KR20010024701A - Novel salts and photosensitive colored resin compositions containing the same - Google Patents

Abstract

The present invention provides a color filter having excellent spectral characteristics without color mixing and decolorization of the color; A composition containing a salt, that is, a composition obtained by dissolving or dispersing a salt and a photosensitive colored resin composition containing the same as a dye; A color filter manufactured using the resin composition; And a water-soluble pigment having a sulfonic acid group and a skeletal structure represented by the formula (1), which is suitable for the production of an image display device and an image pickup device manufactured using the color filter (here, the skeleton structure is directly bonded thereto or through an alkyl group or the like). It relates to a novel salt consisting of an amine having an amino group). The use of this novel salt prevents the spreading of the pattern of the water-soluble dye in the step of developing in water, followed by a patterning process while maintaining the dispersing properties of the dye.

Description

Novel salt and photosensitive colored resin composition containing the same {NOVEL SALTS AND PHOTOSENSITIVE COLORED RESIN COMPOSITIONS CONTAINING THE SAME}

The color filter used for materials, such as a liquid crystal display element and a solid-state image sensor, is conventionally formed by pattern formation and dyeing using a photoresist on a salty resin, or the method of forming a pattern with a salty photoresist and then dyeing it. It is produced. However, this method has problems such as a complicated process for going through the dyeing process, disadvantageous cost reduction, and difficulty in process management such as acidity (pH) of the dye bath and temperature control.

Thus, for example, Japanese Patent Laid-Open Publication No. 60-237403 and Japanese Laid-Open Patent Publication No. Hei 4-163552 have proposed a method of forming a pattern with a photoresist in which a pigment is dispersed and directly creating a color filter. Since this method contains the insoluble pigment which was colored beforehand, after irradiating an ultraviolet-ray, the coloring pattern is obtained by removing the uncured part from a developing solution, and a simplification of a process is expected. However, there are few kinds of pigments used in these, and for example, when a colored film is made to have a transmittance at a wavelength of 540 nm of 10% and the transmittance is measured, a plurality of very small transmittances exist in the range of 520 to 580 nm. There is a point that you cannot be satisfied with the characteristic.

On the other hand, Japanese Patent Application Laid-Open No. 58-100107 proposes a method of forming a color filter using a material in which a dye is dispersed in a silver halide emulsion. Since this material can be used as it is, the dye used in the conventional dyeing method as it is, the spectral characteristics can be satisfied, but there are disadvantages such as silver halide is expensive and requires a special apparatus for the process.

On the other hand, many non-silver salt materials using the soluble dye pigment are proposed. For example, Japanese Patent Application Laid-Open No. 57-16407 and Japanese Patent Application Laid-Open No. 57-74707 have reports of a material in which a water-soluble dye or an oil-soluble dye is dissolved in an organic solvent-based resist material. In addition, Japanese Patent Application Laid-Open Nos. 1-501973, JP-A 2-127602, JP-A 4-128703, JP-A 6-9891, 6 -51115, Japanese Patent Laid-Open No. 6-59114, Japanese Patent Laid-Open No. 6-220339, Japanese Patent Laid-Open No. 6-230210, Japanese Patent Laid-Open No. 6-300913, Japanese Patent Laid-Open No. 7-84114, Japanese Patent Laid-Open No. 7-72323 Japanese Patent Publication No.

However, when dyes with low solubility in organic solvents are used, there is a fear of precipitation during long-term storage, and is particularly unsuitable for the production of color filters for solid-state imaging devices requiring high resolution. In addition, in the method of using the oil-soluble dye which has a relatively high solubility, although the precipitation of the dye dye in storage is prevented, after forming a monochromatic pattern, when apply | coating another coloring composition, the process of providing an overcoat layer, etc. Breeding or migration may occur, and color mixing or contamination may occur, resulting in a decrease in color purity.

Further, the compositions described in Japanese Patent Application Laid-Open No. 1986 77804, Japanese Patent Application Laid-Open No. 1986 180202, and Japanese Patent Application Laid-open No. 1986 180203 dissolve a dye in a polyimide precursor to obtain a composition. However, these compositions use a high boiling point solvent such as N-vinylpyrrolidone to dissolve the dye or polyimide precursor and pre-back the process to obtain a film of the composition on the substrate to form a color filter. In the pre-baking process, the drawback is that the temperature must be increased to remove the solvent.

Moreover, in the case of the composition containing a water-soluble dye, there exists a possibility that a dye may elute from a pattern and a color may stain in the image development process with water after pattern irradiation.

This invention aims at the development of the material which can use the organic solvent in which the dye does not elute from a pattern and is easy to form a film | membrane in the image development process after pattern irradiation, maintaining the spectral characteristic of a water-soluble dye.

The present invention also aims at the development of a material having heat resistance and light resistance while utilizing the richness, transparency, and ease of color adjustment of a kind of water-soluble dye.

The present invention is a novel salt useful as a color filter dye used in color display devices such as televisions, video monitors, computers, and image pickup devices such as color sensors, cameras, video cameras, compositions containing the same, and photosensitive colored resin compositions using the same. And an image display device and / or an imaging device having the colored image using the photosensitive colored resin composition or the colored image.

MEANS TO SOLVE THE PROBLEM The present inventors reached | attained this invention as a result of thorough examination in order to solve the above problems. That is, this invention relates to the following invention.

1. A novel salt comprising a water-soluble dye having a sulfonic acid group and an amine having a skeletal structure shown in the general formula (1).

2, The salt according to the above 1, wherein the amine is a primary amine.

3. The salt according to the above 2, wherein the primary amine is a compound represented by the formula (2).

(In Formula 2, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ each represent a hydrogen atom or an alkyl group of C1 to C5, x is an integer of 1 to 8, y is 1 to (8-x) of An integer, m is an integer of 1 to 3, n is an integer of 1 to 6. In addition, (R ₁ ) y and (H ₂ NH ₂ C) _X represents a substituent on the A ring, (R ₄ ) m is B A substituent on a ring, and (R ₅ ) n shall refer to a substituent on a C ring.)

4. The salt according to the above 2, wherein the primary amine is a compound represented by the formula (3).

5. The salt according to any one of 1 to 4 above, dissolved in an organic solvent having an alcoholic hydroxy group.

6. The salt dispersion composition as described in any one of said 1-4 is disperse | distributed to the organic solvent.

7. The pigment dispersion composition according to 6 above, wherein the organic solvent is an organic solvent having no alcoholic hydroxyl group.

8. Dye composition containing the water-soluble pigment | dye which has the salt and sulfonic acid group in any one of said 1-4.

9. (a) The water-soluble pigment | dye which has the salt in any one of said 1-4 or the said salt and sulfonic acid group, and (b) pigment is contained, The pigment composition characterized by the above-mentioned.

10. The salt according to any one of 1 to 4 is a salt of a red acid dye and an amine represented by the formula (1), (2) or (3), and the water-soluble pigment having a sulfonic acid group is a red acid dye, and the pigment is a red pigment. The pigment composition according to 9 above.

11. The pigment composition according to any one of 8 to 10, wherein the red acid dye is C.I Acid Red 289.

12. The red pigment is C.I. The pigment composition as described in any one of said 8-11 which is pigment red 209.

13. C.I. A salt consisting of an acid red 289 and a compound of the formula (3) or a salt of C.I. When the total content of acid red 289 contains 100 parts of total weight of a pigment, it is the range of 10-90 parts, The pigment composition as described in said 11-12 characterized by the above-mentioned.

14. It is for color filters, The salt in any one of said 1-5 characterized by the above-mentioned. The pigment | dye dispersion composition as described in said 6 or 7, and the pigment | dye composition in any one of said 8-13.

15. The photosensitive colored resin composition containing (1) the salt as described in any one of said 1-4, (2) a water-soluble resin or alkali-soluble resin, and (3) the compound obtained by causing a crosslinking reaction by radiation.

16. The salt according to any one of the above 1 to 4, wherein the salt is dissolved in an organic solvent having an alcoholic hydroxyl group, or the salt is the pigment dispersion composition according to the above 6 or 7 or the dye according to any one of the above 8 to 13. The said photosensitive colored resin composition of Claim 15 used or containing as a composition.

