ratio of the yellow colorant or the orange colorant to the red colorant is 100 parts by mass of the red colorant from the viewpoint of obtaining an appropriate ultraviolet transmittance of the coating film. 150 parts by mass or less is preferable, and 120 parts by mass or less is more preferable.

  When using as a green photosensitive coloring composition, in addition to a green coloring agent, it can use together and use a yellow coloring agent. Moreover, in order to achieve both solvent resistance and sensitivity, the ratio of the yellow colorant to the green colorant is 200 parts by mass with respect to 100 parts by mass of the green colorant from the viewpoint of obtaining an appropriate ultraviolet transmittance of the coating film. The following is preferable, and 150 parts by mass or less is more preferable.

  When using as a blue photosensitive coloring composition, in addition to a blue coloring agent, a purple coloring agent or a red coloring agent can be used together and used. Moreover, in order to achieve both solvent resistance and sensitivity, the ratio of the purple colorant or the red colorant to the blue colorant is 100 parts by mass of the blue colorant from the viewpoint of obtaining an appropriate ultraviolet transmittance of the coating film. 120 parts by mass or less is preferable, and 100 parts by mass or less is more preferable.

[Finening of pigment]
When a pigment is used in the present invention, it is preferable to use it in a finely divided form, but the method of making it finely divided is not particularly limited. For example, any of wet grinding, dry grinding and solution deposition methods can be used. Thus, it is possible to carry out salt milling by a kneader method, which is one of wet grinding. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. In addition, since a color filter having a high contrast ratio can be formed, the thickness is preferably 100 nm or less. The particularly preferred range is in the range of 25 to 85 nm. The primary particle diameter of the pigment was determined by a method of directly measuring the size of the primary particles from an electron micrograph of the pigment by a TEM (transmission electron microscope). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was defined as the particle size of the pigment particles. Next, with respect to 100 or more pigment particles, the volume of each particle is determined by approximating to the cube of the determined particle diameter, and the volume average particle diameter is taken as the average primary particle diameter.

  In the salt milling process, a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent is heated using a kneader such as a kneader, 2-roll mill, 3-roll mill, trimix, ball mill, attritor or sand mill. After mechanical kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and at the time of salt milling, the pigment is crushed using the hardness of the inorganic salt. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

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

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

  When the pigment is subjected to salt milling, a resin may be added as necessary. The resin functions as a colorant carrier. The type of resin to be used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is preferably solid at room temperature, preferably water insoluble, and more preferably partially soluble in the organic solvent. It is preferable that the usage-amount of resin is the range of 5-200 mass parts with respect to 100 mass parts of pigments.

<Photopolymerizable compound (B)>
The photosensitive coloring composition for color filters of the present invention contains a photopolymerizable compound (B).
The photopolymerizable compound (B) contains a monomer or oligomer which is cured by ultraviolet light, heat or the like to form a transparent resin, and these can be used alone or in combination of two or more.

  Examples of monomers and oligomers that cure by ultraviolet light and heat to form a transparent resin include polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate and epoxy (meth) Acrylate, EO modified bisphenol A di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, polyester (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, di- Various acrylic acid esters such as pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra (meth) acrylate, epoxy acrylate, pentaerythritol tetra (meth) acrylate And methacrylic acid esters, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinyl formamide, acrylonitrile And the like, but the effects of the present invention are not limited to these.

  The photopolymerizable compound (B) may contain an acid group. For example, esterified products of free hydroxyl group-containing poly (meth) acrylates of polyhydric alcohol and (meth) acrylic acid with dicarboxylic acids; esterified products of polyvalent carboxylic acid and monohydroxyalkyl (meth) acrylates Can be mentioned. As a specific example, monohydroxy oligo acrylates or mono hydroxy oligo methacrylates such as trimethylol propane diacrylate, trimethylol propane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc. And free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4 -Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And free carboxyl group-containing oligoesters with monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. However, the effects of the present invention are not limited to these.

  These photopolymerizable compounds (B) can be used alone or in combination of two or more at an arbitrary ratio as needed.

  The content of the photopolymerizable compound (B) can be used in an amount of 10 to 300 parts by mass, preferably 10 to 200 parts by mass, with respect to 100 parts by mass of the colorant in the photosensitive coloring composition. If the amount is less than 10 parts by mass, photocrosslinking may be insufficient, and the desired solvent resistance may not be obtained. If the amount is more than 300 parts by mass, the photopolymerization initiator can not be sufficiently contained, the photocrosslinking becomes insufficient, and desired solvent resistance may not be obtained.

<Photoinitiator (C)>
The photosensitive coloring composition for color filters of the present invention contains a photopolymerization initiator (C).
The photopolymerization initiator (C) is for preparation in the form of a solvent-developable or alkali-developable colored resist material when the composition is cured by ultraviolet irradiation and a pattern is formed by photolithography. .

As the photopolymerization initiator (C), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl Acetophenone compounds such as -1-]-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Or benzoin compounds such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4- Thioxanthone compounds such as diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methyl) Xyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoi] Oxime)], or oxime ester compounds such as ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); Phosphine compounds such as 2,4,6-trimethylbenzoyl) phenyl phosphine oxide or 2,4,6-trimethylbenzoyl diphenyl phosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone and the like Borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds.
These photopolymerization initiators (C) can be used alone or in combination of two or more at an arbitrary ratio as needed.

  Among these, in the present invention, it is preferable to contain an oxime ester compound. The oxime ester compound causes the cleavage of the N-O bond of the oxime by absorbing ultraviolet light to generate an iminyl radical and an alkyloxy radical. Since these radicals are further decomposed to generate highly active radicals, the photocrosslinking reaction is promoted with a small exposure amount to enable high sensitivity, and the crosslinking density is improved, so that the pattern is dissolved in the solvent. Also, it becomes difficult for the solvent to penetrate into the pattern, and the recoating resistance and the solvent resistance become even better.

  The oxime ester compound that can be used for the photosensitive coloring composition of the present invention is not particularly limited, but a compound having a carbazole skeleton is more preferably used. Since the absorption wavelength is in the range of 330 nm to 430 nm due to the carbazole skeleton, high reaction efficiency is exhibited over a wide wavelength range from the ultraviolet region to the visible region, and furthermore, the sensitivity and solvent resistance are excellent It becomes.

  Among the oxime ester compounds having a carbazole skeleton, oxime ester compounds represented by the following general formula (4), or general formula (5), or general formula (6) are preferably used.

General formula (4):

General formula (5):

[In the general formula (4) and the general formula (5), R ¹ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group , Substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted Substituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted Or unsubstituted amino group, substituted or unsubstituted phosphino Yl, substituted or unsubstituted carbamoyl, or substituted or unsubstituted sulfamoyl.
R ² represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted group Heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group And a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyloxy group, or a substituted or unsubstituted amino group.
R ³ represents a hydrogen atom, a halogen atom, a cyano group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, Substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted It represents an alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted amino group.
R ⁴ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group Oxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted It represents an unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted amino group. ]

General formula (6):

[In the general formula (6), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted group Alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted Or an unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. ]

Examples of the substituent which may be possessed in the general formulas (4) to (6) include, for example, a halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom, methoxy group, ethoxy group, tert- Alkoxy groups such as butoxy group, aryloxy groups such as phenoxy group and p-tolyloxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group, and acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group Acyl group such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methoxalyl group, alkylsulfanyl group such as methylsulfanyl group and tert-butylsulfanyl group, phenylsulfanyl group, p-tolylsulfanyl group and the like Aryl sulf Alkylamino groups such as sulfonyl group, methylamino group, cyclohexylamino group, etc., dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group, piperidino group etc., arylamino groups such as phenylamino group and p-tolylamino group, methyl group , Alkyl groups such as ethyl, tert-butyl and dodecyl, phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthryl, phenanthryl, benzofuranyl and the like, furyl and thienyl And heterocyclic groups such as hydroxy group, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group Group, trimethylsilyl group, phosphinico group, phosphono group, Trimethyl ammonium Niu mill group, dimethylsulfoxide Niu mill group, triphenyl phenacyl phosphonium Niu mill group, and the like. ]

  Although the following compounds are mentioned as a preferable specific example of the oxime ester compound represented by the said General formula (4), The effect of this invention is not limited to these.

  Although the following compounds are mentioned as a preferable specific example of the oxime ester compound represented by the said Formula (5), The effect of this invention is not limited to these.

Although the following compounds are mentioned as a preferable specific example of the oxime ester compound represented by the said Formula (6), The effect of this invention is not limited to these.

  Although the following compounds are mentioned as a specific example of oxime ester compounds other than the structure represented by the said General formula (4), (5) and (6), The effect of this invention is limited to these Absent.

  These oxime ester compounds can be used alone or in combination of two or more at any ratio as required.

  As commercially available products of these oxime ester compounds, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (IRGACURE OXE-01), ethanone from BASF. 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE-02) is commercially available. Furthermore, in addition to this, the oximes described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc. It is also possible to use ester compounds.

  The content of these photopolymerization initiators (C) is, for example, preferably 1 to 100 parts by mass, and more preferably 2 to 50 parts by mass, with respect to 100 parts by mass of the colorant. If the amount is less than 1 part by mass, photocrosslinking may be insufficient, and desired solvent resistance may not be obtained. If the amount is more than 100 parts by mass, the photopolymerizable monomer can not be sufficiently contained, photocrosslinking becomes insufficient, and desired solvent resistance may not be obtained.

<Sensitizer>
Furthermore, the photosensitive coloring composition of the present invention can contain a sensitizer.
As sensitizers, unsaturated ketones represented by chalcone derivatives, dibenzalacetone etc., 1,2-diketone derivatives represented by benzyl and camphorquinone etc., benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapyrazino porphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalylo porphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrilium derivative, tetraphyrin derivative, anurene derivative, spiropyran derivative, spirooxazine Derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester, acyl phosphine oxide, methylphenyl glyoxylate, benzyl, 9, 10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone , 4,4'-diethylaminobenzophenone and the like.
These sensitizers can be used alone or in combination of two or more at an arbitrary ratio as needed.

  More specifically, edited by Ogawara Shin et al., "Dye Handbook" (1986, Kodansha), edited by Ogawara Shin et al., "Chemicals of functional dyes" (1981, CMC), edited by Ikemori Tadajiro et al. Specific examples thereof include, but are not limited to, the sensitizers described in “Specially functional materials” (1986, CMC). In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be contained.

  The content when using the sensitizer is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the radical photopolymerization initiator contained in the coloring composition, and from the viewpoint of photocurability and developability More preferably, it is 5 to 50 parts by mass.

<Thiol>
The photosensitive coloring composition for color filters of the present invention can contain a thiol. The thiol may be a compound having a thiol (SH) group.

  When used together with the above-mentioned photo radical polymerization initiator, thiol functions as a chain transfer agent in the radical polymerization process after light irradiation, and generates thiyl radical which is less susceptible to inhibition of polymerization by oxygen. Therefore, when the thiol is further contained, the photosensitive coloring composition for color filter becomes more sensitive. Among them, polyfunctional thiols having two or more thiol (SH) groups are preferable in view of high sensitivity, which makes it possible to increase the reaction efficiency.

As the thiol, for example, 1-thioglycerol, glycerol-monothioglycolate, 4-aminothiophenol 4-chloro-2-aminothiophenol, 2-mercaptobenzothiazole, hexanedithiol, decanedithiol, 1,4-butanediol Bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trithio Methylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), pentaerythritol tetrakis thioglycolate, pentaerythritol ester Laxthio propionate, tris (2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine and 2- (N, N-dibutylamino) ) -4,6-dimercapto-s-triazine and the like.
These thiols can be used alone or in combination of two or more at any ratio as required.

  Among these, ethylene glycol bisthiopropionate, trimethylolpropane tris (3-mercaptobutyrate) and trimethylolethane tris (3-mercaptobutyrate) are preferable.

  These thiols can be used, for example, 0.10 to 15% by mass, preferably 0.10 to 10% by mass, in 100% by mass of the solid content of the photosensitive coloring composition.

<Β-hydroxyalkylamide (D)>
The photosensitive coloring composition for color filters of the present invention contains β-hydroxyalkylamide (D).
The β-hydroxyalkylamide (D) of the present invention is not particularly limited in its structure as long as it is soluble in an organic solvent. For example, polymer derivatives obtained by polymerizing β-hydroxyethyl acrylamide, tris (2-hydroxyethyl) isocyanurate derivatives and the like can be mentioned.
Not only is the alkali developability imparted to the photosensitive coloring composition for color filters by the carboxyl group, but the thermosetting reaction between the carboxyl group and the β-hydroxyalkylamide (D) promotes the formation of higher molecular weight components in the coating film. The heat flow resistance of the coating film is expressed by the improvement of the glass transition temperature.
Among them, preferred is a compound having a structure represented by the general formula (1).

