JPH1039127A - Resist composition for color filter, and production of color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter with high accuracy and of a low cost, and especially to provide a production method for a flexible color filter by which the production processes are largely reduced without using a mask and can be adopted for the production for various kinds with small lots. SOLUTION: This resist compsn. for color filter contains a binder resin, a crosslinking agent, an IR absorbing dye having absorption in a near infrared wavelength region, a photoacid producing agent and a pigment. The compsn. is applied on a transparent substrate, directly exposed to laser light and developed to form a color image.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for manufacturing a color filter used in combination with a liquid crystal display device or a solid-state image sensor. In particular, the present invention relates to a method of manufacturing a color filter for directly forming a color pattern without a mask by combining a negative chemically amplified color resist having high sensitivity to a near infrared region and a laser beam.

[0002]

2. Description of the Related Art A color filter is formed by forming fine pixels such as red, green and blue on a glass substrate by a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method or the like. These conventional methods have the following features and problems. A color filter by a dyeing method is manufactured by forming an image with a photosensitive resin obtained by mixing a dichromate as a photosensitive agent in gelatin, polyvinyl alcohol, or the like, and then dyeing the resultant. Although the dyeing method is excellent in terms of color reproducibility, in order to form multiple colors on the same substrate, an anti-staining step is essential, and there is a problem that the step becomes complicated. In addition, light resistance is poor because a dye is used. Bichromic acid used as a photosensitive agent is also a problem from the viewpoint of preventing pollution.

A color filter formed by a printing method transfers a thermosetting or photocuring ink to a glass substrate by a method such as screen printing or flexographic printing. Although the process is simple because image formation and dyeing are unnecessary, a high-definition image cannot be obtained and there is a problem in ink smoothness. A color filter by an electrodeposition method is a method in which a glass substrate provided with electrodes is immersed in a bath containing a pigment or a dye, and a color is attached by electrophoresis. Although excellent in smoothness, it is difficult to form a complicated pattern because an electrode is required on the glass substrate in advance.

In the pigment dispersion method, an image is formed by using a colored resist in which a pigment is dispersed in a photocurable resin. It has advantages such as high heat resistance and no need for dyeing, and enables high-precision image formation. In terms of quality, the pigment dispersion method is superior to the above-mentioned production method, and is currently the mainstream of color filter production. As described above, the conventional color filter manufacturing technology has advantages and disadvantages, and a new color filter manufacturing technology is desired.

In recent years, with the progress of computer image processing technology, attention has been paid to a technology for directly forming a resist image by laser light without producing a mask film for exposure from digital image information. In particular, semiconductor lasers have high output,
Since it has a long life and is small, high efficiency and stable image formation is possible. Since a mask is not required, the manufacturing process can be significantly shortened. In addition, laser lithography is also advantageous for improving the accuracy of color filters, and providing photosensitive materials for color filters suitable for semiconductor lasers. Is desired.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems. That is, the present invention provides a high-efficiency, high-precision color printing method using a novel manufacturing method combining laser light and a specific color resist. This enables the production of a filter.

[0007]

The object of the present invention is to provide (a) a binder resin, (b) a crosslinking agent, (c) an infrared absorbing dye having absorption in the near infrared wavelength region, and (d) photoacid generation. Agent,
(E) A method for producing a color filter which forms a colored image by applying the resist composition for a color filter containing a pigment and the composition onto a transparent substrate, and directly exposing and developing the photosensitive material with a laser beam. You.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The color resist used in the present invention comprises (a) a binder resin, (b) a crosslinking agent, (c) an infrared absorbing dye having absorption in a near infrared wavelength region, (d) a photoacid generator, and (e) a pigment. It contains. (A) The binder resin is not particularly limited as long as it has a coating film forming function, and the following can be specifically exemplified.

1) Polyolefin-based polymer Polyethylene, polypropylene, polyisobutylene, etc. 2) Diene-based polymer Polybutadiene, polyisoprene, etc. 3) Polymer having a conjugated polyene structure Polyacetylene-based polymer, polyphenylene-based polymer, etc.

4) Vinyl polymer polyvinyl chloride, polystyrene, vinyl acetate, polyvinyl alcohol, polyacrylic acid, polyacrylate, polyacrylamide, polyacrylonitrile, polyvinylphenol, etc. 5) polyether, polyphenylene ether, polyoxirane, polyoxetane, Polytetrahydrofuran, polyetherketone,
Polyetheretherketone, polyacetal, etc.

6) Phenol resin Novolak resin, resol resin, etc. 7) Polyester Polyethylene terephthalate, polyphenolphthalein terephthalate, polycarbonate, alkyd resin, unsaturated polyester resin, etc.

8) Polyamide Nylon-6, Nylon 66, water-soluble nylon, polyphenyleneamide, etc. 9) Polypeptide gelatin, casein, etc. 10) Epoxy resin and its modified products Novolak epoxy resin, bisphenol epoxy resin, novolak epoxy acrylate and acid anhydride 11) Others Polyurethane, polyimide, melamine resin, urea resin, etc.
Polyimidazole, polyoxazole, polypyrrole,
Polyaniline, polysulfide, polysulfone, celluloses, etc.