17. The color filter which has a hardened | cured material layer of the photosensitive coloring composition of said 15.

18. An image display device or imaging device comprising the color filter according to 17.

19. The colored image forming method using the photosensitive coloring resin composition of said 15 is formed, The coloring pattern by a photolithography method is characterized.

The salt of this invention consists of a water-soluble pigment | dye containing a sulfonic acid group, and the amine which has a skeletal structure shown by the said General formula (1). The amine having a skeletal structure represented by Chemical Formula 1 is a compound in which a primary to third amino group, preferably a primary amino group capable of forming a salt with a sulfonic acid group, on the skeletal structure represented by Chemical Formula 1 is bonded directly or through a bonding ring. to be. As a coupling ring, methylene, ethylene, propylene, a propylene, pentylene, etc. can mention C1-C5 alkylene ring, for example, methylene is preferable. This amine is also a compound that is soluble in acidic water and insoluble in alkaline water.

As an amine which has a skeletal structure shown by the said General formula (1), the compound shown by General formula (2) is mentioned, for example. As an alkyl group in R <_1> , R <_2> , R <_3> , R <_4> and R <_5> of general formula (2), for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, ter-bromine Linear or branched C1-C5 alkyl groups, such as a methyl group, n-pentyl group, isoamyl group, are mentioned, Preferably a C1-C3 alkyl group is mentioned.

In Formula 2, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , m, n. As a preferable combination of x and y, R <_1> , R <_3> is a methyl group, R <_2> , R <_4> is a hydrogen atom, R <_5> is isopropyl group, and m, n, x, and y are either one. Specifically, the abiethylamine shown in the said General formula (3) is mentioned.

As a water-soluble pigment | dye which has a sulfonic acid group used by this invention, it is not limited only to the water-soluble pigment | dye which has a sulfonic acid group, For example, acidic dye and direct dye are mentioned. Although there is no restriction | limiting in particular in the number of sulfonic acid groups in the said water-soluble pigment | dye, Generally, it is about 1-6.

Illustrative acidic dyes with color index (C.I.) numbers include the following dyes. These dyes are exemplary and the acid dyes usable in the present invention are not limited thereto.

C.I. Acid Yellow

1, 3, 4, 5, 7, 7: 1, 9, 11, 14, 17, 17: 1, 18, 19, 23, 23: 1, 24, 25, 25: 1, 27, 29, 29: 1, 34, 36, 38, 40, 40: 1, 41, 42, 44, 48, 49, 53, 54, 56, 57, 59, 60, 61, 63, 64, 65, 65: 1, 72, 73, 75, 76, 78, 79, 83, 96, 98, 99, 104, 105, 107, 110, 112, 114, 116, 116: 1, 117, 119, 123, 127, 128, 131, 132, 133, 135, 136, 137, 141, 142, 143, 151, 155, 157, 158: 1, 159, 161, 165, 166, 167, 169, 172, 174, 176, 184, 185, 189, 193, 194, 196, 197, 199, 200, 203, 204, 207, 208, 214, 215: 1, 216, 218, 219, 219: 1, 220, 221, 228, 230, 231, 232, 235, 236, 237, 239, 240, 241, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, etc.

C.I. Acid orange

1, 3, 5, 6, 7, 8, 10, 10: 1, 11, 12, 14, 17, 19, 20, 24, 25, 28, 33, 39, 43, 45, 47, 51, 51: 1, 52, 56, 60, 61, 62, 63, 64, 67, 69, 70, 74, 77, 78, 80, 81, 82, 85, 86, 87, 87: 1, 88, 88: 1, 89, 93, 94, 95, 96, 102, 105, 106, 107, 108, 116, 122, 124, 127, 128, 130, 134, 135, 140, 141, 142, 144, 145, 149, 154, 155, 156, 159, 160, 161, 162, 166, 168, 170, 171, 172, 173, etc.

C.I. Acid red

1, 4, 5, 6, 7, 8, 9, 10, 13, 14, 17, 18, 24, 26, 27, 29, 32, 33, 35, 37, 40, 41, 42, 44, 49, 50, 51, 51: 1, 52, 56, 57, 66, 70, 73, 80, 82, 85, 87, 88, 89, 91, 92, 93, 94, 95, 97, 98, 99, 106, 111, 114, 115, 116, 117, 118, 119, 119: 1, 127, 128, 129, 131, 134, 135, 137, 138, 141, 143, 145, 148, 150, 151, 154, 158, 167, 170, 174, 176, 179, 180, 182, 183, 184, 186, 191, 194, 195, 199, 201, 209, 211, 211: 1, 213, 213: 1, 214, 215, 217, 219, 221, 211: 1, 213, 213: 1, 214, 215, 217, 219, 221, 225, 225: 1, 226, 227, 228, 234, 246, 247, 249, 251, 252, 254, 256, 257, 259, 260, 261, 262, 263, 264, 265, 266, 274, 276, 277, 278, 279, 281, 282, 283, 289, 296, 299, 300, 301, 303, 307, 308, 310, 314: 1, 315, 316, 316: 1, 317, 318, 321, 322, 331, 336, 337, 341, 353, 354, 355, 356, 357, 359, 360, 361, 362, 364, 366, 374, 382, 383, 384, 388, 389, 392, 395, 396, 397, 399, 400, 403, 404, 405, 407, 410, 412, 413, 414, 415, 416, 417, 418, 419, 420, 421, 422, 423, 424, 425, 426, 427, 428, 429, 430, 431, 432, 433, etc. .

C.I. Acid Violet

1, 3, 5: 1, 6, 7, 9, 12, 13, 15, 17, 19, 21, 31, 34, 41, 42, 43, 47, 48, 49, 54, 56, 58, 66, 68, 75, 78, 80, 84, 85, 87, 89, 90, 97, 102, 103, 104, 105: 1, 106, 109, 120, 121, 122, 126, 128, 129, etc.

C.I. Acid blue

1, 3, 4, 5, 6, 7, 9, 13, 15, 20, 22, 23, 25, 27, 29, 40, 41, 43, 45, 47, 48, 59, 61: 1, 62, 72, 74, 78, 80, 82, 83, 89, 90, 92, 93, 93: 1, 100, 102, 103, 104, 106, 110, 112, 113, 116, 118, 119, 120, 123, 126, 127, 127: 1, 129, 129: 1, 133, 134, 138, 140, 142, 145, 147, 151, 156, 158, 158: 1, 158: 2, 161, 167, 168, 170, 171, 172, 175, 177, 182, 183, 185, 191, 192, 193, 198, 199, 201, 203, 204, 205, 207, 208, 209, 213, 220, 221, 224, 225, 227, 229, 229: 1, 230, 231, 232, 234, 235 239, 243, 245, 247, 249, 250, 254, 258, 260, 264, 270, 274, 276, 277, 278, 279, 280, 281 , 283, 284, 285, 288, 290, 296, 298, 300, 312, 314, 315, 317, 321, 324, 327, 328, 330, 331, 333, 335, 336, 338, 340, 341, 342 , 343, 344, 345, 346, 348, 349, 350, 351, 352, etc.

C.I. Acid green

1, 3, 5, 9, 12, 16, 19, 20, 25, 26, 27, 28, 35, 40, 40: 1, 41, 43, 50, 51, 52, 53, 60, 61, 65: 1, 66, 68: 1, 70: 1, 73, 79, 81, 82, 84, 87: 1, 91, 92, 94, 99, 100, 102, 103, 104, 106, 107, 108, 108: 1, 109, 111, 112, 114, 115, 117, 118, 119, 120, etc.