General formula (1)

In the general formula (1), X is an n-valent group consisting of carbon, hydrogen, oxygen, nitrogen, sulfur or halogen, and n is an integer of 2 to 6.

  Specific examples of X include an n-valent aliphatic hydrocarbon group having 2 or more carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group having a hetero atom.

  As the halogen, fluorine, chlorine, bromine, iodine and the like can be mentioned, and from the viewpoint of transparency, fluorine is preferable. From the viewpoint of imparting flame retardancy, chlorine and bromine are preferred.

The n-valent group is a group obtained by removing n hydrogen atoms from the compound. Hereinafter, this is referred to as an n-valent group derived from a compound.

  Examples of n-valent aliphatic hydrocarbon groups include n-valent groups derived from alkanes, alkenes and alkynes.

  As the alkane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tridecane, tetradecane, tetradecane, pentadecane, heptadecane, hexadecane, octadecane, nonadecane, icosane, henicosane, docosan, isobutane, isopentane, Neopentane, methylpentane, dimethylpentane, ethylmethylpentane, diethylpentane, methylhexane, tetramethylheptane and the like can be mentioned. Examples of n-valent groups derived from alkanes include, for example, 1,6-hexyl group, 1,7-heptyl group, 1,8-octyl group, 1,9-nonyl group, 1,10-decyl group, 1,11 Undecyl, 1,12-dodecyl, 1,13-tridecyl, 1,14-tetradecyl, 1,15-pentadecyl, 1,16-hexadecyl, 1,17-heptadecyl, 1,18- Octadecyl, 1,19-nonadecyl, 1,3,6-hexyl, 1,4,7-heptyl, 1,2,8-octyl, 1,3,9-nonyl, 1,3,3 4,6-hexyl group, 1,4,6,7-heptyl group, 1,4,5,6,7-heptyl group, 1,2,3,4,5,6-hexyl group is mentioned.

  Examples of alkenes include ethylene, propylene, butylene, pentene, hexene, heptene, octene, nonene, decene, undecene, docene, tricene, tetracene, tetracene, pentadecene, heptadecene, hexadecene, octadecene, nonadecene, icosene, henicosene, dococene, methylpentene, etc. Can be mentioned. Examples of n-valent groups derived from alkenes include, for example, 1,6- (2-hexenyl) group, 1,7- (2-heptenyl) group, 1,8- (2-octenyl) group, 1,9- (2-nonenyl) group, 1,10- (2-decenyl) group, 1,11- (2-undecenyl) group, 1,12- (2-dodecenyl) group, 1,13- (2-tridecenyl) group 1,14- (2-tetradecenyl), 1,15- (2-pentadecenyl), 1,16- (2-hexadecenyl), 1,17- (2-heptadecenyl), 1,18- ( 2-octadecenyl) group, 1,19- (2-nonadecenyl) group, 1,3,6- (2-hexenyl) group, 1,4,7- (3-heptenyl) group, 1,2,8- ( 4-octenyl group, 1,3,9- (5-nonenyl) group, 1,3,4,6- (2-hexenyl) group ) Group, 1,4,6,7- (3-Hepuseniru) group, 1,4,5,6,7- (3- Hepuseniru) group.

  Examples of alkynes include ethyne, propyne, butyne, pentyne, hexin, peptin, octin, nonin, decin, undecin, dodecin, tolysin, icosin, henicosin, docosin and the like. Examples of n-valent groups derived from alkynes include, for example, 1,6- (2-hexynyl) group, 1,7- (2-heptynyl) group, 1,8- (2-occinyl) group, 1,9- (2-nonyl) group, 1,10- (2-decynyl) group, 1,11- (2-undecynyl) group, 1,12- (2-dodecynyl) group, 1,13- (2-tridecynyl) group 1,14- (2-tetradecynyl) group, 1,15- (2-pentadecynyl) group, 1,16- (2-hexadecynyl) group, 1,17- (2-heptadecynyl) group, 1,18- ( 2-octadecynyl) group, 1,19- (2-nonadecynyl) group, 1,3,6- (2-hexynyl) group, 1,4,7- (3-heptynyl) group, 1,2,8- ( 4-Occynyl) group, 1,3,9- (5-nonyl) group, 1,3,4,6- (2-hexinyl) ) Group, 1,4,6,7- (3-Hepushiniru) group, and 1,4,5,6,7- (3- Hepushiniru) group.

  Examples of n-valent alicyclic hydrocarbon groups include cyclopropane, cyclobutane, cyclopentane, methylcyclopentane, dimethylcyclopentane, trimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cyclohexene, methylcyclohexene, norbornane, norbornene, bicyclo Examples thereof include n-valent groups derived from octene, decahydronaphthalene, adamantane, dimethyl adamantane and the like. For example, 1,1-cyclohexyl group, 1,2-cyclohexyl group, 1,3-cyclohexyl group, 1,4-cyclohexyl group, 1,2,4-cyclohexyl group, 1,3,5-cyclohexyl group, 1, 2,4,5-cyclohexyl, 1,2,3,4,5,6-cyclohexyl, 2,6-decahydronaphthyl, 1,3-adamantyl, 1,3,5-adamantyl. .

  Examples of n-valent aromatic hydrocarbon groups include n-valent aromatic hydrocarbons derived from benzene, naphthalene, biphenyl, anthracene, toluene, xylene, ethylbenzene, tert-butylbenzene, diphenylethane, diphenylacetylene, 9,9-diphenylfluorene, etc. Groups are mentioned. For example, as a group in which a carbon atom bonded to a carbonyl group is contained in an aromatic ring, a phenylene group and a tolylene group can be mentioned. Examples of the group in which a carbon atom bonded to a carbonyl group is not contained in an aromatic ring include toluene-α, α-diyl group, ethylbenzene-α, β-diyl group, ethylbenzene-β, β-diyl group, 1,2-diphenyl Ethan-1,2-diyl group and the like can be mentioned.

  As the n-valent group having a hetero atom (oxygen, sulfur, nitrogen, halogen atom), ethanol, ethylene glycol, ethylene diacetate, ethylene dipivalate, ethylene dibenzoate, ethylene bis (methyl benzoate), ethylene bis (methoxy benzoate) Benzoate), propanol, isopropanol, ethyl acetate, erythritol, ethylene oxide, acetaldehyde, acetone, dipropyl ketone, γ-pentadecanolactone, 1,2-cyclohexane, γ-butyrolactone, ethylamine, ethylmethylamine, propylamine, N- Propylacetamide, ethanethiol, ethanedithiol, tetrafluoroethane, dibromoethane, hexafluoropropane, octofluorobutane, dodecafluorohexane, hexadecaf Fluorooctane, 1,2,3,4,7,7-hexachloronorbornene, anisole, fluorobenzene, tetrafluorobenzene, trifluoromethylbenzene, chlorobenzene, dichlorobenzene, tetrafluorobenzene, bromobenzene, tetrabromobenzene, nitrobenzene, phenol Aniline, benzenesulfonic acid, anthraquinone, butanephosphonic acid, triethyl triazine, tripropyl triazine, triethyl isocyanurate, tripropyl isocyanurate, benzophenone, thiophene, diethyl sulfide, diphenyl sulfone, 2,2-diphenyl-1,1,1,1 And n-valent groups derived from 3,3,3-hexafluoropropane, diphenyl ether and the like.

  Among them, as X, from the viewpoint of reactivity, it is preferable that the atom in X directly bonded to the carbonyl group is a carbon atom not included in the aromatic ring. Furthermore, a linear aliphatic hydrocarbon group having 6 to 18 carbon atoms or an alicyclic hydrocarbon group is preferable, and more preferably, a linear aliphatic hydrocarbon group having 6 to 12 carbon atoms, or It is an alicyclic hydrocarbon group, more preferably a linear aliphatic hydrocarbon group having 6 to 12 carbon atoms.

In the formula, R ¹ and R ² each independently represent a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by the general formula (2), or a general formula (3) represents a group represented by (3), and at least one of one or more of R ¹ and R ² bonded to one or more nitrogen atoms is a group represented by the general formula (2) One is a group represented by the following general formula (3).

General formula (2)

General formula (3)

[In general formulas (2) and (3), R ^{3 to} R ⁶ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxyl group, and R ⁷ may react with a hydroxyl group Represents a residue of a compound having a functional group. ]

  The aliphatic hydrocarbon group includes an alkyl group, an alkenyl group and an alkynyl group.

As the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, decyl group And dodecyl, pentadecyl and octadecyl.

  As an alkenyl group, a vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-octenyl group, 1-decenyl group, 1-octadecenyl group Groups are mentioned.

  Examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 3-butynyl group, 1-octynyl group, 1-decynyl group and 1-octadecynyl group. .

  As an alicyclic hydrocarbon group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, 2-indeno group, decahydronaphthyl group, adamantyl group, dicyclopenta And cycloalkyl groups such as nyl group.

The aromatic hydrocarbon group includes a single ring, a fused ring, and a ring-aggregated aromatic hydrocarbon group.
As a monocyclic aromatic hydrocarbon group, monocyclic aromatic compounds such as phenyl group, benzyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, p-cumenyl group, mesityl group and the like Group hydrocarbon groups.
As a fused ring aromatic hydrocarbon group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 5-anthryl group, 1-phenanthryl group, 9-phenanthryl group, 1-acenaphthyl group, Examples thereof include fused ring aromatic hydrocarbon groups such as 2-azulenyl group, 1-pyrenyl group and 2-triphenylyl group.
As a ring assembly aromatic hydrocarbon group, ring assembly aromatic hydrocarbon groups, such as o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, etc. are mentioned.

Among them, an aliphatic hydrocarbon group, an alicyclic hydrocarbon or a monocyclic aromatic hydrocarbon group is preferable as R ¹ and R ² other than the formula (2) and the formula (3), and more preferably Or an aliphatic hydrocarbon group or an alicyclic hydrocarbon, more preferably an aliphatic hydrocarbon group having 4 or more carbon atoms.

R ^{3 to} R ^{6 in the} groups represented by formulas (2) and (3) each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group partially substituted with a hydroxyl group, and R ⁷ is a hydroxyl group Represents a residue of a compound having a functional group capable of reacting with

The hydrocarbon groups are as described above for R ¹ and R ² . Examples of the hydrocarbon group substituted with a hydroxyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxyphenyl group, a hydroxycyclohexyl group and the like.

  The residue of the compound having a functional group capable of reacting with a hydroxyl group is not particularly limited, and isocyanate, carboxylic acid, carboxylic acid halide, carboxylic acid anhydride, carboxylic acid ester, silanol, alkoxysilane, silanol ester, amino A resin, a compound having an epoxy, etc. may be mentioned, and an isocyanate, a carboxylic acid, a carboxylic acid halide and a carboxylic acid anhydride are preferable, and a monofunctional isocyanate or a monofunctional carboxylic acid is more preferable.

Among them, R ⁷ in the general formula (3) is more preferably represented by the following general formula (7) from the viewpoint of easy preparation.

General formula (7)

here,
R ¹⁶ is a single bond, a (m ¹ +1) -valent hydrocarbon group, or a urethane bond, a urea bond, an allophanate bond, a biuret bond, at least one of an isocyanurate ring, a carbon atom, and a hydrogen atom (m ¹ +1) represents a valent group,
A ¹ represents a single bond, a urethane bond or a urea bond,
R ¹⁷ represents a divalent hydrocarbon group,
A ² represents an ether bond or an ester bond,
R ¹⁸ represents a monovalent hydrocarbon group,
m ¹ represents an integer of ¹ to 5;
p ¹ represents an integer of 0 to 100.

From the viewpoint of easy preparation, it is more preferable that β-hydroxyalkylamide (D) in which R ⁷ in the general formula (3) is represented by the following general formula (8) is obtained.

General formula (8)

here,
R ¹⁹ represents a single bond, a (m ² +1) -valent hydrocarbon group, or a (m ² +1) -valent group consisting of a carbon atom, a hydrogen atom and an oxygen atom,
A ³ represents a single bond, an ester bond or an amide bond,
R ²⁰ represents a divalent hydrocarbon group,
A ⁴ represents an ether bond or an ester bond,
R ²¹ represents a monovalent hydrocarbon group,
m ² represents an integer of 1 to 5;
p ² represents an integer of 0 to 100;

The β-hydroxyalkylamide (D) is not particularly limited in its structure as long as it is soluble in an organic solvent. For example, polymer derivatives obtained by polymerizing β-hydroxyethyl acrylamide, tris (2-hydroxyethyl) isocyanurate derivatives and the like can be mentioned. Preferably, as the β-hydroxyalkylamide (D), an amide of a carboxylic acid having two or more valences (d1) or a derivative thereof and a primary or secondary amine (d2) having one or more hydroxyl groups at the β position The compound having a structure obtained by reacting a part of the hydroxyl groups of the formed β-hydroxyalkylamide (D1) with a compound (d3) containing one or more functional groups capable of reacting with hydroxyl groups is used Be
Examples of the divalent or higher carboxylic acid (d1) used in the present invention include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecane Acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanediacid, methylmalonic acid, dimethylmalonic acid, ethylmalonic acid, dipropylmalonic acid Isopropylmalonic acid, methylsuccinic acid, dimethylsuccinic acid, butylsuccinic acid, octylsuccinic acid, decylsuccinic acid, dodecylsuccinic acid, tetradecylsuccinic acid, hexadecylsuccinic acid, octadecylsuccinic acid, allylsuccinic acid, methallylsuccinic acid, hexenylsuccinic acid, Octenyl succinic acid, doco Nylsuccinic acid, decadiene-1,2-dicarboxylic acid, methyl glutaric acid, dimethyl glutaric acid, ethyl methyl glutaric acid, diethyl glutaric acid, methyl adipic acid, tetramethyl pimelic acid, cyclopentyl malonic acid, phenyl malonic acid, benzyl malonic acid , Thiophene malonic acid, phenyl succinic acid, diphenyl succinic acid,
Fumaric acid, maleic acid, acetylene dicarboxylic acid, muconic acid, itaconic acid, citraconic acid, mesaconic acid, tartaric acid, diacetyl tartaric acid, dipivaloyl tartaric acid, dibenzoyl tartaric acid, ditoluoyl tartaric acid, di (p-anisoyl) tartaric acid, malic acid, acetyl malic acid Citric acid, Citramaric acid, Hydroxymethyl glutaric acid, Galactaric acid, Aspartic acid, N-Methyl aspartic acid, N- (tert-Butoxycarbonyl) -aspartic acid, N- (benzyloxycarbonyl) aspartic acid, N-carbamoyl asparagine Acid, N-[(9H-fluoren-9-ylmethoxy) carbonyl] aspartic acid, glycylaspartic acid, 3-hydroxyaspartic acid, glutamic acid, N-acetyl glutamic acid, N- (tert-butokiki) Carbonyl) -glutamic acid, N- (benzyloxycarbonyl) glutamic acid, N-benzoyl glutamic acid, N- (4-aminobenzoyl) glutamic acid, N-[(9H-fluoren-9-ylmethoxy) carbonyl] glutamic acid, methyl glutamic acid, glycyl Glutamic acid, guazinoglutaric acid, N-phthalylglutamic acid, aminoadipic acid, aminopimelic acid, diaminopimelic acid, aminosuberic acid,
Tetrafluorosuccinic acid, dibromosuccinic acid, dimercaptosuccinic acid, thiomalic acid, epoxysuccinic acid, oxalacetic acid, hexafluoroglutaric acid, oxoglutaric acid, octafluoroadipic acid, dodecafluorosuberic acid, hexadecafluorosebacic acid, oxoazelae Aliphatic dicarboxylic acids such as acid, 4,5-dicarboxy-γ-pentadecanolactone, etc.
Cyclopropanedicarboxylic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, camphoric acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, methylcyclohexenedicarboxylic acid, norbornanedicarboxylic acid, norbornene dicarboxylic acid, bicyclo [2.2.2 ] Oct-5-ene-2,3-dicarboxylic acid, 3,6-epoxy-1,2,3,6-hexahydrophthalic acid, adamantanedicarboxylic acid, chlorendic acid (hetic acid), cyclopentanediacetic acid, cyclohexane Alicyclic dicarboxylic acids such as diacetic acid, adamantane diacetic acid, butyrolactone dicarboxylic acid,
Phthalic acid, methylphthalic acid, tert-butylphthalic acid, ethynylphthalic acid, (phenylethynyl) phthalic acid, methoxyphthalic acid, fluorophthalic acid, tetrafluorophthalic acid, trifluoromethylphthalic acid, chlorophthalic acid, dichlorophthalic acid, tetrachloro Phthalic acid, bromophthalic acid, tetrabromophthalic acid, nitrophthalic acid, hydroxyphthalic acid, aminophthalic acid, sulfophthalic acid, isophthalic acid, methylisophthalic acid, tert-butyl isophthalic acid, methoxyisophthalic acid, tetrafluoroisophthalic acid, bromoisophthalic acid, Nitroisophthalic acid, hydroxyisophthalic acid, aminoisophthalic acid, aminotriiodoisophthalic acid, sulfoisophthalic acid, terephthalic acid, dimethylterephthalic acid, tetrafluoroterephthalic acid, diku Loteterephthalic acid, tetrachloroterephthalic acid, bromoterephthalic acid, tetrabromoterephthalic acid, nitroterephthalic acid, dihydroxyterephthalic acid, aminoterephthalic acid, sulfoterephthalic acid, naphthalene dicarboxylic acid, anthracene dicarboxylic acid, anthraquinone dicarboxylic acid, 1,3-dibenzyl Aromatic dicarboxylic acids, such as -2-oxo-4,5-imidazolidine dicarboxylic acid,
Tricarballylic acid, anicot acid, butene tricarboxylic acid, cyclohexane tricarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 3-butene-1,2,3-tricarboxylic acid, cyclohexane tricarboxylic acid, pentane tricarboxylic acid, tri Tricarboxylic acids such as mellitic acid, hemimellitic acid, benzophenone tricarboxylic acid, etc., butanetetracarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, thiodisuccinic acid, tetrahydrofurantetracarboxylic acid, bicyclo [2.2 .2] Oct-7-ene-2,3,5,6-tetracarboxylic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid Oxydiphthalic acid, hexafluoroisopropylidenediphthalic acid, naphthalenetetracarboxylic acid, 5- (1,2-dicarboxyethyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, 4- (1,2- (1,2-dicarboxylic acid) Tetracarboxylic acids such as dicarboxyethyl) 1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid,
Benzene pentacarboxylic acid, cyclohexane hexacarboxylic acid, mellitic acid, folic acid, methotrexate, etc. may be mentioned.

  Further, as a divalent or higher carboxylic acid (d1), polyester having a carboxylic acid at the terminal and / or side chain, polybutadiene, polyisoprene, acrylic oligomer, or polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene Polyol Polyol Polyol Polyol and other polyols are modified with acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. And compounds obtained by

As a primary or secondary amine (d2) having one or more hydroxyl groups at the β position,
Ethanolamine, N-methyl ethanolamine, N-ethyl ethanolamine, N-butyl ethanolamine, N-tert-butyl ethanolamine, 3-tert-butylamino-1,2-propanediol, N-cyclohexyl ethanolamine, N -Phenylethanolamine, N-benzylethanolamine, diethanolamine, 2-[(hydroxymethyl) amino] ethanol, 2- (2-aminomethylaminoethanol), 2-amino-1-propanol, 2-amino-1-butanol 2-amino-2-phenyl-ethanol, 2-amino-2-methyl-1-propanol, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2 -Amino-2-ethyl-1,3-propanedi , 2-amino-1- (4-nitrophenyl) -1,3-propanediol, 2-amino-1-phenyl-1,3-propanediol, tris (hydroxymethyl) aminomethane, serine, serine methyl Ester, N- (2,4-dinitrophenyl) serine, isoleucinol: 2-amino-3-methyl-1-pentanol, 2-isopropylamino-3-methyl-1-butanol, leucinol: 2-amino-4- Methyl-1-pentanol, tert-leucinol: 2-amino-3,3-dimethyl-1-butanol, methioninol: 2-amino-4-methylthio-1-butanol, N- (5-nitro-2-pyridyl) Alaninol, phenylalaninol: 2-amino-3-phenyl-1-propanol, pyrrolinol: 2- ( Droxymethyl) piperidine, 1-amino-2-propanol (isopropanolamine), 1-amino-2-butanol, 2-amino-1-phenylethanol, 3-amino-1,2-propanediol, 3- (methylamino) -1,2-propanediol, 4-amino-3-hydroxybutyric acid, diisopropanolamine, 3-hydroxypiperidine, isoserine, N-methylglucamine: 6- (methylamino) -1,2,3,4,5 Hexane pentaol, phenylephrine: 1- (3-hydroxyphenyl) -2- (methylamino) ethanol, 2-aminocyclohexanol, threonine, 1-amino-2-indanol, glucosamine, 2-amino-1-phenyl- 1-propanol, 1,3-bis [tris (hydroxymethyl) Methylamino] propane, 1,3-diamino-2-propanol, atenolol, adrenaline, α, α-diphenyl-2-pyrrolidinemethanol, ethyephrine: 2-ethylamino-1- (3-hydroxyphenyl) ethanol, etc. Be

Examples of the derivative of the divalent or higher valent carboxylic acid (d1) include carboxylic acid esters and carboxylic acid anhydrides.

As (beta) -hydroxyalkyl amide (D1) formed by amidating (d1) and (d2), the amide compound by the combination of a dialkyl dialkane carboxylic acid and diethanolamine is mentioned, for example.

The functional group capable of reacting with a hydroxyl group in the present invention is at least selected from the group consisting of a carboxyl group, an isocyanate group, a carboxylic acid anhydride group, a carboxylic acid halide group, a hydroxymethylamino group, an alkoxysilyl group and an epoxy group. It is one kind. Among them, from the viewpoint of reactivity, an isocyanate group, a carboxyl group, a carboxylic acid anhydride group, and a carboxylic acid halide group are particularly preferable, and a carboxyl group is more preferable.

Among the compounds (d3) having at least one functional group capable of reacting with a hydroxyl group used in the present invention, examples of the compound having an isocyanate group include methyl isocyanate, butyl isocyanate, hexyl isocyanate, heptyl isocyanate, lauryl isocyanate , Monofunctional isocyanates such as stearyl isocyanate, phenyl isocyanate, cyclopropyl isocyanate, phenethyl isocyanate, tosyl isocyanate, acryloyloxyethyl isocyanate, methacryloyloxyethyl isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate , Isophorone diisocyanate Phenylene diisocyanate, tolidine isocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, isopropylidene bis (cyclohexyl isocyanate), 3- (2'-isocyanatocyclohexyl) propyl isocyanate, dianisidine isocyanate , Multifunctional isocyanates such as diphenyl ether diisocyanate, dimeric isocyanate, tetramethyl xylylene diisocyanate, lysine triisocyanate, tris (isocyanatophenyl) methane and tris (isocyanatophenyl) thiophosphate, and biurets and uretdiones of these polyfunctional isocyanates , Isocyanurate Adduct, and the like.

  In addition, the above-mentioned polyfunctional isocyanate and the activity of methanol, ethanol, propanol, butanol, pentanol, phenol, benzyl alcohol, methylamine, ethylamine, dibutylamine, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, polycaprolactone, etc. The compound which makes a hydrogen compound react is also mentioned.