C.I. Acid brown

2, 4, 6, 10, 11, 13, 14, 15, 17, 19, 19: 1, 20, 21, 24, 28, 30, 37, 40, 43, 44, 45, 46, 47, 48, 50, 52, 53, 58, 59, 64, 65, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 80, 83, 84, 85, 88, 96, 97, 98, 100, 101, 102, 103, 104, 105, 106, 107, 107: 1, 108, 108: 1, 110, 110: 1, 112, 112: 1, 113, 113: 1, 119, 121, 122, 125, 126, 127, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 147, 156 157, 159, 160, 161, 162, 165, 167, 174, 175, 188, 188 : 1, 189, 191, 194, 196, 213, 214, 215, 216, 216: 1, 217, 218, 223, 224, 266, 227, 228, 231, 232, 235, 237, 238, 239, 240 , 248, 251, 253, 254, 258, 264, 266, 267, 268, 270, 276, 282, 282: 1, 283, 284, 286, 287, 289, 290, 294, 297, 298, 298: 1 , 301, 303, 304, 311, 314, 321, 322, 324, 325, 326, 327, 328, 330, 331, 332, 332: 1, 333, 338, 341, 342, 343, 343: 1, 345 , 347, 348, 349, 351, 354, 355, 356, 357, 358, 359, 360, 361, 362, 363, 364, 365, 366, 373, 380, 381, 382, 383, 384, 386, 387 , 390, 392, 395, 396, 397, 402, 403, 404, 406, 408, 409, 413, 414, 415, 416, 417, 418, 419, 420, 422, 425, 427, 428, 429, 430, 431, 432, 433, 434, 435, 436, 437, 438, 439, 440, etc.

C.I. Acid Black

1, 2, 7, 9, 21, 24, 26, 29, 31, 41, 47, 48, 50, 52, 52: 1, 58, 60, 60: 1, 61, 62, 63, 63: 1, 63: 2, 64, 65, 71, 75, 76, 77, 78, 79, 82, 83, 84, 92, 94, 102, 107, 109, 110, 112, 113, 115, 118, 119, 121, 122, 127, 128, 131, 131: 1, 132, 139, 140, 155, 157, 159, 164, 170, 172, 173, 179, 180, 187, 187: 1, 189, 191, 192: 2, 194, 196, 197, 199, 207, 208, 209, 210, 213, 215, 217, 218, 220, 221, 222, 224, 225, 226, 227, 228 and the like.

As a direct dye which can be used in order to obtain the color filter pigment | dye of this invention, the following dye is mentioned when illustrated by a color index number. These dyes are exemplary, and the direct dye which can be used for this invention is not limited to these.

C.I. Direct yellow

1, 2, 4, 5, 6, 6: 1, 8, 9, 11, 12, 14, 17, 22, 24, 26, 27, 28, 29, 30, 33, 34, 39, 44, 48, 49, 50, 50: 1, 53, 54, 58, 68, 83, 84, 86, 87, 93, 95, 96, 98, 99, 100, 103, 105, 105: 1, 106, 107, 109, 110, 118, 126, 127, 130, 132, 133, 134, 137, 137: 1, 138, 139, 142, 144, 147, 148, 148: 1, 149, 150, 152, 153, 154, 157, 159, 160, 161, 162, 163, 164, 165, etc.

C.I. Direct orange

1, 6, 7, 8, 10, 15, 17, 25, 26, 29, 29: 1, 32, 34, 35, 37, 37: 1, 39, 40, 41, 46, 49, 51, 57, 61, 62: 1, 70, 72, 73, 80, 102, 106, 107, 108, 118, 121 and the like.

C.I. Direct red

1. 2. 4. 7. 9. 10, 11, 13, 16, 17, 20, 21, 22, 23, 24, 26, 28, 31, 36, 37, 38, 39, 44, 45, 46, 47, 54, 59, 62, 63, 67, 72, 75, 76, 79, 80, 81, 83, 83: 1, 84, 89, 92, 95, 99, 107, 111, 112, 118, 121, 123, 126, 127, 127: 1, 149, 153, 155, 173, 176, 184, 187, 195, 205, 207, 209, 211, 212, 216, 217, 218, 221, 223, 224, 225, 226, 227, 230, 232, 233, 236, 238, 239, 240, 241, 242, 243, 250, 251, 252, 253, 254, 255, 257, 258, 259, 260, 261, etc.

C.I. Direct violet

1, 6, 7, 9, 12, 14, 21, 22, 35, 40, 41, 46, 47, 48, 51, 53, 56, 62, 66, 83, 93, 94, 95, 98, 100, 102, 103, 104 and the like.

C.I. Direct blue

1, 2, 3, 6, 8, 8: 1, 9, 10, 14, 15, 21, 22, 25, 35, 54, 55, 59, 65, 67, 68, 70, 71, 74, 75, 76, 77, 78, 80, 80: 1, 81, 84, 85, 86, 87, 90, 94, 95, 96, 98, 100, 106, 108, 109, 120, 120: 1, 121, 126, 150, 151, 154, 158, 158: 1, 160, 162, 165, 168, 173, 189, 191, 192, 193, 199, 200, 201, 202, 203, 207, 211, 212, 213, 214, 215, 218, 219, 222, 225, 229, 236, 237, 243, 244, 248, 249, 251, 252, 253, 255, 256, 257, 261, 262, 265, 267, 270, 273, 274, 277, 278, 281, 283, 284, 285, 286, 288, 289, 290, 291, 292, 293, 294, 295, 296, 297 and the like.

C.I. Direct green

1, 6, 8, 8: 1, 26, 27, 28, 29, 30, 31, 47, 51: 1, 59, 66, 67, 68, 69, 80, 83, 84, 85, 85: 1, 90, 92, 94, 95, 96, 97, 98, 99, etc.

C.I. Direct brown

1, 1: 2, 2, 6, 14, 25, 27, 30, 31, 33, 39, 44, 44: 1, 51, 53, 57, 59, 61, 78, 79, 80, 95, 100, 101, 103, 106, 111, 112, 113, 115, 116, 154, 157, 169, 170, 172, 184, 195, 200, 208, 209, 210, 212, 214, 218, 219, 221, 222, 223, 225, 229, 230, 231, 232, 235, 238, 240, 241, etc.

C.I. Direct Black etc.

4, 5, 9, 11, 14, 17, 19, 19: 1, 22, 28, 29, 32, 36, 38, 49, 51, 56, 62, 71, 74, 75, 80, 91, 94, 101, 103, 108, 112, 113, 115, 117, 118, 121, 122, 132, 146, 150, 154, 155, 159, 160, 161, 162: 1, 163, 164, 165, 168, 169, 170, 171, 173, 174, 175, 176, 177, 179, 180 and the like.

As a red acid dye used for this invention, the following dye is mentioned, for example when illustrated by a color index (C.I.) number. These dyes are exemplary and the red acid dyes usable in the present invention are not limited to these.

C.I. Acid red

1, 4, 5, 6, 7, 8, 9, 10, 13, 14, 17, 18, 24, 26, 27, 29, 32, 33, 35, 37, 40, 41, 42, 44, 49, 50, 51, 51: 1, 52, 56, 57, 66, 70, 73, 80, 82, 85, 87, 88, 89, 91, 92, 93, 94, 95, 97, 98, 99, 106, 111, 114, 115, 116, 117, 118, 119, 119: 1, 127, 128, 129, 131, 134, 135, 137, 138, 141, 143, 145, 148, 150, 151, 154, 158, 167, 170, 174, 176, 179, 180, 182, 184, 186, 191, 194, 195, 199, 201, 209, 211, 211: 1, 213, 213: 1, 214, 215, 217, 219, 221, 225, 225: 1, 226, 227, 228, 234, 246, 247, 249, 251, 252, 254, 256, 257, 259, 260, 261, 262, 263, 264, 265, 266, 274, 276, 277, 278, 279, 281, 282, 283, 289, 296, 299, 300, 301, 303, 307, 308, 310, 314: 1, 315, 316, 316: 1, 317, 318, 321, 322, 331, 336, 337, 341, 353, 354, 355, 356, 357, 359, 360, 361, 362, 364, 366, 374, 382, 383, 384, 388, 389, 392, 395, 396, 397, 399, 400, 403, 404, 405, 407, 410, 412, 413, 414, 415, 416, 417, 418, 419, 420, 421, 422, 423, 424, 425, 426, 427, 428, 429, 430, 431, 432, 433, etc.

In addition to these, C.I. Acid red 289 is particularly good.

As a red pigment used for this invention, C.I. When illustrated by a number, the following red pigments are mentioned. These red pigments are exemplary and the red pigment which can be used by this invention is not limited to these.

C.I. Pigment red

1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 112, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 185, 187, 193, 209, 216, 224, 243, 245 and the like.

Among these, C.I. Pigment Red 122 or C.I. Pigment Red 209 is particularly good.