  Among the compounds (d3) containing one or more functional groups capable of reacting with a hydroxyl group, compounds having a carboxyl group include, for example, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid: pentanoic acid, 2 -Methyl butyric acid, isovaleric acid: 3-methyl butyric acid, pivalic acid: 2, 2- dimethyl propionic acid, caproic acid: hexanoic acid, methyl valeric acid, dimethyl butyric acid, ethyl butyric acid, enantanoic acid: heptanoic acid, caprylic acid: octane Acid, 2-ethylhexanoic acid, pelargonic acid: nonanoic acid, capric acid: decanoic acid, undecanoic acid, lauric acid: dodecanoic acid, tridecanoic acid, myristic acid: tetradecanoic acid, pentadecanoic acid, palmitic acid: hexadecanoic acid, margaric acid: Heptadecanoic acid, stearic acid: octadecanoic acid, isostearic acid: 2-heptylun Succinic acid, nonadecanoic acid, arachidic acid: icosanoic acid, henicosanoic acid, behenic acid: docosanoic acid, trichosanic acid, lignoceric acid: tetracosanoic acid, pentacosanoic acid, serotic acid: hexacosanoic acid, heptacosanoic acid, montanic acid: octacosanoic acid, nonacosanoic acid , Melisic acid: Triactantanic acid, acrylic acid, methacrylic acid, crotonic acid, undecenoic acid, palmitoleic acid: 9-hexadecenoic acid, petroselinic acid: 6-octadecenoic acid, oleic acid: 9-octadecenoic acid, elaidic acid: 9-octadecene Acid, vacenic acid, linoleic acid: 9,12-octadecadienoic acid, linolenic acid: 9, 12, 15-octadecatrienoic acid, γ-linolenic acid: 6, 9, 12-octadecatrienoic acid, eleostearin Acid, arachidonic acid: 5, 8, 11, 14- Eicosa tetraenoic acid, 5,8, 11, 14, 17-eicosapentaenoic acid, erucic acid: 13-docosenoic acid, docosahexaenoic acid, 22-tricosenic acid, 15-tetracosenoic acid, nervonic acid, benzoic acid, toluic acid, Dimethylbenzoic acid, trimethylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, isopropylbenzoic acid, butylbenzoic acid, tert-butylbenzoic acid, vinylbenzoic acid, fluorobenzoic acid, chlorobenzoic acid, bromobenzoic acid, iodobenzoic acid, Trifluoromethylbenzoic acid, cyanobenzoic acid, hydroxybenzoic acid, hydroxymethylbenzoic acid, aminobenzoic acid, mercaptobenzoic acid, naphthoic acid, methylnaphthoic acid, hydroxynaphthoic acid, anthranoic acid: anthracenecarboxylic acid, pyrenecarboxylic acid, cyclo Propane carbo Acid, dimethyl cyclopropane carboxylic acid, tetramethyl cyclopropane carboxylic acid, mercaptomethyl cyclopropane carboxylic acid, cyclobutane carboxylic acid, cyclopentane carboxylic acid, cyclopentyl acetic acid, aminocyclopentane carboxylic acid, cyclopentene carboxylic acid, cyclohexane carboxylic acid, cyclohexyl acetic acid , Cyclohexylpropionic acid, cyclohexylbutyric acid, methylcyclohexanecarboxylic acid, propylcyclohexanecarboxylic acid, isopropylcyclohexanecarboxylic acid, butylcyclohexanecarboxylic acid, tert-butylcyclohexanecarboxylic acid, hydroxycyclohexanecarboxylic acid, (hydroxymethyl) cyclohexanecarboxylic acid, cyclohexene carbonic acid Acid, norbornene carboxylic acid, norbornanka Bonic acid, noradamantane carboxylic acid, adamantane carboxylic acid, glycolic acid, lactic acid, hydroxypalmitic acid, ricinoleic acid, hydroxystearic acid, arolytic acid: trihydroxyhexadecanoic acid, (meth) acrylic acid, acrylic acid dimer, 2- (meth) ) Acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, ethylene oxide modified succinic acid ( Meta) acrylate, β-carboxyethyl (meth) acrylate, ω-carboxypolycaprolactone (meth) acrylate, crotonic acid, α- (hydroxymethyl) acrylic acid, α- (hydroxymethyl) methacrylic acid Jasmonic acid: monovalent carboxylic acid such as 3-oxo-2- (2-pentenyl) cyclopentaneacetic acid, cucurbinic acid: 3-hydroxy-2- (2-pentenyl) cyclopentaneacetic acid, and the like; And the compounds listed as carboxylic acid (d1) of

  Among them, it is preferable to use a compound represented by the following general formula (9) or (10), because the solubility in organic solvents is easily imparted.

General formula (9)

[In the general formula (9), R ₁ is a linear, cyclic or branched, saturated or unsaturated hydrocarbon group having 2 to 18 carbon atoms. ]

General formula (10)

[In general formula (10), R ₂ is a hydrogen atom or a methyl group, R ₃ is a linear or branched alkylene group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon R ₄ is a linear or branched alkylene group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. ]

  These compounds may be used alone or in combination.

Examples of the linear saturated hydrocarbon group having 2 to 18 carbon atoms in the present invention include ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, and dodecyl group. . In the present invention, the cyclic or branched saturated or unsaturated hydrocarbon group having 2 to 18 carbon atoms is a cyclic or branched saturated or unsaturated functional group corresponding to the alkyl group described above.
The linear or branched alkylene group having 2 to 8 carbon atoms, the divalent alicyclic hydrocarbon group, or the divalent aromatic hydrocarbon group is a divalent functional group corresponding to the alkyl group described above. It is a group.

  The compound (d3) containing one or more functional groups capable of reacting with a hydroxyl group, which contains a photopolymerizable functional group used in the present invention, will be described. The photopolymerizable functional group referred to in the present invention is a photoradical polymerizable, photo cationic polymerizable, photo anionic polymerizable photo polymerizable functional group, and as the photo radical polymerizable functional group, a (meth) acrylic group, There is a vinyl group and the like, an epoxy group, an oxetane group, a lactone group, a lactam group and the like as a photocationic polymerizable functional group, and a (meth) acrylic group, a vinyl group and the like as a photoanion polymerizable group. As a specific example of the compound (d3) containing one or more functional groups capable of reacting with a hydroxyl group, containing a photopolymerizable functional group, the compounds having a (meth) acrylic group and a carboxyl group are The compound represented by Formula (3) is mentioned. In addition, it may be in a (meth) acrylic copolymer containing a carboxyl group.

As a compound which has a (meth) acryl group and a carboxylic acid anhydride group, the acid anhydride of the compound which has the said carboxyl group is mentioned.

As a compound which has a (meth) acrylic group and a carboxylic acid halide group, the acid halide of the compound which has the said carboxyl group is mentioned.

Examples of the compound having a (meth) acrylic group and an isocyanate group include (meth) acryloyl isocyanate, 1,1-bis ((meth) acryloyl methyl) ethyl isocyanate, m- (meth) acryloyl phenyl isocyanate, 2- (meth) Acryloyl oxyethyl isocyanate, 2- (meth) acryloyl oxyethyl isocyanate, 2- (meth) acryloyl oxyethoxy ethyl isocyanate, etc. are mentioned.

The compound having a (meth) acrylic group and a hydroxymethylamino group is a compound in which a carbonyl group, a thiocarbonyl group, a triazine ring or the like is bonded to a nitrogen atom of an amino group. These compounds may be etherified by capping the hydroxyl group of the hydroxymethylamino group with alcohol. For example, acrylamide, methacrylamide and the like in which at least one of a hydroxymethyl group, a methoxymethyl group and a butoxymethyl group is bonded to a nitrogen atom can be mentioned.

As a compound having a (meth) acrylic group and an alkoxysilyl group, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldi Ethoxysilane and the like.

Examples of the compound having a (meth) acrylic group and an epoxy group include glycidyl (meth) acrylate, diglycidyl cyclohexanedicarboxylate, and glycidyl terephthalate.

As a compound obtained by reacting a part of the hydroxyl group of (D1) with (d3), four compounds are obtained if (D1) is an amide compound by combination of a dialkyl dialkane carboxylic acid and diethanolamine. What was esterified with the carboxylic acid which is said (d3) among 1-3 of hydroxyl groups is mentioned.
As the β-hydroxyalkylamide (D) containing a photopolymerizable functional group used in the present invention, four hydroxyl groups can be used if (D1) is an amide compound by combination of a dialkyl dialkane carboxylic acid and diethanolamine. What was esterified with the carboxylic acid which is said General formula (3) among 1-3 is mentioned among groups. When the number of carboxylic acids having the general formula (3) is one or two, carboxylic acids having no photopolymerizable functional group (d3) as described above can be further added to the extent that all hydroxyl groups are not esterified. May be used in combination with esterification.

<Carboxyl group-containing oxetane compound (E)>
The photosensitive coloring composition for color filters of the present invention contains a carboxyl group-containing oxetane compound (E).
The carboxyl group-containing oxetane compound (E) of the present invention not only imparts alkali developability to the photosensitive color composition for color filter by the carboxyl group possessed, but also the carboxyl group and β-hydroxyalkylamide (D) As a result of the thermosetting reaction, the molecular weight of the component in the coating system proceeds and the glass transition temperature is improved. In addition, the oxetane group in the same molecule is ring-opened, and the polymerization reaction with the component in the coating film system having a high molecular weight further increases the molecular weight and improves the glass transition temperature, thereby the heat flow resistance of the coating film Is expressed.

  The carboxyl group-containing oxetane compound (E) can be used without limitation as long as it has a carboxyl group and an oxetane group. For example, an ethylenic unsaturated monomer having a carboxyl group and an oxetane group can be used. Unsaturated monomer, or resin having carboxyl group and ethylenic unsaturated monomer having oxetane group, or resin having ethylenic unsaturated monomer having carboxyl group and oxetane group, or resin having carboxyl group And a resin having an oxetane group by polymerization or reaction.

(Resin having a carboxyl group)
Examples of resins having a carboxyl group include acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, And-(meth) acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, and ω-carboxypolycaprolactone (meth) acrylate. Itaconic acid, maleic acid, fumaric acid, crotonic acid, α- (hydroxymethyl) acrylic acid, α- (hydroxymethyl) methacrylic acid, p-vinylbenzoic acid and the like can also be used.

(Resin having oxetane group)
The resin having an oxetane group is not particularly limited as long as it is a curable compound having an oxetane ring in the molecule and capable of being cured. For example, 3-ethyl-3-hydroxymethyl oxetane, 1,4-bis {[ (3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3- (2-) Ethyl hexyloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, oxetanyl silsesquioxane and the like. As a commercial item, for example, Ube Industries, Ltd. product "Etana call EHO, Etana call OXMA, Etana call OXTP, Etana call OXBP", Toagosei Co., Ltd. product "Aron oxetane OXT-101, Aron oxetane OXT-121, Aron oxetane OXT- 211, Aron oxetane OXT-221, Aron oxetane OXT-212, Aron oxetane OXT-610, and others OX-SQ, PNOX-1009 "and the like.

(Ethylenic unsaturated monomer having a carboxyl group)
Examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, acrylic acid dimer, caprolactone adduct of acrylic acid ( The addition mole number can be selected from 1 to 5 or more, and from caprolactone adduct of methacrylic acid (addition mole number is 1 to 5) and the like.

(Ethylene unsaturated monomer having an oxetane group)
As an ethylenically unsaturated monomer having an oxetane group, (3-methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, (3-butyl-3) -Oxetanyl) methyl (meth) acrylate, (3-hexyltyl 3- oxetanyl) methyl (meth) acrylate etc. can be mentioned.
As a commercial item, ETERNACOLL OXMA (made by Ube Industries, Ltd.), OXE-10, OXE-30 (above, Osaka organic chemical industry company make) etc. are mentioned, for example.
When the resin has an oxetane group, the colored composition containing the resin is excellent in heat resistance after curing.

(Resin having carboxyl group and oxetane group)
As the resin having a carboxyl group and an oxetane group, in addition to having an ethylenic unsaturated monomer having a carboxyl group and a vinyl polymer portion formed by radical polymerization of an ethylenically unsaturated monomer, an ethylenic unsaturated It is essential that the monomer comprises an ethylenically unsaturated monomer having an oxetane group.

 As an ethylenically unsaturated monomer which has an oxetane group, ETERNACOLL OXMA (made by Ube Industries, Ltd.) etc. are mentioned, for example.

  The ethylenically unsaturated monomers having an oxetane group are preferably used in a total amount of 5 to 90% by mass in the ethylenically unsaturated monomer, and particularly preferably 20 to 60% by mass. If the amount is less than 5% by mass, the effect of crosslinking is small, and if it exceeds 90% by mass, the vinyl polymer may cause a crosslinking reaction during synthesis and may gel.

  The ethylenically unsaturated monomer having an oxetane group alone can achieve the crosslinking effect, but is more preferably used in combination with a carboxyl group. At high temperatures, oxetane groups self-polymerize and crosslink with carboxyl groups. It is preferable that c × d be 2 or more, and more preferably 5 or more, on the average that c number of oxetane groups and d number of carboxyl groups per one molecule of curable dispersant.