In order to obtain the salt of the present invention, for example, the following may be performed. In other words, if a pigment having a sulfonic acid group is required, it is heated and dissolved in water, and in a basic aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate or potassium hydrogen carbonate, or in an acidic aqueous solution such as hydrochloric acid, lactic acid or acetic acid. The pH is adjusted to 5-9, and then, the product is precipitated by adding an aqueous solution in which the amine having a skeletal structure shown in Chemical Formula 1 is dissolved in the solution so that the amount of the amine is equal to or greater than the equivalent amount of sulfonic acid group per molecule of dye. It can be filtered, washed and dried.

The obtained salt shows solubility in the organic solvent which has an alcoholic hydroxyl group. However, benzene solvents such as benzene, toluene and xylene, cellosolve acid group esters such as methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether Propylene esters such as propylene glycol monoalkyl ether acetates such as acetate and propylene glycol monobutyl ether acetate, methyl methoxypropionate, methyl ethoxypropionate and ethyl ethoxypropionate, methyl acetate, ethyl acetate, ethyl acetate and amyl acetate It shows little solubility in organic solvents or pure water having no alcoholic hydroxyl group, such as ketones such as acetic acid esters, acetone, methyl ethyl ketone, and methyl butyl ketone.

The salt of this invention can be melt | dissolved in the organic solvent which has an alcoholic hydroxyl group, and can be filtered if necessary, and can obtain a pigment dissolution composition (salt of this invention which was dissolved in the organic solvent which has an alcoholic hydroxyl group). At this time, in order to adjust the developability of the photosensitive coloring composition mentioned later, you may be a pigment dissolution composition containing the water-soluble pigment | dye which has a sulfonic acid group, and the salt of this invention of the said pigment | dye. In the dye dissolution composition, when the total weight of the dye is 100 parts, the salt of the present invention is 75 to 100 parts by weight, preferably 80 to 100 parts by weight, more preferably 85 to 100 parts by weight, and the remainder is a sulfonic acid group. It is a water-soluble pigment | dye which has.

As an organic solvent which has an alcoholic hydroxy group in this invention, it is good that it is a liquid normally at normal temperature (about 25 degreeC), and a mono or polyacoholic hydroxy compound of about 1-10 carbon atoms is mentioned. The number of hydroxy groups in the polyalcoholic hydroxy compound is not particularly limited, but is usually about 2-3. These hydroxy compounds may further have substituents other than a hydroxy group, and the type and number of these substituents are not particularly limited as long as the salt of the present invention is not insoluble, but the number of substituents is usually about 1 to 3. As a typical kind of substituent, a C1-C5 alkoxy group, More preferably, a C1-C3 alkoxy group is mentioned.

Examples of the organic solvent having an alcoholic hydroxyl group include alcohols such as methanol, ethanol, propanol and benzyl alcohol, glycols such as ethylene glycol and propylene glycol, cellosols such as methyl cellosolve, ethyl cellosolve, and methyl cellosolve And propylene glycol monoalkyl ethers such as butyl glycol, propylene glycol monomethyl ether, and propylene glycol motoethyl ester, and lactic acid esters such as methyl lactate, ethyl lactate, and methyl lactate.

In addition, the salt of the present invention can be used not only as the dye dissolving composition (the salt of the present invention dissolved in an organic solvent having an alcoholic hydroxyl group) but also as a dye dispersing composition. One embodiment used as the dye dispersion composition may be used as the dye dispersion composition by dispersing the salt of the present invention in an insoluble solvent of the salt, for example, an organic solvent having no alcoholic hydroxyl group. As another aspect used as a dye dispersion composition, since the salt of this invention is used together with a pigment, for example, a red pigment, in this case, when the organic solvent which has an alcoholic hydroxyl group is used, the solution of the salt of this invention is dissolved. It is possible to obtain a pigment dispersion composition in which a pigment is dispersed, and a dye dispersion composition in which both are dispersed in this solvent can be obtained by using an insoluble solvent of this salt, for example, an organic solvent having no alcoholic hydroxyl group. The case of using together the salt of this invention and a red pigment is demonstrated as a pigment composition of this invention later.

As a dispersion method of a pigment | dye, a pigment component and dispersing agents, such as anionic, cationic, or nonionic polymeric surfactant, are added to the said organic solvent, and a ball mill and a sand are added. It can carry out by disperse | distributing by a conventional method using dispersers, such as a sand mill, a dissolver, two roll mills, and three roll mills. The quantity of the dispersing agent added at this time is 1-40 weight part with respect to a pigment | dye according to the particle diameter of a pigment | dye and the molecular weight of a dispersing agent. Moreover, when using the polymeric dispersing agent which may become a gel by heat during dispersion | distribution, you may carry out post-dispersion later as needed, and may mix, after disperse | distributing each pigment | dye.

In the present invention, the term "dye or dye component" means a salt of the present invention unless it is specifically defined, when it contains a water-soluble dye and / or a pigment having a sulfonic acid group together with the salt of the present invention or the salt of the present invention. It is used by the meaning containing the water-soluble pigment | dye and / or pigment which have a sulfonic acid group.

the dye composition of the present invention wherein (a) a water-soluble dye having a sulfonic acid group and an amine having a skeleton structure represented by the formula (1), (2) or (3), or a water-soluble dye having the salt and a sulfonic acid group, and (b) a pigment at the same time, Preferably, the water-soluble pigment | dye which has a sulfonic acid group is a red acid dye, and the pigment composition whose pigment is a red pigment uses the dye (water-soluble pigment | dye which has a sulfonic acid group) and a pigment simultaneously, and is easy to adjust the abundance, transparency, and chromaticity of the kind of dye. It is characterized by having both heat resistance and weather resistance of the pigment while utilizing.

Of the pigment composition containing the pigment of the present invention, the component (a) (the water-soluble pigment having the sulfonic acid group and the amine salt having the skeleton structure shown in the formulas (1), (2) and (3) or the water-soluble pigment having the salt and sulfonic acid group) The content ratio is 10 to 90 parts, preferably when the total weight of the dye (when the salt and the pigment of the present invention and the water-soluble dye having a sulfonic acid group is also included) is 100 parts. It is preferable to exist in the range of 20-85 parts. In this range, when the film is formed so that both the heat resistance and the light resistance are excellent and the transmittance at the wavelength of 540 nm is 10%, the maximum transmittance at the wavelength of 400 to 500 nm is not preferable. It is preferable because there is no plurality of microtransmittances in the range of 520 to 580 nm, not in the range.

The pigment composition of the present invention can be used by being dispersed in an organic solvent having an alcoholic hydroxy group or an organic solvent having no alcoholic hydroxy group as described above. As an organic solvent which does not have an alcoholic hydroxyl group, the said solvents illustrated as what does not show the solubility of the salt of this invention are mentioned.

The photosensitive colored resin composition of the present invention contains a compound capable of causing a crosslinking reaction by radiation such as the salt of the present invention, a water-soluble resin or an alkali-soluble resin, ultraviolet rays or electron beams, and a photopolymerization initiator as necessary. . Moreover, if necessary, a solvent may be contained, and if necessary, it may contain a preparation such as a surfactant. In the photosensitive colored resin composition of this invention, after dissolving or dispersing each said component as it is or as needed in a solvent, and also adding additives, such as surfactant, as needed, and fully mixing, and filtering by a filter as needed. It can prepare by making it.

Although the salt of this invention may be used as it is, you may use as the said pigment | dye dissolution composition (the salt of this invention dissolved in the organic solvent which has an alcoholic hydroxyl group), the said pigment dispersion composition, or the said pigment composition. When the salt of this invention is used as the said dye dissolution composition, the said dye dispersion composition, or the said dye composition, the photosensitive colored resin composition of this invention will contain these.