The carboxyl group-containing oxetane compound (E) of the present invention includes an ethylenically unsaturated compound containing an ethylenically unsaturated monomer having an oxetane group in the presence of a compound having two hydroxyl groups and one thiol group in the molecule. It is preferable that it is a compound in which a hydroxyl group of a vinyl polymer having two hydroxyl groups in a terminal region of a radically polymerized saturated monomer (Step R) and an acid anhydride group of tetracarboxylic acid anhydride are reacted.
The above compound radically polymerizes an ethylenically unsaturated monomer containing an ethylenically unsaturated monomer having an oxetane group in the presence of a compound having two hydroxyl groups and one thiol group in the molecule. A step of obtaining a vinyl polymer having two hydroxyl groups in one end region, and a step of reacting a hydroxyl group of the vinyl polymer having two hydroxyl groups in one end region with an acid anhydride group of tetracarboxylic acid anhydride Since the compound has a complicated structure obtained through the method and it is impossible or almost not practical to represent by the general formula (structure), it will be described by the manufacturing method.

  Examples of compounds having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, and 3-mercapto-1,2- Propanediol (alias: thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, Examples thereof include 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

  According to the molecular weight of the target vinyl polymer, a compound having two hydroxyl groups and one thiol group in the molecule is mixed with an ethylenically unsaturated monomer and optionally a polymerization initiator and heated. Thus, a vinyl polymer can be obtained. The compound having two hydroxyl groups and one thiol group is preferably subjected to bulk polymerization or solution polymerization using 1 to 30 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated monomer, and more preferably The amount is 3 to 12 parts by mass, more preferably 4 to 12 parts by mass, and particularly preferably 5 to 9 parts by mass. The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C.

  In the polymerization, 0.001 to 5 parts by mass of a polymerization initiator can be optionally used with respect to 100 parts by mass of the ethylenically unsaturated monomer. As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane 1-carbonitrile), 2 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methyl propionate) 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), 2,2'-azobis [2- (2-imidazolin-2-yl) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxy dicarbonate, di-n-propyl peroxy dicarbonate, di (2-ethoxyethyl) peroxy Dicarbonate, t-butyl peroxy neodecanoate, t-butyl peroxy bivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like can be mentioned. These polymerization initiators can be used alone or in combination of two or more.

  In the case of solution polymerization, as a polymerization solvent, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone and the like are used, but it is not particularly limited thereto. These polymerization solvents may be used as a mixture of two or more.

As the ethylenically unsaturated monomer, in addition to the above-mentioned ethylenically unsaturated monomer having an oxetane group, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl ( Meta) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, trimethylcyclohexyl (meth) acrylate Alkyl (meth) acrylates such as isobornyl (meth) acrylate;
Aromatic (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate;
Heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate and oxetane (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and ethoxy polyethylene glycol (meth) acrylate;
(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, N-substituted (meth) acrylamide such as acryloyl morpholine Acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate;
And nitriles such as (meth) acrylonitrile. Here, (meth) acrylate indicates methacrylate or acrylate, and (meth) acrylamide indicates methacrylamide or acrylamide.

  Also, as monomers that can be used in combination with the above acrylic monomers, styrenes, styrenes such as α-methylstyrene, ethyl vinyl ethers, n-propyl vinyl ethers, isopropyl vinyl ethers, vinyl ethers such as n-butyl vinyl ethers, isobutyl vinyl ethers, acetic acid Examples thereof include fatty acid vinyls such as vinyl and vinyl propionate.

  Furthermore, as the resin having a carboxyl group and an oxetane group, it is preferable to use a monomer represented by the following general formula (11) among the ethylenically unsaturated monomers exemplified above. 20-100 mass% is preferable in an ethylenically unsaturated monomer, and, as for the usage-amount of the monomer represented by following General formula (11), 20-70 mass% is more preferable. When the monomer represented by the general formula (11) is used, the solvent affinity is improved and the pigment dispersibility is improved.

General formula (11)

In General formula (11), R ² is a linear or branched alkyl group having 1 to 4 carbon atoms. ]

As a tetracarboxylic acid anhydride used for resin which has a carboxyl group and an oxetane group, 1,2,3,4- butane tetracarboxylic acid anhydride, 1,2,3,4- cyclobutane tetracarboxylic acid anhydride, for example is used. , 1,3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3,4-cyclopentanetetracarboxylic anhydride, 2,3,5-tricarboxycyclopentylacetic anhydride , 3,5,6-Tricarboxynorbornane-2-acetic anhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic anhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl- 3-cyclohexene-1,2-dicarboxylic acid anhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic acid anhydride Aliphatic tetracarboxylic acid anhydrides;
Pyromellitic anhydride, ethylene glycol trimellitic anhydride ester, propylene glycol trimellitic anhydride ester, butylene glycol trimellitic anhydride ester, 3,3 ', 4,4'-benzophenonetetracarboxylic acid anhydride, 3,3 ', 4,4'-biphenyl sulfone tetracarboxylic acid anhydride, 1,4,5,8-naphthalene tetracarboxylic acid anhydride, 2,3,6,7-naphthalene tetracarboxylic acid anhydride, 3, 3 ', 4,4'-biphenyl ether tetracarboxylic acid anhydride, 3,3', 4,4'-dimethyl diphenylsilane tetracarboxylic acid anhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic acid Acid anhydride, 1,2,3,4-furan tetracarboxylic acid anhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl Nil sulfide anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfone anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane anhydride, 3,3 ′, 4,4'-perfluoroisopropylidenediphthalic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride, bis (phthalic acid) phenyl phosphine oxide anhydride, p-phenylene-bis (trilic acid) Phenyl phthalic acid anhydride, m-phenylene-bis (triphenyl phthalic acid) anhydride, bis (triphenyl phthalic acid) -4,4'-diphenyl ether anhydride, bis (triphenyl phthalic acid) -4,4 ' -Diphenylmethane anhydride, 9,9-bis (3,4-dicarboxyphenyl) fluoric acid anhydride, 9,9-bis [4- (3,4-dicarboxylic acid) [Sypheny] phenyl] fluorenic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic anhydride, 3,4-dicarboxy-1,2,3,4- Aromatic tetracarboxylic acid anhydrides such as tetrahydro-6-methyl-1-naphthalenesuccinic anhydride and the like can be mentioned.

  The tetracarboxylic acid anhydride used in the resin having a carboxyl group and an oxetane group is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic acid anhydride groups. These may be used alone or in combination. Further, those which are preferably used in the present invention are aromatic tetracarboxylic acid anhydrides from the viewpoint of lowering the viscosity of the pigment dispersion, and more preferably tetracarboxylic acid anhydrides having two or more aromatic rings. . Further, a compound having one carboxylic anhydride group or a compound having three or more can be used in combination.

(Other ethylenically unsaturated monomers)
As other ethylenically unsaturated monomers, in addition to the above-mentioned ethylenically unsaturated monomers, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, isobornyl Alkyl (meth) acrylates such as (meth) acrylates;
Aromatic (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate;
Heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and ethoxy polyethylene glycol (meth) acrylate;
(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, N-substituted (meth) acrylamide such as acryloyl morpholine Acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate;
And nitriles such as (meth) acrylonitrile. Here, (meth) acrylate indicates methacrylate or acrylate, and (meth) acrylamide indicates methacrylamide or acrylamide.

  Also, as monomers that can be used in combination with the above acrylic monomers, styrenes, styrenes such as α-methylstyrene, ethyl vinyl ethers, n-propyl vinyl ethers, isopropyl vinyl ethers, vinyl ethers such as n-butyl vinyl ethers, isobutyl vinyl ethers, acetic acid Examples thereof include fatty acid vinyls such as vinyl and vinyl propionate.

  The carboxyl group-containing oxetane compounds (E) can be used alone or in combination of two or more.

  Moreover, it is preferable that the molecular weight in the coating film formed by crosslinking reaction becomes larger, and, as for the weight average molecular weight of the carboxyl group-containing oxetane compound (E) in this invention, 5,000-20,000 are preferable. The weight average molecular weight of 5,000 to 20,000 is preferable because coexistence of excellent heat flow of the coating film and alkali developability becomes possible.

<Resin>
The photosensitive coloring composition for color filters of the present invention may further contain a resin.
The resin contained in the photosensitive coloring composition for color filters of the present invention is one in which a coloring agent is dispersed, and examples thereof include thermoplastic resins and the like. The resin is preferably a transparent resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light range. When used in the form of an alkali-developable photosensitive coloring composition, it is preferable to use an alkali-soluble vinyl-based resin obtained by copolymerizing an acidic substituent-containing ethylenically unsaturated monomer. Furthermore, in order to further improve the photosensitivity, an active energy ray curable resin having an ethylenically unsaturated double bond can also be used.

  As a thermoplastic resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin And polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  As a vinyl type alkali-soluble resin which copolymerized the acidic substituent containing ethylenic unsaturated monomer, resin which has acidic substituents, such as a carboxyl group and a sulfone group, is mentioned, for example. Specifically as the alkali-soluble resin, an acrylic resin having an acidic substituent, an α-olefin / (maleic anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, Or isobutylene / (anhydride) maleic acid copolymer and the like. Among them, at least one resin selected from an acrylic resin having an acidic substituent and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic substituent, is preferably used because it is high in heat resistance and transparency. Be

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins in which an ethylenically unsaturated double bond is introduced by the method of (I) or (II) shown below.

[Method (I)]
As the method (I), for example, to a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers. A carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is added, and a polybasic acid anhydride is further reacted with the produced hydroxyl group to form an ethylenically unsaturated double bond and a carboxyl group There is a way to introduce it.

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

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano-substituted, etc. Monocarboxylic acids and the like can be mentioned, and these may be used alone or in combination of two or more.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, which may be used alone or in combination of two or more. I do not mind. The remaining anhydride is obtained by using tricarboxylic acid anhydride such as trimellitic acid anhydride or using tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride, if necessary, such as increasing the number of carboxyl groups. It is also possible to hydrolyze the group, etc. In addition, when tetrahydrophthalic anhydride having an ethylenically unsaturated double bond, or maleic anhydride is used as a polybasic acid anhydride, the number of ethylenically unsaturated double bonds can be further increased.

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

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

  As the ethylenically unsaturated monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol There may be mentioned hydroxyalkyl methacrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, which may be used alone or in combination of two or more. In addition, polyether mono (meth) acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and / or butylene oxide etc. to the above hydroxyalkyl (meth) acrylate, poly γ-valerolactone, poly ε-caprolactone, and / or Polyester mono (meth) acrylates to which poly 12-hydroxystearic acid or the like is added can also be used. 2-hydroxyethyl methacrylate or glycerol methacrylate is preferable from the viewpoint of coating foreign matter suppression.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis [methacryloyloxy] ethyl isocyanate, but not limited thereto. Two or more types can be used in combination.

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

  In addition, from the viewpoints of dispersibility, stability, developability, and heat resistance of the colorant, the colorant adsorption group and the carboxyl group acting as an alkali-soluble group during development, and the aliphatic group acting as an affinity group for the colorant carrier and solvent The balance between the group and the aromatic group is important for the dispersibility of the pigment, the permeability of the developer in the coating, the developer solubility of the uncured portion, and the durability, and a resin having an acid value of 20 to 300 mg KOH / g It is preferred to use. If the acid value is less than 20 mg KOH / g, the solubility in a developer is poor, and it is difficult to form a fine pattern. When it exceeds 300 mg KOH / g, fine patterns may not be left.

  The resin is preferably used in an amount of 30 parts by mass or more based on 100 parts by mass of the total amount of the colorant (A) because the film formability and the various resistances are good, and the concentration of the colorant is high and good. It is preferable to use in an amount of 500 parts by mass or less because color characteristics can be exhibited. More preferably 100 to 400 parts by mass. More preferably, it is 160-320 mass parts. The chromaticity range can be expanded by the composition ratio of such a pigment.

  Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin modified maleic resin, rosin modified fumaric resin, melamine resin, urea resin, and phenol resin. Among them, epoxy resin and melamine resin are more preferably used from the viewpoint of heat resistance improvement.

<Solvent>
A solvent can be contained in the photosensitive coloring composition for color filters of the present invention. By this, the colorant is sufficiently dispersed and permeated into the photosensitive coloring composition, and it is applied on a substrate such as a glass substrate so as to have a dry film thickness of 0.5 to 5.0 μm to form a pattern. It can be easy.

As the solvent, for example, ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2 -Heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl- 1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m- Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dime L-formamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-Butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol mono Propyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol Propylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin alcohol, tripropylene, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl Ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl Sobuchiruketon, methylcyclohexanol, acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents may be used alone or in combination of two or more at an arbitrary ratio as needed.

  Among them, glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, from the viewpoint of storage stability of the coloring composition for color filter of the present invention It is preferable to use aromatic alcohols such as benzyl alcohol and ketones such as cyclohexanone.

  The content of the solvent is 800 to 4000 parts by mass with respect to 100 parts by mass of the coloring agent because the photosensitive coloring composition for color filter can be adjusted to an appropriate viscosity and a pattern having an intended uniform film thickness can be formed. It is preferred to use in amounts.

<Leveling agent>
In order to improve the leveling property of the photosensitive coloring composition on a transparent substrate, it is preferable to add a leveling agent to the photosensitive coloring composition for color filters of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by BYK Chemie, and the like. As a specific example of dimethylsiloxane which has a polyester structure in a principal chain, BYK-310 by BYK-Chemie company, BYK-370, etc. are mentioned. The dimethylsiloxane having a polyether structure in the main chain and the dimethylsiloxane having a polyester structure in the main chain can also be used in combination. In general, the content of the leveling agent is preferably 0.003 to 0.5% by mass in 100% by mass of the photosensitive coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a low solubility in water while having a hydrophilic group, and when it is added to a coloring composition, It is characterized by low surface tension reduction ability, and in addition to low surface tension reduction ability, it is useful that the wettability to the glass plate is good, and the addition amount at which defects of the coating film due to foaming do not appear. Those which can sufficiently suppress the chargeability can be preferably used. As a leveling agent which has such a preferable characteristic, dimethylpolysiloxane which has a polyalkylene oxide unit can use it preferably. The polyalkylene oxide unit may be a polyethylene oxide unit or a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit to dimethylpolysiloxane is a pendent type in which the polyalkylene oxide unit is bonded to a repeating unit of dimethylpolysiloxane, a terminal-modified type bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane It may be any of linear block copolymer types alternately and repeatedly bonded. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2203. -2-207, but not limited thereto.

The leveling agent may be supplemented with an anionic, cationic, nonionic or amphoteric surfactant. The surfactant may be used as a mixture of two or more.
Examples of anionic surfactants to be added to leveling agents include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphoric acid Ester etc. are mentioned.

  Examples of the cationic surfactant added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. As a nonionic surfactant which is added to the leveling agent as auxiliaries, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate And alkylbetaines such as alkyldimethylaminoacetic acid betaines; amphoteric surfactants such as alkylimidazolines; and fluorine-based and silicone-based surfactants.

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

<Other additive components>
The photosensitive coloring composition for color filters of the present invention may contain a storage stabilizer in order to stabilize the viscosity over time of the composition. Further, in order to enhance the adhesion to the transparent substrate, an adhesion improver such as a silane coupling agent may be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butyl pyrocatechol, tetraethyl phosphine, tetraphenyl phosphine and the like. Organic phosphine, phosphite and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant.

  Adhesion improvers include vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinylsilanes such as vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3,3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyl trie Xysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the colorant.

<Method of producing photosensitive coloring composition for color filter>
The photosensitive coloring composition for color filters of the present invention can be prepared as a solvent developing type or an alkali developing type photosensitive coloring composition. The solvent-developable or alkali-developable photosensitive coloring composition generally comprises a binder resin which is a thermoplastic resin, a thermosetting resin or a photosensitive resin, a photopolymerizable monomer, and a photoradical polymerization initiator. And a solvent in which the colorant is dispersed or dissolved.

  The photosensitive coloring composition for color filters of the present invention comprises a colorant, a binder resin, and, if necessary, a dispersion aid, a solvent, an additive and the like mixed to form a three roll mill, a two roll mill, a kneader The colorant dispersion is prepared by dispersing the pigment in a resin solution by dispersing with a horizontal sand mill, a vertical sand mill, an annular type bead mill, an attritor, etc., and then, the above-mentioned colorant dispersion and light radical The polymerization initiator, the photopolymerizable monomer, and if necessary, the solvent, other dispersion aids, additives, and the like can be mixed and adjusted.

[Dispersion aid]
When the colorant is dispersed in the colorant carrier, dispersion aids such as dye derivatives, resin type dispersants, surfactants and the like can be used as appropriate. Since the dispersion aid is excellent in the dispersion of the colorant and has a large effect of preventing the reaggregation of the colorant after the dispersion, a coloring composition comprising the colorant dispersed in a carrier such as a resin using the dispersion aid When is used, a color filter with high spectral transmittance is obtained.

(Dye derivative)
Examples of dye derivatives include compounds in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced into an organic pigment, anthraquinone, acridone or triazine.

Examples of dye derivatives include those described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102 and JP-B-5-9469. What is used can be used and these can be used individually or in mixture of 2 or more types.
The compounding amount of the dye derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more with respect to 100 parts by mass of the colorant from the viewpoint of improving the dispersibility. Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 40 parts by mass or less, and most preferably 35 parts by mass or less, with respect to 100 parts by mass of the colorant.

(Resin type dispersant)
The resin type dispersant has a colorant affinity site having a property of adsorbing to the additive colorant, and a site compatible with the colorant carrier, and is adsorbed to the additive colorant and dispersed in the colorant carrier Work to stabilize the Specific examples of the resin type dispersant include polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt , Polysiloxane, long chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkyleneimine) with polyester having free carboxyl group, and salts thereof Etc., (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Water-soluble resin, water-soluble polymer compound, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, used phosphoric acid ester and the like, they may be used alone or in combination, is not necessarily limited thereto.

As the dispersant used in the present invention, a polymer dispersant having a basic functional group is preferable, and a nitrogen atom-containing graft copolymer, a tertiary amino group in a side chain, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, etc. A nitrogen atom-containing acrylic block copolymer and a urethane polymer dispersant having a functional group containing The resin-type dispersant is preferably used at about 5 to 200% by mass with respect to the total amount of the colorant, and more preferably about 10 to 100% by mass from the viewpoint of film formability.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, manufactured by BIC Chem. Japan. 167, 168, 170, 171, 174, 180, 181, 182, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2070, 2095, 2150, 2155, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P 104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen et al., SOLSPERSE-3000, 9000, 1300, manufactured by Nippon Lebrizole. , 13240, 13650, 13940, 16000, 17000, 18000, 20000, 20000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32500, 32500, 34750, 35100, 36600, 38500, 41000, 41090, 53095 , 55000, 56000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 453, 454, 4540, 4550, 4560, 4800, 010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of Ajisupa -PA111, PB711, PB821, PB822, PB824, and the like are preferable.

Moreover, as a resin type dispersing agent used by this invention, it is preferable to contain following (S1) or (S2) as a resin type dispersing agent which has a carboxyl group.
(S1) A resin type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride.
(S2) a weight obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride Resin type dispersant which is united.

[Resin type dispersant (S1)]
The resin type dispersant (S1) can be produced by a known method such as WO 2008/007776, JP 2008-029901, JP 2009-155406 and the like. The polymer having a hydroxyl group is preferably a polymer having a hydroxyl group at an end, and can be obtained, for example, as a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a compound having a hydroxyl group. The compound having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Among them, a compound having two hydroxyl groups and one thiol group in the molecule is preferably used because the terminal hydroxyl group is preferably plural.

  That is, a polymer having two hydroxyl groups at one end, which is a more preferable example, is an ethylenically unsaturated single monomer containing a monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer obtained by polymerizing a monomer. The hydroxyl group of the polymer having a hydroxyl group reacts with the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride to form an ester bond, while the anhydride ring opens to form a carboxylic acid.

[Resin type dispersant (S2)]
The resin type dispersant (S2) can be produced by a known method such as JP2009-155406A, JP2010-185934A, JP2011-157416A, etc. For example, a compound having a hydroxyl group It is obtained by polymerizing an ethylenically unsaturated monomer in the presence of the reaction product of the hydroxyl group of the above and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. Among them, in the presence of a reaction product of a hydroxyl group of a compound having two hydroxyl groups and one thiol group in the molecule and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride, It is preferable that it is the polymer which superposed | polymerized the ethylenically unsaturated monomer containing a monomer.

  (S1) and (S2) are differences in whether the introduction of the polymer portion obtained by polymerizing the ethylenically unsaturated monomer is performed first or later. Although molecular weight etc. may differ somewhat depending on various conditions, if the raw material and the reaction conditions are the same, theoretically the same one can be obtained.

(Surfactant)
As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; alkyl dimethylamino There may be mentioned amphoteric surfactants such as alkyl betaines such as betaine acetate and alkyl imidazolines, which may be used alone or in combination of two or more, but it is not necessarily limited thereto.

  When a resin type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant. When the compounding amount of the resin type dispersant and the surfactant is less than 0.1 parts by mass, the added effect is hardly obtained, and when the compounding amount is more than 55 parts by mass, the dispersing agent is influenced by the excessive dispersing agent. May affect.

<Removal of coarse particles>
The photosensitive coloring composition for color filters of the present invention may be coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to carry out removal of coarse particles and mixed dust. Thus, the coloring composition preferably contains substantially no particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter provided with the filter segment formed using the photosensitive coloring composition for color filters of this invention is demonstrated.

  The color filter of the present invention comprises a red filter segment, a green filter segment, and a blue filter segment, and the red filter segment and the green filter segment and the blue filter segment have photosensitivity for the color filter of the present invention. It is formed of a coloring composition. In addition, the color filter may further include a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment.

  The red filter segment can be formed using a conventional red coloring composition. Examples of red coloring compositions include C.I. I. Pigment red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 255, 264, 270, 272, 273, 274, 277, 278, 279, Mention may be made of red pigments such as 280, 281, 282, 283, 284, 285, 286 or 287. In addition, red dyes such as xanthene dyes, azo dyes, disazo dyes, and anthraquinone dyes can also be used. Specifically, C.I. I. Salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289, 338 and the like can be mentioned.

  In addition, C.I. I. Orange pigments such as CI pigment orange 43, 71 or 73, and / or C.I. I. Pigment yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 181, 181, 181, 181, 82,185,187,188,193,194,198,199,213,214,218,219,220, or may be used in combination of a yellow pigment 221, and the like. In addition, orange dyes and / or yellow dyes such as quinoline dyes, azo dyes, disazo dyes, and methine dyes can also be used.

  Green filter segments can be formed using conventional green coloring compositions. For example, C.I. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, etc., a composition obtained by using a green pigment. Green coloring compositions include C.I. I. Pigment yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 181, 181, 181, 181, 82,185,187,188,193,194,198,199,213, or may be used in combination of a yellow pigment 214, and the like.

  The blue filter segment can be formed using a conventional blue coloring composition comprising a blue pigment and a colorant carrier. Examples of blue pigments include C.I. I. Pigment blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. In addition, a violet pigment can be used in combination with the blue coloring composition. As a purple pigment which can be used in combination, C.I. I. And violet pigments such as CI pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like. In addition, it is also possible to use a salt forming compound of a basic dye or an acid dye exhibiting a blue or purple color. When a dye is used, triarylmethane dyes or xanthene dyes are preferred in terms of lightness.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereby. In addition, unless otherwise indicated, "part" means "mass part" and "%" means "mass%." Moreover, the measuring method of the weight average molecular weight (Mw) of resin, and the acid value of resin is as follows.

(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin was measured using a TSK gel column (manufactured by Tosoh Corp.) and a GPC equipped with an RI detector (GPC manufactured by Tosoh Corp., HLC-8120GPC) using polystyrene as the developing solvent and polystyrene conversion molecular weight It is.

(Acid number of resin)
The acid value of the resin is an acid value (KOH-mg / g) measured according to the potentiometric titration method of JIS K 0070.

(Average primary particle size of pigment)
The average primary particle size of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, with respect to 100 or more pigment particles, the volume (weight) of each particle is determined by approximating to the cube of the determined particle diameter, and the volume average particle diameter is defined as the average primary particle diameter.

  Then, the manufacturing method of the coloring agent used for the Example and the comparative example, a coloring agent dispersion, and a binder resin solution is demonstrated.

<Method of producing coloring agent>
[Green pigment (A-1)]
C. I. Pigment Green 58 ("FASTOGEN GREEN A110" manufactured by DIC Corporation), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 80 ° C for 6 hours. The mixture is poured into 2000 parts of hot water and stirred for about 1 hour with a high speed mixer while heating to about 80 ° C. to form a slurry, repeated filtration and washing with water to remove salt and solvent, and drying overnight at 80 ° C. To give 95 parts of a green pigment (A-1).