As water-soluble resin used for the photosensitive coloring resin composition of this invention, resin which melt | dissolves in the organic solvent which has an alcoholic hydroxyl group used in order to obtain a pigment | dye dissolution composition, melt | dissolving in water is preferable. Specifically, a polymer compound having a monomer unit such as vinylpyrrolidone, acryloyl morpholine, (meth) acrylamide, 2-hydroxyethyl (meth) acrylate and the like can be used. As this water-soluble resin, poly (meth) acrylamide, polyvinylpyrrolidone, etc. are mentioned, for example. Moreover, the water-soluble resin used here, for example, combines the said monomers individually or in combination of 2 or more types, and if necessary, monomers, such as ethylene, (meth) acrylate, vinylphenol, (meth) acrylonitrile, etc. Alcohols such as methanol, ethanol, propanol and benzyl alcohol; glycols such as ethylene glycol and propylene glycol; cellosolves such as methyl cellosolve, ethyl cellosolve, and butylsenrosolve, and propylene glycol mono Also obtained by polymerization methods such as radical polymerization among organic solvents having alcoholic hydroxyl groups such as propylene glycol monoalkyl ethers such as methyl ether and propylene glycol monoethyl ether, and lactic acid esters such as methyl lactate, ethyl lactate, and methyl lactate. Can be.

Examples of the alkali-soluble resin used in the photosensitive colored resin composition of the present invention include a polymer compound having a helical hydroxyl group such as polyvinylphenol and novolak resin, and a resin having a carboxyl group. As resin which has the said carboxyl group, For example, the ring-opening thing by water of the compound which has a (meth) acrylic acid unit, the copolymerization compound of a maleic anhydride, and another monomer, or the said copolymerization compound is ring-opened by alcohols or amines ( And (b) resins having a partial ester unit or a partial amide unit obtained by virtue of the above.

Examples of the compound having a (meth) acrylic acid unit include monomers such as (meth) acrylic acid alone or vinyl acetate, styrene, (meth) acrylonitrile, and (meth) acrylic acid ester esters, and (meth) acrylic acid. The compound copolymerized by methods, such as a knife polymerization and an ionic polymerization, is mentioned.

Moreover, as a copolymer compound of the said maleic anhydride and another monomer, the copolymer compound of the monomers of styrene, such as styrene and (alpha)-alkylstyrene, or its derivative (s), and a maleic anhydride is mentioned, for example in a conventional method. Thereby, resin which has a carboxyl group ring-opened by adding water to a maleic acid part can be obtained.

Moreover, as alcohols used in order to obtain resin which has the said partial ester unit, For example, alcohol, such as methanol, ethanol, a propanol, 2-hydroxyethyl (meth) acrylate, pentaerythritol triacrylate, polyethyleneglycol mono (Meth) acrylic acid ester etc. are mentioned.

Moreover, aniline, benzylamine, etc. are mentioned as amines used in order to obtain resin which has the said partial amide unit.

As a compound which can cause a crosslinking reaction by the radiation used for the photosensitive coloring resin composition of this invention, For example, an epoxy (meth) acrylate resin, C1-C6 polyhydric (preferably 2-6) alcohol Acrylate resin obtained by making (meth) acrylic acid react, N-metholol compound, and the acrylate resin obtained by making (meth) acrylic acid react, a (di)-azide compound, etc. are mentioned. These compounds can be used individually or in combination of 2 or more types as needed.

Examples of the epoxy (meth) acrylate resins include bisphenol-A type epoxy resins, bisphenol-F type epoxy resins, bisphenol-S type epoxy resins, novolak type epoxy resins, polycarboxylic acid glycidyl esters, and polyolglycidyl esters. . Aliphatic or alicyclic epoxy resins, amine epoxy resins, triphenol methane type epoxy resins, dihydroxy benzene type epoxy resins, and the like (meth) acrylic acid reactants.

As the acrylate resin obtained by reacting a lower alcohol or a polyhydric alcohol with (meth) acrylic acid, for example, lower alcohols such as methanol, ethanol and propanol, or (poly) ethylene glycol, (poly) propylene glycol, And a reaction product of a polyhydric alcohol such as glycerin, metyrolpropane, pentaerythritol, dipentaerythritol, and (meth) alkaline acid.

As an acrylate resin obtained by making an N-metholol compound and (meth) acrylic acid react, for example, N-metholol melamine, N-metholol benzoguanamine, (poly) N-metholol (meth) acrylamide And a reactant with (meth) acrylic acid. Examples of the (di) amide compound include (di) amide benzophenone, (di) amide carcon, (di) amide styrenebene, and (di) amide benzalzik. Rohexanone etc. are mentioned.

As a photoinitiator which can be used for the photosensitive coloring resin composition of this invention as needed, benzyl, benzoin methyl ether, benzoin isopropyl ether, benzoin bethyl ether, benzophenone 3, 3-dimethyl-4-methoxybenzo Phenone, benzoyl benzoic acid, esterified benzoyl benzoic acid, 4-benzoyl-4'-methyldiphenyl sulfide, benzyldimethyl ketal, 2-butoxyl ethyl-4-methylaminobenzoate, chlorothioxanthone, methylchioxanthone , Ethyl thioxanthone, isopropyl thioxanthone, dichloro thioxanthone, dimethyl thioxanthone, diethyl thioxanthone, diisoproyl thioxanthone, dimethylaminobenzoate, dimethylamino benzoic acid isoamyl ester, 1- ( 4-dodicylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-methyl-1-phenylpropan-1-one, 1- (4 Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, methylbenzoylisofoam Yit, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-methylamino-1- (4-morpholinophenyl) -butane- 1-one, 2,2'-bis (2-chlorophenyl) -4-4 ', 5, 5'-tetraphenylbisimidazole, 2,2'-bis (2-chlorophenyl) -4,4' , 5,5'-tetra (4-methoxyphenyl) bisimidazole, 2,4-bis (trichloromethyl) -6- (4'-methoxyphenyl) -1,3,5-s-triazine , 2,4,6-tris (trichloromethyl) -1,3,5-s-triazine, 2,4-bis (tribromomethyl) -6- (4'-methoxyphenyl) -1, 2,5-s-triazine, 2,4,6-tris (tribromomethyl) -1,3,5-s-crazine and tribromomethylphenyl sulfone are mentioned. These compounds can be used individually or in combination of 2 or more types as needed.

Surfactants that can be used as needed in the photosensitive colored resin composition of the present invention may be any nonionic, cationic or anionic, but the use of nonionic surfactants that do not decompose the salts of the present invention into pigments and amines. This is particularly preferred. As surfactant used, the brand name Celeron S-380 marketed by Seimi Chemicals, and the brand name Florard FC 430 marketed by 3M are mentioned, for example. As addition amount, 5000 ppm or less, Preferably 3000 ppm or less are used for the photosensitive coloring resin composition.

Each component amount (ratio) used in the photosensitive colored resin composition of the present invention is not particularly limited as long as the object of the present invention is achieved. However, when the total solid content of the composition is 100 parts by weight, the salt of the present invention is usually used. Silver is in the range of 1 part by weight or more, preferably 3 parts by weight or more, more preferably 5 parts by weight or more, 35 parts by weight or less, preferably 30 parts by weight or less, and more preferably 25 parts by weight or less. Binder resin, such as resin or alkali-soluble resin, is 10 weight part or more, Preferably it is 20 weight part or more, 80 weight part or less, Preferably it is 70 weight part or less, The compound obtained by causing a crosslinking reaction by radiation Silver is 2 weight part or more, Preferably it is 5 weight part or more, 50 weight part or less, Preferably it is the range of 5-40 weight part, The photoinitiator is 0-40 weight part, wind It is preferably 0 to 30 parts by weight.

The photosensitive colored resin composition of this invention can be used, disperse | distributing and / or dissolving in a solvent. As a solvent which can be used at this time, benzene solvents, such as benzene, toluene, and xylene, a cellosolve acetate ester, such as methyl cellosolve acetate, an ethyl cellosolve acetate, a butyl cellosolve acetate, a propylene glycol monomethyl ether acetate Propylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propionic acid esters such as methyl methoxy propionate, ethoxy propionate, ethyl ethoxy propionate, methyl acetate, ethyl acetate Acetic acid esters, such as benzyl acetate, acetone, methyl ethyl ketone, methyl benzyl ketone, ketones, alcohols such as methanol, ethanol, propanol, and benzyl alcohol, glycols such as ethylene glycol and propylene glycol, and methyl cello Solve, ethyl cellosolve, butyl cellosolve Solves, propylene glycol mono methyl ether. Although propylene glycol mono alkyl ethers, such as propylene glycol mono ethyl ether, lactic acid esters, such as methyl lactate, ethyl lactate, and a butyl butyl, etc. are mentioned, It is not limited to these.