[Green pigment (A-2)]
To 1200 parts of concentrated sulfuric acid, 100 parts of pigment (Q-1) represented by the following formula was gradually added at room temperature. The sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. while stirring at 40 ° C. for 3 hours. The blue precipitate was filtered, washed with water and dried to obtain 92 parts of a pigment (Q-2) represented by the following formula.
In a reaction vessel, 2000 parts of N, N-dimethylformamide, 100 parts of pigment (Q-2) and 52 parts of diphenyl phosphate were added. After reacting at 85 ° C. for 3 hours, the solution was poured into 8000 parts of water. The reaction product was then filtered, washed with 16000 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 95 parts of a green pigment (A-2).

[Green pigment (A-3)]
In a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of the pigment 1 (Q-1), 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) are added and stirred at 20 ° C. React for 6 hours. Thereafter, the reaction mixture was poured into 5,000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. In a beaker, 500 parts of 2.5% aqueous sodium hydroxide solution and the collected residue were added and stirred at 80 ° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water and dried to obtain a pigment in which an average of 10.1 bromine atoms was substituted on the phthalocyanine ring.
Next, to a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of a pigment in which an average of 10.1 bromine atoms is substituted on the obtained phthalocyanine ring, and 13.9 parts of diphenyl phosphate are added. The mixture was heated to ° C and allowed to react for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol and dried to give 95 parts of a green pigment (A-3).

[Red pigment (A-4)]
C. I. Pigment green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), C.I. I. Pigment red 254 ("IRGAFORE RED B-CF" manufactured by BASF Corporation) was produced in the same manner as in the preparation of the green pigment (A-1) to obtain 96 parts of a red pigment (A-4).

[Blue pigment (A-5)]
C. I. Pigment green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), C.I. I. Pigment blue 15: 6 ("Lionol blue ES" manufactured by Toyo Color Co., Ltd.), except that it was changed to a green pigment (A-1), to obtain 96 parts of a blue pigment (A-5) .

[Yellow pigment (A-6)]
C. I. Pigment green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), C.I. I. Pigment yellow 138 ("Palitol yellow K0961 HD" manufactured by BASF Corporation) was produced in the same manner as in the preparation of the green pigment (A-1) to obtain 96 parts of a yellow pigment (A-6).

<Method for producing resin solution>
[Acrylic resin solution 1]
(Preparation of Acrylic Resin Solution 1)
196 parts of cyclohexanone is charged into a reaction vessel in which a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirrer are attached to a separable four-necked flask, the temperature is raised to 80 ° C., and the inside of the reaction vessel is purged with nitrogen and then dropped. From tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumyl phenol ethylene oxide modified acrylate ("Alonix M110" manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1 part and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, approximately 2 parts of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and propylene glycol monomethyl is obtained so that non-volatile content is 20% by mass in the resin solution synthesized above. Ether acetate was added to prepare an acrylic resin solution 1. The mass average molecular weight (Mw) was 26,000, and the acid value was 95 mg KOH / g.

[Acrylic resin solution 2]
Add 100 parts of propylene glycol monomethyl ether acetate to a reaction vessel equipped with a separable 4-neck flask, a thermometer, a condenser, a nitrogen gas inlet pipe, and a stirrer, and heat it at 120 ° C while injecting nitrogen gas into the vessel. A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 parts of azobisisobutyronitrile is added dropwise over 2.5 hours from the dropping tube at a temperature for 2.5 hours. The reaction was done. Next, the inside of the flask is replaced with air, and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone are added to 17.0 parts of acrylic acid, and the reaction is continued at 120 ° C. for 5 hours, and tetrahydrophthalic anhydride is further added. 30.4 parts and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 8400 and an acid value of 79 mg KOH / g. After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, so that the non-volatile content becomes 40 mass% in the resin solution synthesized above An acetate was added to prepare an acrylic resin solution 2.

<Method of producing colorant dispersion>
[Colorant Dispersion (P-1)]
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm The mixture was filtered through a filter of to prepare a colorant dispersion (P-1).
Green pigment (A-1): 5.40 parts Dispersant 1 (manufactured by BASF, "EFKA 4300"): 13.50 parts Acrylic resin solution 1: 38. 38 parts Propylene glycol monomethyl ether acetate (PGMAC): 42.72 parts

[Colorant Dispersion (P-2 to 6)]
Colorant pigments (P-2 to 6) were produced in the same manner as the colorant pigment (P-1) except that the colorants shown in Table 1 were changed.

<Method for producing β-hydroxyalkylamide (D)>
[Β-hydroxyalkylamide (D-1)]
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean Stark tube, reflux condenser, and gas inlet tube, add 266 parts of diisopropanolamine, 10 parts of potassium hydroxide, 202 parts of sebacic acid, and keep at 120 ° C for 4 hours Heated. Toluene (100 parts) was added, the Dean-Stark tube was filled with toluene, and water generated by azeotropic distillation with toluene was removed. The refluxing toluene was allowed to return to the reaction vessel. After sufficient removal of water, the slurry-like product formed in the vessel was taken out and vacuum dried. 433 parts of this product was again put into a reaction vessel, and was heated and stirred at 150 ° C. for melting. Into this, 72 parts of 2-ethylhexanoic acid was dropped from a dropping device over 1 hour. After the dropwise addition, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, and the Dean-Stark tube was filled with toluene, and water generated by azeotroping with toluene was removed. The refluxing toluene was allowed to return to the reaction vessel. After sufficient removal of water, all toluene was distilled off. Thereafter, the temperature was lowered to 60 ° C., and 1983 parts of cyclohexanone were added. A homogeneous yellow-brown clear photopolymerizable functional group free [beta] -hydroxyalkylamide (D-1) having a solids content of 20% was obtained.

[Β-hydroxyalkylamide (D-2)]
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean Stark tube, reflux condenser, and gas inlet tube, 178 parts of 1-amino-2-butanol and 10 parts of potassium hydroxide are added and heated to 60 ° C. Then, 100 parts of succinic anhydride was added little by little over 1 hour. After heating to 120 ° C. and heating for 4 hours, 100 parts of toluene was added, and the Dean-Stark tube was filled with toluene, and water generated by azeotroping with toluene was removed. The refluxing toluene was allowed to return to the reaction vessel. After sufficient removal of water, the slurry-like product formed in the vessel was taken out and vacuum dried. 260 parts of this product was again put into a reaction vessel, and was heated and stirred at 150 ° C. for melting. Into this, 60 parts of phenyl isocyanate was dropped over 1 hour from a dropping device. After dropping, the mixture was stirred at 150 ° C. for 1 hour, then the temperature was lowered to 60 ° C., and 1280 parts of cyclohexanone were added. A homogeneous yellow-brown clear photopolymerizable functional group free [beta] -hydroxyalkylamide (D-2) having a solids content of 20% was obtained.

[Β-hydroxyalkylamide (D-3)]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas inlet tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were charged and heated to 100 ° C. while nitrogen was blown. Into this, 174 parts of dimethyl adipate was dropped from a dropping device over 4 hours. After completion of the dropwise addition, the inside of the reaction vessel was heated while reducing the pressure to 205 mmHg to remove the generated methanol. The slurry-like product formed in the vessel was taken out and vacuum dried. 320 parts of this product was again put into a reaction vessel, and was heated and stirred at 150 ° C. for melting. Into this, 144 parts of 2-ethylhexanoic acid was dropped from a dropping device over 1 hour. After the dropwise addition, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, and the Dean-Stark tube was filled with toluene, and water generated by azeotroping with toluene was removed. The refluxing toluene was allowed to return to the reaction vessel. After sufficient removal of water, all toluene was distilled off. 1H-NMR measurement was carried out, and the integral ratio of the methylene group of the ester bond (near δ = 4.1) and the methyl group derived from 2-ethylhexanoic acid (near δ = 0.85) was 2: 6 From the above, it was confirmed that the desired product was generated. Furthermore, the structure was also confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., cyclohexanone was added, and the solid content was adjusted to 20%. The resulting homogeneous yellow-brown transparent photopolymerizable functional group-free β-hydroxyalkylamide (D-3) was removed.

[Β-hydroxyalkylamide (D-4)]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas inlet tube, N, N, N ', N'-tetrakis (hydroxyethyl) adipamide (Emschemy Primid XL-552) 320 parts were added and melted by heating to 150 ° C. with stirring. Into this, 144 parts of 2-ethylhexanoic acid was dropped from a dropping device over 1 hour. After the dropwise addition, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, and the Dean-Stark tube was filled with toluene, and water generated by azeotroping with toluene was removed. The refluxing toluene was allowed to return to the reaction vessel. After sufficient removal of water, all toluene was distilled off. 1 H-NMR measurement was performed to confirm that the desired product had been produced. Furthermore, the structure was also confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., cyclohexanone was added, and the solid content was adjusted to 20%. The resulting homogeneous yellow-brown transparent photopolymerizable functional group-free β-hydroxyalkylamide (D-4) was removed.

[Β-hydroxyalkylamide (D-5)]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas inlet tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were charged and heated to 100 ° C. while nitrogen was blown. Into this, 174 parts of dimethyl adipate was dropped from a dropping device over 4 hours. After completion of the dropwise addition, the inside of the reaction vessel was heated while reducing the pressure to 205 mmHg to remove the generated methanol. The slurry-like product formed in the vessel was taken out and vacuum dried. 320 parts of this product was again put into a reaction vessel, and was heated and stirred at 150 ° C. for melting. Into this, 158 parts of 3,5,5-methylhexanoic acid (Kyowa Hakko Chemical Co., Ltd. Kyo-Wanoic-N) was dropped from a dropping device over 1 hour. After the dropwise addition, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, and the Dean-Stark tube was filled with toluene, and water generated by azeotroping with toluene was removed. The refluxing toluene was allowed to return to the reaction vessel. After sufficient removal of water, all toluene was distilled off. In a second reaction vessel equipped with a stirrer, thermometer, dropping device, Dean Stark tube, reflux condenser, gas inlet tube, 222 parts of isophorone diisocyanate, 116 parts of 2-hydroxyethyl acrylate, 0.1 part of tetrabutyl titanate In addition, the reaction was carried out at 60 ° C. for 8 hours while blowing in dry air. 461 parts of the above slurry-like product was added to the second reaction vessel, and the reaction was carried out at 60 ° C. for 8 hours. 1 H-NMR measurement was performed to confirm that the desired product had been produced. Furthermore, the structure was also confirmed by IR. Thereafter, propylene glycol monomethyl ether acetate was added to adjust the solid content to 20%. The obtained homogeneous yellow-brown transparent photopolymerizable functional group was taken out and the β-hydroxyalkylamide (D-5) represented by the following formula was taken out.

<Method of producing carboxyl group-containing oxetane compound (E)>
[Carboxyl group-containing oxetane compounds (E-1)]
In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 80 parts of n-butyl acrylate, 60 parts of methyl methacrylate, ETERACOLL OXMA: 20 parts of (3-methyl-3-oxetanyl) methyl methacrylate (manufactured by Ube Industries, Ltd.) 40 parts of t-butyl methacrylate was charged and replaced with nitrogen gas. The reaction vessel is heated to 80 ° C., and a solution of 0.1 part of 2,2′-azobisisobutyronitrile dissolved in 12 parts of 3-mercapto-1,2-propanediol is added, It reacted for time. Solid content measurement confirmed that 95% had reacted. Next, PMA: pyromellitic anhydride, 9 parts (manufactured by Daicel Chemical Industries, Ltd.), 16 parts of trimellitic anhydride, 238 parts of cyclohexanone, 1,8-diazabicyclo- [5.4.0] as a catalyst An additional 0.40 part of 7-undecene was added and allowed to react at 100 ° C. for 7 hours. It was confirmed by measurement of the acid value that the acid anhydride of 98% or more was half-esterified, and the reaction was terminated to obtain a compound (E-1) having an acid value of 60 mg KOH / g and a weight average molecular weight of 9700.

[Carboxyl group-containing oxetane compound (E-2)]
In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 40 parts of n-butyl acrylate, 80 parts of OXE-10: (3-ethyl oxetan-3-yl) methyl acrylate (Osaka organic chemical industry corporation) Then, 80 parts of t-butyl methacrylate was charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and 12 parts of 2-mercapto-2-methyl-1,3-propanediol was added and reacted for 10 hours. Solid content measurement confirmed that 95% had reacted. Next, PMA: 19 parts of pyromellitic anhydride (Dycel Corporation), 231 parts of cyclohexanone, and 0.40 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst, and 100 The reaction was allowed to proceed for 7 hours. It was confirmed by measurement of the acid value that the acid anhydride of 98% or more was half-esterified, and the reaction was terminated to obtain a compound (E-2) having an acid value of 42 mg KOH / g and a weight average molecular weight of 6,400.