When using a solvent, solid content concentration is 5 weight part or more, Preferably it is 10 weight part or more, 60 weight part or less, Preferably it is 50 weight part or less, More preferably, 40 weight part with respect to the whole photosensitive coloring resin composition whole. It is good to use so that it may become a range below negative.

The obtained photosensitive coloring resin composition can obtain a coloring pattern by the photolithographic method. That is, the coating is applied on a substrate such as a chromium substrate, a glass substrate, a silicon wafer, or the like by a spin coating method, a roller coating method, a printing method, or a barcode method so that the film thickness is usually 0.3 to 10 µm, and the surface temperature is 50 to Soft-baking is performed on the hot plate of 130 to produce a colored photosensitive film. Radiation (e.g., through a mask depicting a desired pattern such as a dot pattern or a stripe pattern, using an exposure apparatus such as a projection aligner and a stepper) is applied to the film. For example, electron beams, X-rays, ultraviolet rays, visible light, and the like) are irradiated. In the case of using a water-soluble resin, it is developed in water of pH 4-9, preferably pure water, and in the case of using an alkaline water-soluble paper, it is developed in an aqueous alkali solution of pH 9-12 and the unirradiated portion is removed to form a colored pattern. , Post-exposure, post-bake and the like are performed to obtain a colored image of the present invention.

The curley filter which consists of a coloring image of this invention mentioned above using the photosensitive coloring resin composition containing the pigment | dye of red, green, blue, or the complementary color of red, green, blue, or complementary colors which are three primary colors of light, and especially the light, The photolithography method can be repeatedly produced for each color.

Moreover, as aqueous alkali solution used at this time, aqueous solution of inorganic salts, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium metasilicate, potassium metasilicate, monomethanolamine, diethanolamine, tri Aqueous solutions of organic amines such as ethanolamine, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine or quaternary ammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide The aqueous solution of etc. can be used.

You may use these aqueous solutions individually or in mixture of 2 or more types. Moreover, additives, such as surfactant and an antifoamer, can be added as needed.

These developer can be used without limitation as long as it is in the range of pH mentioned above. When using the photosensitive resin composition of this invention especially on a semiconductor substrate, it is especially preferable to use pure water or an organic alkali developing solution.

In the image display device including the color filter of the present invention, for example, in the case of a liquid crystal display device, a back light, a polarizing film part, a liquid crystal part, the color filter part of the present invention, a polarizing film part, and the like are used in this order. In the case of an image pickup device, the color filter unit of the present invention is formed on a protective layer or the like by using a charge transfer device, a phototransistor, a photodiode and the like formed on a semiconductor such as silicon.

Example

Although an Example demonstrates this invention further more concretely, this invention is not limited only to these Examples.

Example 1 (dye for indigo filter)

3400 ml of water is added to a 10 l beaker and the C.I. 180 g of Acid Blue 185 was added, and the temperature was raised to 65 ° C. to completely dissolve it. The pH of this solution was then adjusted to 8, and 1010 g of a solution consisting of 140 g of compound of formula 3, 30 g of acetic acid and 700 g of water was slowly added. After completion of the dropwise addition, the mixture was stirred for 2 hours, and the precipitated product was filtered, washed, and dried to obtain the color filter dye of the present invention. This color filter dye was dissolved in propylene glycol monomethyl ether.

Example 2 (yellow color filter)

Into a 5 L beaker, 2000 ml of water was added and C.I. 180 g of Acid Yellow 110 was added, and the temperature was raised to 70 ° C. to completely dissolve it. The pH of this solution was then adjusted to 9, and 710 g of a solution consisting of 140 g of compound of formula 3, 30 g of acetic acid and 700 g of water was slowly added. After completion of the dropwise addition, the mixture was stirred for 2 hours, and the precipitated product was filtered, washed, and dried to obtain the color filter dye of the present invention.

Example 3 (yellow color filter)

Into a 5 L beaker, 2000 ml of water was added and C.I. 200g of Direct Yellow 142 was added, and it heated up at 70 degreeC and melt | dissolved completely. The pH of this solution was then adjusted to 8, and 1000 g of a solution consisting of 140 g of compound of formula 3, 30 g of acetic acid and 700 g of water was slowly added. After completion of the dropwise addition, the mixture was stirred for 2 hours, and the precipitated product was filtered, washed, and dried to obtain the color filter dye of the present invention.

Example 4 (Dye for Red Filter)

1000 ml of water was added to a 5 l beaker and the C.I. 200 g of Acid Red 257 was added, and the temperature was raised to 70 ° C. to completely dissolve it. The pH of this solution was then adjusted to 8, and 820 g of a solution consisting of 140 g of compound of formula 3, 30 g of acetic acid and 700 g of water was slowly added. After completion of the dropwise addition, the mixture was stirred for 2 hours, and the precipitated product was filtered, washed, and dried to obtain the color filter dye of the present invention.

Example 5 (Dye for Red Filter)

1000 ml of water was added to a 5 l beaker and the C.I. 200 g of Acid Red 257 was added, and the temperature was raised to 70 ° C. to completely dissolve it. The pH of this solution was then adjusted to 8, and 820 g of a solution consisting of 140 g of compound of formula 3, 30 g of acetic acid and 700 g of water was slowly added. After completion of the dropwise addition, the mixture was stirred for 2 hours, and the precipitated product was filtered, washed, and dried to obtain the color filter dye of the present invention.

Example 6 (photosensitive magenta resin composition)

51.6 parts by weight of rubiscol K-30, a polyvinylpyrrolidone resin sold by BASF as a water-soluble resin, and a compound obtained by crosslinking reaction by radiation; a acrylate resin sold by Nippon Kayaku Co., Ltd. 8.6 parts by weight, and 8.6 parts by weight of Cayarrad TMPTA, 17.2 parts by weight of Triazine-A commercially available from Sanwakei Cal as a photopolymerization initiator, and 14.0 parts by weight of the dye obtained in Example 5 as a color filter dye. After dissolving so that a solid content concentration might be 15 weight part in ether, and also the surfactant commercially available by Seika Chemical, brand name surflon-S383, it filtered by the filter of 1 micrometer of pore diameters, and the photosensitive coloring of this invention. A resin composition (magenta) was obtained.

Example 7 (photosensitive magenta resin composition)

5 parts by weight of rubiscol K-30, which is a polyvinylpyrrolidone resin sold by BASF as a water-soluble resin, and a compound obtained by crosslinking reaction by radiation; trade name Kayarard TMPTA, which is an acrylate resin sold by Nippon Kayaku Co., Ltd. 18 parts by weight, 18 parts by weight of Triazine-A available from Sanwakei Cal as a photopolymerization initiator, 9.5 parts by weight of the dye obtained in Example 5 as a color filter dye, CI After dissolving 1.5 parts by weight of acid red 289 in lactic acid ether to a solids concentration of 15.4 parts by weight, and adding a commercially available surfactant, Surflon-S383, which is commercially available from Seimi Chemical, a filter having a pore diameter of 1 μm. It filtered by and obtained the photosensitive coloring resin composition (magenta) of this invention.

Example 8 (magenta image formation)

On a bare silicone wafer, a trade name Kayayamiror UC-1, a thermosetting protective film sold by Nippon Gunpowder, was applied to a thickness of 1 μm, and the protective film layer was heated on a hot plate having a surface temperature of 220 ° C. for 5 minutes. Formed. On this protective film, the photosensitive colored resin composition obtained in Example 6 was spin-coated so that the film thickness was 1 micrometer, and the soft baking was performed for 90 second on the hotplate of surface temperature 80 degreeC. This film was then subjected to close exposure using a chrome mask depicting a resolution test pattern. The light source is a 500W ultra-high pressure mercury lamp equipped with a UVD-35 filter and a V-42 filter commercially available from Toshiba Glass, and emits ultraviolet rays having a wavelength of 365 nm. Moreover, irradiation energy was 150 mJ / cm <2>.

Subsequently, after developing for 60 second with pure water of the temperature of 25 degreeC, post-baking was performed for 5 minutes on the hotplate of surface temperature 200 degreeC, and the cured film was obtained. When observed with an optical microscope, the pattern of 2 micrometers without a residue was resolved. Moreover, when the color characteristic was measured, very favorable spectral characteristic was shown.