[Carboxyl group-containing oxetane compounds (E-3)]
In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 80 parts of n-butyl acrylate, 60 parts of methyl methacrylate, 20 parts of methacrylic acid, 20 parts of KALEN MOI-BM (manufactured by Showa Denko), OXE-30: Twenty parts of (3-ethyloxetan-3-yl) methyl methacrylate (Osaka Organic Chemical Industry Co., Ltd.) was charged and purged with nitrogen gas. The reaction vessel is heated to 80 ° C., and a solution of 0.1 part of 2,2′-azobisisobutyronitrile dissolved in 14 parts of 2-mercapto-2-methyl-1,3-propanediol is added And reacted for 10 hours. Solid content measurement confirmed that 95% had reacted. Next, BPAF: 30 parts of 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.), C-1015N (bifunctional polycarbonate polyol, trade name: Kuraray polyol C-1015N (Hydroxyl value 112 mg KOH / g, manufactured by Kuraray Co., Ltd.) 81 parts, trimellitic anhydride 25 parts, cyclohexanone 298 parts, catalyst 1,8-diazabicyclo- [5.4.0] -7-undecene 0.40 Part was added and allowed to react at 100.degree. C. for 7 hours. It was confirmed by acid value measurement that an acid anhydride of 98% or more was half-esterified, and the reaction was terminated to obtain a compound (E-3) having an acid value of 71 mg KOH / g and a weight average molecular weight of 19,000.

[Carboxyl group-containing oxetane compounds (E-4)]
40 parts of n-butyl acrylate, 40 parts of ETERNACOLL OXMA: (3-methyl-3-oxetanyl) methyl methacrylate (manufactured by Ube Industries, Ltd.), t-butyl methacrylate in a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer Forty parts were charged and purged with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and 12 parts of 2-mercapto-2-methyl-1,3-propanediol was added and reacted for 10 hours. Solid content measurement confirmed that 95% had reacted. Next, PMA: pyromellitic anhydride, 19 parts (Daicel Corporation), 231 parts of cyclohexanone, and 0.40 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst are added, The reaction was allowed to proceed at 100 ° C. for 7 hours. It was confirmed by acid value measurement that an acid anhydride of 98% or more was half-esterified, and the reaction was terminated to obtain a compound (E-4) having an acid value of 35 mg KOH / g and a weight average molecular weight of 4,200.

[Carboxyl group-containing oxetane compounds (E-5)]
In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 80 parts of n-butyl acrylate, 60 parts of methyl methacrylate, 20 parts of methacrylic acid, 20 parts of KALEN MOI-BM (manufactured by Showa Denko), ETERNACOLL OXMA: ( Twenty parts of 3-methyl-3-oxetanyl) methyl methacrylate (manufactured by Ube Industries, Ltd.) was charged and purged with nitrogen gas. The reaction vessel is heated to 80 ° C., and a solution of 0.1 part of 2,2′-azobisisobutyronitrile dissolved in 14 parts of 2-mercapto-2-methyl-1,3-propanediol is added And reacted for 10 hours. Solid content measurement confirmed that 95% had reacted. Next, BPAF: 39 parts of 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.), C-1015N (bifunctional polycarbonate polyol, trade name: Kuraray polyol C-1015N (Hydroxyl value 112 mg KOH / g, manufactured by Kuraray Co., Ltd.) 106 parts, 33 parts trimellitic anhydride, 392 parts cyclohexanone, 1,8-diazabicyclo- [5.4.0] -7-undecene 0.40 as a catalyst Part was added and allowed to react at 100.degree. C. for 7 hours. It was confirmed by acid value measurement that an acid anhydride of 98% or more was half-esterified, and the reaction was terminated to obtain a compound (E-5) having an acid value of 73 mg KOH / g and a weight average molecular weight of 25,000.

<Production of Photosensitive Colored Composition for Color Filter>
Example 1
(Photosensitive coloring composition (L-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered and mixed with a 5.0 μm filter to prepare a photosensitive coloring composition (L-1).
Green coloring dispersion (P-1): 42.00 parts Acrylic resin solution 2: 0.75 parts Photopolymerizable compound (B-1): 2.80 parts (Dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate Mixture, Toon Gosei "Aronix M-402")
Photopolymerization initiator (C-1): 0.31 part ("IRGACURE OXE-02" manufactured by BASF Corp.)
β-hydroxyalkylamide (D-1): 2.74 parts Carboxyl group-containing oxetane compound (E-1): 1.93 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.46 parts

[Examples 2 to 24]
(Photosensitive coloring composition (L-2 to 24))
Hereinafter, as shown in Tables 2 to 4, the photosensitivity is different except that the kind and the blending amount (parts by mass) of the coloring dispersion, the resin solution, the β-hydroxyalkylamide, and the compound having a carboxyl group-containing oxetane group are changed. Photosensitive coloring compositions (L-2 to 24) were obtained in the same manner as the coloring composition (L-1).

Comparative Example 1
(Photosensitive coloring composition (L-25)
The following mixture was stirred and mixed so as to be uniform, then filtered through a 5.0 μm filter and mixed to prepare a photosensitive coloring composition (L-25).
Green colorant dispersion (P-1): 42.00 parts Acrylic resin solution 2: 0.75 parts Photopolymerizable compound (B-1): 4.97 parts (Dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate Mixture, Toho Gosei "Aronix M-402")
Photopolymerization initiator (C-1): 0.31 part ("IRGACURE OXE-02" manufactured by BASF Corp.)
Propylene glycol monomethyl ether acetate (PGMAC): 51.97 parts

[Comparative Examples 2 to 6]
(Photosensitive coloring composition (L-26 to 30))
As shown in Tables 2 to 4, except that the type and the blending amount (parts by mass) of the colorant dispersion, the resin solution, the compound having β-hydroxyalkylamide, and the carboxyl group-containing oxetane compound are changed, the photosensitive coloring is Photosensitive coloring compositions (L-26 to 30) were obtained in the same manner as the composition (L-25).

<Evaluation of photosensitive coloring composition>
The following evaluation was performed about the obtained photosensitive coloring composition. The results are shown in Tables 2 to 4.

<Heat flow (pattern shape linearity) evaluation>
The photosensitive resin composition was coated on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater so that the finished film thickness would be 2.0 μm after heating at 230 ° C. for 50 minutes. Next, after holding for 2 minutes on a hot plate heated to 90 ° C., ultraviolet exposure was performed with an illuminance of 30 mW / cm ² and an exposure amount of 60 mJ / cm ² using an extra-high pressure mercury lamp. The exposed coating was then spray developed to form a pattern on the filter segment. After spray development, it was heated at 230 ° C. for 50 minutes in a clean oven. The pattern in the 100 μm photomask portion formed on the filter segment after heating at 230 ° C. for 50 minutes is observed using an optical microscope, and the maximum width / minimum width ratio of the pattern in the 100 μm photomask portion is evaluated. The The ranks of the ratings are as follows.
:: Maximum width / minimum width ratio of pattern is less than 101% ○: Maximum width / minimum width ratio of pattern is 101% or more and less than 103% Δ: Maximum width / minimum width ratio of pattern is 103% or more and less than 105% ×: The maximum width / minimum width ratio of the pattern is 105% or more

<Evaluation of developability>
The photosensitive resin composition was coated on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater so that the finished film thickness would be 2.0 μm after heating at 230 ° C. for 50 minutes. Next, after holding for 2 minutes on a hot plate heated to 90 ° C., ultraviolet exposure was performed with an illuminance of 30 mW / cm ² and an exposure amount of 60 mJ / cm ² using an extra-high pressure mercury lamp. The coated film after exposure was spray developed, and the time to form a pattern on the filter segment was evaluated in comparison with the appropriate development time. The suitable development time was taken as the shortest time for which pattern formation was possible without any development remaining for the coating film with each photosensitive coloring composition. The ranks of the ratings are as follows.
◎: less than 5% fluctuation with respect to the appropriate development time.
○: 5% or more and less than 10% fluctuation with respect to the appropriate development time
Δ: 10% or more and less than 30% fluctuation with respect to the appropriate development time ×: 30% or more change with respect to the appropriate development time

<Water stain>
The photosensitive resin composition was coated on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater so that the finished film thickness would be 2.0 μm after heating at 230 ° C. for 50 minutes. Next, after holding for 2 minutes on a hot plate heated to 90 ° C., ultraviolet exposure was performed with an illuminance of 30 mW / cm ² and an exposure amount of 60 mJ / cm ² using an extra-high pressure mercury lamp. The coated film after exposure was spray developed, and the pattern on the 100 μm photomask portion of the filter segment formed after spray development was observed and evaluated using an optical microscope. The ranks of the ratings are as follows.
:: no water stain ○: water stain in an area of 1% to less than 10% Δ: water stain in an area of 10% to less than 50% x: water stain in an area of 50% or more

  The abbreviations in Tables 2 to 4 are shown below.

<Compound having a melamine skeleton>
(Melamine / formaldehyde / alkyl monoalcohol (C1 to C12) condensate: “Nikalac MW-30” manufactured by Sanwa Chemical Co., Ltd.)
<Compound 1 having an epoxy group>
(1,2-Epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol: Daicel Co., Ltd. "EHPE 3150")
<Compound 2 having an epoxy group>
(Sorbitol polyglycidyl ether: Nagase ChemteX Co., Ltd. "EX-611")

  As shown in Tables 2 to 4, the colorant (A), the photopolymerizable compound (B), the photopolymerization initiator (C), the β-hydroxyalkylamide (D), and the carboxyl group-containing oxetane of the present invention By forming the compound (E), the formation of a pattern having good linearity, developability, and resistance to water stain were all good results.

  Among them, the photosensitive coloring composition in which the colorant (A) is a green pigment has a better result of pattern shape linearity.

  On the other hand, as in Comparative Example 1, the photosensitive coloring composition for a color filter when it does not contain the β-hydroxyalkylamide (D) and the carboxyl group-containing oxetane compound (E) has a pattern shape and development. Sex and water stain resistance could not be satisfied at the same time.

Further, as in Comparative Examples 2 and 3, the photosensitive coloring composition for a color filter has a pattern shape only by containing any one of β-hydroxyalkylamide (D) and carboxyl group-containing oxetane compound (E). It was not possible to simultaneously satisfy the formation and developability and the resistance to water stain.

  Further, as in Comparative Examples 4 to 6, in the photosensitive coloring composition for a color filter in which the β-hydroxyalkylamide (D) is substituted with another thermally crosslinkable compound, formation of a pattern shape and developability, water stain resistance I was not satisfied at the same time.

  From the above results, it was confirmed that the photosensitive coloring composition for a color filter of the present invention simultaneously satisfies the formation of a pattern shape having good linearity, the developability, and the water stain resistance.

Claims (6)

  Photosensitive coloring composition for color filter containing a colorant (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a β-hydroxyalkylamide (D), and a carboxyl group-containing oxetane compound (E) object.   The photosensitive coloring composition for color filters of Claim 1 whose weight average molecular weight (Mw) of a carboxyl group-containing oxetane compound (E) is 5,000-20,000. The photosensitive coloring composition for color filters according to claim 1 or 2, wherein the β-hydroxyalkylamide (D) is a compound represented by the following general formula (1).
General formula (1)
[In general formula (1), X is an n-valent group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom, n is an integer of 2 to 6, and R ¹ and Each R ² independently represents a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by the general formula (2), or a group represented by the general formula (3) At least one of R ¹ and R ² which is a group and is bonded to one or more nitrogen atoms is a group represented by the general formula (2), and at least one is a general formula (3) Is a group represented by
General formula (2)

General formula (3)
[In general formulas (2) and (3), R ^{3 to} R ⁶ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxyl group, and R ⁷ may react with a hydroxyl group Represents a residue of a compound having a functional group. ]   The color according to any one of claims 1 to 3, wherein the content of the β-hydroxyalkylamide (D) is 1 to 20 parts by mass with respect to the total solid content in the photosensitive coloring composition for color filters. Photosensitive coloring composition for filters.   The photosensitive coloring composition for color filters of any one of Claims 1-4 in which a coloring agent (A) contains a green pigment.   The color filter which comprises the filter segment formed with the photosensitive coloring composition for color filters of any one of Claims 1-5 on a base material.