Example 9 (production of complementary color filter)

The photosensitive coloring resin composition of indigo blue and yellow was obtained instead of the color filter pigment | dye obtained in Example 1 or the color filter pigment | dye obtained in Example 2, respectively. Using these photosensitive coloring resin compositions, the complementary color filter was produced. That is, the indigo photosensitive resin composition is apply | coated on the magenta pattern obtained in Example 7, soft-baking, pattern exposure, image development, and post bake are performed, and the yellow photosensitive resin composition is apply | coated on this magenta and indigo pattern, Was performed to obtain a complementary color filter. When observed with an optical microscope, it was a color filter excellent in color purity characteristics without mixing and decolorization.

Example 10 (Navy Pigment Dispersion Composition)

3400 ml of water was added to a 10 l beaker and the C.I. 180 g of Acid Blue 185 was added, and the temperature was raised to 65 ° C. to completely dissolve. Then, the pH of the solution was adjusted to 8, and then 1010 g of a solution consisting of 140 g of compound of formula 3, 30 g of acetic acid and 700 g of water was slowly added. After completion of the dropwise addition, the mixture was stirred for 2 hours, and the precipitated product was filtered, washed, dried, and ground to obtain a salt for use in the present invention. 10 g of this salt, 2 g of the brand name Solsperse 24000 which is a commercially available polymer dispersant sold by Genca, 11.5 g of cyclohexanone, and 26.5 g of propylene glycol monomethyl ether acetate are dispersed in a bead mill to disperse the pigment dispersion composition of the present invention. Got.

Example 11 (yellow pigment dispersion composition)

2000 ml of water was added to a 5 l beaker and the C.I. 180 g of Acid Yellow 110 was added, and the temperature was raised to 70 ° C. to completely dissolve it. The pH of this solution was then adjusted to 9, and 710 g of a solution consisting of 140 g of compound of formula 3, 30 g of acetic acid and 700 g of water was slowly added. After completion of the dropwise addition, the mixture was stirred for 2 hours, and the precipitated product was filtered, washed, dried, and ground to obtain a salt for use in the present invention. 10 g of this salt, 2 g of the brand name Solsperse 24000 which is a commercially available polymer dispersant sold by Genca, 11.5 g of cyclohexanone, and 26.5 g of propylene glycol monomethyl ether acetate are dispersed in a bead mill to disperse the pigment dispersion composition of the present invention. Got.

Example 12 (Yellow Pigment Dispersion Composition)

2000 ml of water was added to a 5 l beaker and the C.I. 200g of Direct Yellow 142 was added, and it heated up at 70 degreeC and melt | dissolved completely. The pH of this solution was then adjusted to 8, and 1000 g of a solution consisting of 140 g of compound of formula 3, 30 g of acetic acid and 700 g of water was slowly added. After completion of the dropwise addition, the mixture was stirred for 2 hours, and the precipitated product was filtered, washed, dried, and ground to obtain a salt for use in the present invention. 10 g of this salt, 2 g of the brand name Solsperse 24000 which is a commercially available polymer dispersant sold by Genca, 11.5 g of cyclohexanone, and 26.5 g of propylene glycol monomethyl ether acetate are dispersed in a bead mill to disperse the pigment dispersion composition of the present invention. Got.

Example 13 (red pigment dispersion composition)

1000 ml of water was added to a 5 l beaker and the C.I. 200 g of Acid Red 257 was added, and the temperature was raised to 70 ° C. to completely dissolve it. The pH of this solution was then adjusted to 8, and 820 g of a solution consisting of 140 g of compound of formula 3, 30 g of acetic acid and 700 g of water was slowly added. After completion of the dropwise addition, the mixture was stirred for 2 hours, and the precipitated product was filtered, washed, dried, and ground to obtain a salt for use in the present invention. 10 g of this salt, 2 g of the brand name Solsperse 24000 which is a commercially available polymer dispersant sold by Genca, 11.5 g of cyclohexanone, and 26.5 g of propylene glycol monomethyl ether acetate are dispersed in a bead mill to disperse the pigment dispersion composition of the present invention. Got.

Example 14 (magenta pigment dispersion composition)

1250 ml of water was added to a 5 l beaker and the C.I. 100 g of Acid Red 289 was added, and the temperature was raised to 60 ° C. to completely dissolve it. The pH of this solution was then adjusted to 9, and 710 g of a solution consisting of 320 g of compound of formula 3, 30 g of acetic acid and 700 g of water was slowly added. After completion of the dropwise addition, the mixture was stirred for 2 hours, and the precipitated product was filtered, washed, dried, and ground to obtain a salt for use in the present invention. 10 g of this salt, 2 g of the brand name Solsperse 24000 which is a commercially available polymer dispersant sold by Genca, 11.5 g of cyclohexanone, and 26.5 g of propylene glycol monomethyl ether acetate are dispersed in a bead mill to disperse the pigment dispersion composition of the present invention. Got.

Example 15 (Photosensitive Magenta Resin Composition)

As an alkali-soluble resin, 4.6 g of a weight average molecular weight 30,000 polymer compound consisting of 70 mol% of benzyl methacrylate and 30 mol% of methacrylic acid, a compound obtained by crosslinking reaction by radiation, is an acrylate resin commercially available from Nippon Kayaku Pharmaceutical. Kayarrad DPHA 4.2 g by weight, trade name Irgacure-369 1,5 g, a photopolymerization initiator marketed by Shivagaigi as a photopolymerization initiator, trade name Kayayacure, a photopolymerization initiator marketed by Nippon Gunpowder 0.75 g of -DETX-S and 0.75 g of a trade name biimidazole, which is a photopolymerization initiator sold by Kugogan Kasei, are added to 45 g of propylene glycol monomethyl ether acetate, and a commercial trade name Surflon which is a surfactant commercially available from Seimi Chemical Co., Ltd. After adding -S-383, it was filtered through a filter having a pore diameter of 2.5 μm to obtain a photosensitive colored resin composition (magenta) of the present invention. .

Example 16 (magenta image formation)

A trade name Kayaya Mirror-UC-1, a thermosetting protective film sold by Nippon Gunpowder, was applied on a bare silicon wafer at a thickness of 1 µm, and heated on a hot plate having a surface temperature of 220 ° C. for 5 minutes to form a protective film layer. On this protective film, the photosensitive colored resin composition obtained in Example 15 was spin-coated so that the film thickness was 1 micrometer, and the soft baking was performed for 90 second on the hotplate of surface temperature 80 degreeC. This film was then subjected to close exposure using a chrome mask depicting a resolution test pattern. The light source is a 500W ultra-high pressure mercury lamp equipped with a UVD-35 filter and a V-42 filter commercially available from Toshiba Glass, and emits UV rays having a wavelength of 365 nm. Moreover, irradiation energy was 150 mJ / cm <2>. Subsequently, after developing for 60 second in brand name Kaya mirror-DVL-T50D (organic alkali developing solution marketed by Nippon Kayaku) with the temperature of 25 degreeC, it wash | cleaned with water and post-baked for 5 minutes on the hotplate of surface temperature 200 degreeC, and obtained the cured film. . When observed with an optical microscope, the pattern of 2 micrometers without a residue was resolved. Moreover, when the color characteristic was measured, very favorable spectral characteristic was shown.

Example 17 (Complementary Color Filter Production)

The dye for color filters (indigo dye dispersion composition) obtained in Example 10 or the dye for yellow filters (yellow pigment dispersion composition) obtained in Example 11 was carried out similarly to Example 15 instead of the dye for color filters of Example 15. Indigo and yellow, photosensitive colored resin composition was obtained, respectively. The complementary color filter was produced using these photosensitive colored resin compositions. That is, the indigo photosensitive resin composition is apply | coated on the magenta pattern obtained in Example 16, soft-baking, pattern exposure, image development, and post-baking are carried out, and the yellow photosensitive resin composition is apply | coated on this magenta and indigo pattern, Was performed to obtain a complementary color filter. When observed with an optical microscope, it was a color filter excellent in color purity characteristics without mixing and decolorization.

Creation example 1

1250 ml of water was added to a 5 l beaker and the C.I. 100 g of Acid Red 289 was added and the temperature was raised to 60 ° C. to completely dissolve it. The pH of this solution was then adjusted to 9, and 710 g of a solution consisting of 320 g of compound of formula 3, 30 g of acetic acid and 700 g of water was slowly added. After completion of the dropwise addition, the mixture was stirred for 2 hours, and the precipitated product was filtered, washed, dried, and ground to obtain a salt.

Examples 18-22

Salts obtained in Preparation Example 1 and C.I. Pigment Red 122 was mixed in the weight shown in Table 1, and each was added to 20 g of a brand name Solsperse 24000, a cyclohexanone 115 g, and 265 g of propylene glycol monomethyl ether acetate, each of which is a commercially available polymer dispersant from Genca. ) To obtain a dye dispersion composition of the present invention. The obtained composition was uniform without color discrimination. Subsequently, as a resin capable of developing an aqueous solution, 196.8 g of each of the obtained pigment compositions, 91.8 g of a polymer compound having a weight average molecular weight of 30,000 consisting of 70 mol% of benzyl methacrylate and 30 mol% of methacrylic acid, obtained by crosslinking reaction by radiation As a compound, 61.2 g of trade name Kayayarad DPHA, an acrylate resin sold by Nippon Kayaku, and 19.0 g of Irgacure-369, a photopolymerization initiator commercially available from Ciba Kaigi, as a photopolymerization initiator, 9.6 g of a commercially available photopolymerization initiator, Kayacure-DETX-S, and 9.6 g of a biimidazole, a photopolymerization initiator commercially available from Kurogane Kasei, were added to 612 g of propylene glycol monomethyl ether acetate. After adding the brand name Surflon-S-383 which is a surfactant marketed by a knife, it filtered by the filter of 1.2 micrometers of pore diameters, and the photosensitive property of this invention. The colored resin composition was obtained. After forming a film by spin-coating on a glass substrate so that the transmittance at 540 nm might be 10%, the transmittance was measured. This is summarized in Table 1.

Example Salt (g) Pigment (g) T (min) (nm) T (max) nm% T (50%) nm nm 18 78 22 538 430 81 490 582 19 70 30 538 432 83 492 580 20 47 53 539 439 87 493 575 21 28 72 540 440 89 492 571 22 15 85 540 440 92 492 570

Salts in the table are C.I. Acid Red 289 and a salt consisting of Formula 3, the pigment is C.I. Pigment Red 122 is shown. Further, T (minimum) represents a wavelength having a minimum transmittance at a wavelength of 520 to 580 nm, T (maximum) represents a wavelength having a maximum transmittance at a wavelength of 430 to 450 nm and a transmittance at that time, and T (50 %) Represents the wavelength in the case of 50% transmittance.

Example 23

The photosensitive colored resin composition of Example 20 was spin-coated on a glass substrate, and soft-baked for 90 second on the hotplate of surface temperature 80 degreeC. This film was then subjected to close exposure using a chrome mask depicting a resolution test pattern. The light source is a 500W ultra-high pressure mercury lamp, equipped with a UVD-35 filter and a V-42 filter made of Toshiba glass, and having a wavelength of 365 nm. Moreover, irradiation energy was 150 mJ / cm <2>. Subsequently, after developing for 60 second in Kaya mirror-DVL-T50D (brand name, Nippon Chemical Co., Ltd. organic alkali developing solution) of temperature 25 degreeC, it wash | cleaned with water and post-baked on the hotplate of surface temperature 200 degreeC for 5 minutes, and obtained the cured film. . When observed with an optical microscope, the pattern of 2 micrometers without a residue was resolved. In addition, when the weather resistance of the film was irradiated with a fade meter for 1000 hours, the color difference ΔE was 5, indicating good light / heat resistance.

Example 24

Complementary color filter was produced on the board | substrate obtained in Example 23 using the photosensitive coloring resin composition of indigo blue and yellow, respectively. That is, indigo blue photosensitive resin composition is apply | coated on a magenta pattern, soft baking, pattern exposure, image development, and post bake are performed, and a yellow photosensitive resin composition is apply | coated on this magenta and indigo pattern, and the same operation is performed, The color filter of a complementary color system was obtained. When observed with the optical microscope, it was the color filter excellent in the color purity characteristic without mixing and discoloration.

When the salt of this invention is used, the elution from the pattern of a dye can be suppressed in the image development process by water after pattern irradiation, maintaining the spectral characteristic of a water-soluble dye. In addition, since it is not necessary to use a high boiling point solvent such as N-vinylpyrrolidone as the solvent for film formation of the photosensitive colored resin composition, the film can be formed at a relatively low temperature. The color filter prepared using the dye for the color filter, the dissolving or dispersing composition or the dye composition using the salt of the present invention and the photosensitive colored resin composition using the same has no color mixing and discoloration, and has excellent color purity and spectral characteristics. A color filter that can be used in color display devices such as video monitors, computers, and imaging devices such as color sensors, video cameras, and digital cameras can be manufactured with high quality.

Claims (19)

The novel salt which consists of a water-soluble pigment | dye which has a sulfonic acid group, and an amine which has a skeletal structure shown by following General formula (1). [Formula 1] The novel salt of claim 1, wherein the amine is a primary amine. The novel salt of claim 2, wherein the primary amine is a compound represented by formula (2). [Formula 2] (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ each represent a hydrogen atom or an alkyl group of C 1 to C 5, x is an integer of 1 to 8, y is an integer of 1 to (8−x), m is an integer of 1 to 3, n is an integer of 1 to 6. In addition, (R ₁ ) y and (H ₂ NH ₂ C) _X represent a substituent on the A ring, (R ₄ ) m is on the B ring A substituent, and (R ₅ ) n shall refer to a substituent on the C ring.) The novel salt of claim 2, wherein the primary amine is a compound represented by the following Chemical Formula 3. [Formula 3] The novel salt according to any one of claims 1 to 4, dissolved in an organic solvent having an alcoholic hydroxy group. The salt as described in any one of Claims 1-4 is disperse | distributed to the organic solvent, The pigment dispersion composition characterized by the above-mentioned. The dye dispersion composition according to claim 6, wherein the organic solvent is an organic solvent having no alcoholic hydroxyl group. The pigment composition containing the salt as described in any one of Claims 1-4, and the water-soluble pigment | dye which has a sulfonic acid group. (a) the salt according to any one of claims 1 to 4 or a water-soluble dye having the salt and a sulfonic acid group, (b) Pigment composition containing pigment. The salt according to any one of claims 1 to 4, wherein the salt according to any one of claims 1 to 4 is a salt of a red acid dye and an amine represented by Formula 1, 2 or 3, and the water-soluble pigment having a sulfonic acid group is a red acid dye. And the pigment is a red pigment. The water-soluble dye or red acid dye having any of the sulfonic acid groups according to any one of claims 8 to 10, wherein C.I. Acid Red 289 is a pigment composition. 12. The red pigment of any one of claims 9-11, wherein the red pigment is C.I. Pigment Red 122 and / or C.I. Pigment Red 209 described pigment composition. 12. The method of claim 10 or 11, wherein C.I. A salt consisting of Acid Red 289 and the compound of Formula 3 or C.I. The pigment composition characterized in that it is the range of 10-90 parts when the total content of Acid Red 289 makes a total weight of a pigment | dye 100 parts. It is for a color filter, The salt as described in any one of Claims 1-5, The pigment dispersion composition as described in any one of Claims 6 or 8, and as described in any one of Claims 8-13. Pigment composition. (1) The photosensitive colored resin composition containing the salt as described in any one of Claims 1-4, (2) water-soluble resin or alkali-soluble resin, and (3) the compound obtained by causing a crosslinking reaction by radiation. The salt according to claim 15, wherein the salt according to any one of claims 1 to 4 is dissolved in an organic solvent having an alcoholic hydroxy group, or the salt is dispersed in the dye according to claim 6 or 7. The photosensitive colored resin composition used or contained as a composition or the pigment composition as described in any one of Claims 8-13. The color filter which has a hardened | cured material layer of the photosensitive coloring composition of Claim 15. An image display device or an imaging device comprising the color filter according to claim 17. The coloring pattern by photolithographic method is formed using the photosensitive coloring resin composition of Claim 15, The coloring image formation method characterized by the above-mentioned.