Among these resins, those having a carboxyl group or a phenolic hydroxyl group in the side chain or main chain of the resin are preferable from the viewpoint of preventing pollution since they can be developed with alkali. Further, a resin having an aromatic ring is preferable because of its excellent reactivity with a crosslinking agent. Novolak resins, polyvinyl phenol resins, and the like are more preferable resins that satisfy the above requirements.

As the novolak resin, (o, m, p)
-Cresol, 2,5-xylenol, 3,5-xylenol, resorcinol, pyrogallol, bisphenol,
Bisphenol-A, trisphenol, (o, m,
At least one aromatic hydrocarbon such as p) -ethylphenol, (o, m, p) -propylphenol, n-butylphenol, t-butylphenol, (1,2) -naphthol is subjected to formaldehyde, Examples include aldehydes such as acetaldehyde, propionaldehyde, benzaldehyde, and furafur, and polycondensation with at least one aldehyde selected from ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone or ketones.

In particular, (o, m, p) -cresol,
A novolak resin obtained by condensing at least one phenol selected from 2,5-xylenol, 3,5-xylenol, and resorcinol with an aldehyde such as formaldehyde and acetaldehyde is preferable. In particular, a novolak containing 50 mol% or more of m-cresol has high developability and is preferable.

Instead of formaldehyde and acetaldehyde, paraformaldehyde and paraacetaldehyde, respectively, may be used. Novolak resin GP
Weight average molecular weight in terms of polystyrene by C measurement (Mw)
Is 1000 to 50,000, more preferably 1500 to 4
0000 is used.

As the polyvinyl phenol resin,
(O, m, p) -hydroxystyrene, 2- (o, m,
A resin obtained by homopolymerization or copolymerization of hydroxystyrene such as (p-hydroxyphenyl) propylene is exemplified. Hydroxystyrenes chlorine in the aromatic ring, bromine, iodine, an alkyl group of halogens or C ₁ -C _4, such as fluorine may be substituted.

The polyvinyl phenol resin is usually obtained by polymerizing hydroxystyrenes in the presence of a radical polymerization initiator or a cationic polymerization initiator. Such a polyvinyl phenol resin may be partially hydrogenated. The weight average molecular weight in terms of polystyrene by GPC measurement of the polyvinyl phenol resin is 1000 to 100.
000, more preferably 1500 to 70000.

When the Mw of both the novolak resin and the polyvinylphenol resin is below the above range, the function of forming a coating film is reduced and it is difficult to obtain a uniform coating film. Next, the crosslinking agent (b) used in the present invention will be described. The cross-linking agent is a compound that causes a cross-linking reaction under an acidic catalyst, and specifically includes a compound obtained by reacting melamine, benzoguanamine, glycoluril, or urea with formaldehyde, or an alkyl-modified compound thereof, an epoxy compound, a resol compound, and the like. Can be

Specifically, Cymel (registered trademark) 300, 301, 303, 350, 73 manufactured by Mitsui Cyanamid Co., Ltd.
6, 738, 370, 771, 325, 327, 70
3,701,266,267,285,232,23
5, 238, 1141, 272, 254, 202, 11
56 and 1158 are examples of a compound obtained by reacting melamine with formaldehyde or an alkyl-modified product thereof. Cymel® 1123, 1125, 1128
This is an example of a compound obtained by reacting benzoguanamine with formaldehyde or an alkyl-modified product thereof. Cymel (registered trademark) 1170, 1171, 1174, 1172 is an example of a compound obtained by allowing formaldehyde to act on glycoluril or an alkyl-modified product thereof. Examples of a compound obtained by reacting urea with formaldehyde or an alkyl-modified product thereof include UFR (registered trademark) 6 of Mitsui Cyanamid Co., Ltd.
5,300.

Examples of epoxy compounds include novolak epoxy resins (VDPN-638, 701, manufactured by Toto Kasei Co., Ltd.).
702, 703, 704, etc.), amine epoxy resin (YH-434, manufactured by Toto Kasei), bisphenol A epoxy resin, sorbitol (poly) glycidyl ether,
(Poly) glycerol (poly) glycidyl ether, pentaerythritol (poly) glycidyl ether, triglycidyl trishydroxyethyl isocyanurate,
Allyl glycidyl ether, ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, lauryl alcohol glycidyl ether, glycidyl adipic ether, glycidyl phthalate, dibromophenyl glycidyl ether,
Dibromoneopentyl glycol diglycidyl ether, glycidyl phthalimide, (poly) ethylene glycol glycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, butyl glycidyl ether, etc. be able to.

Examples of resol compounds include PP-3000s, PP-3000A and RP-297 manufactured by Gunei Chemical Co., Ltd.
8, SP-1974, SP-1975, SP-197
6, SP-1977, RP-3993 and the like.
Among them, a particularly preferred compound is -N (C
A compound having an H ₂ OR) ₂ group (wherein, R represents a hydrogen atom or an alkyl group). Specifically, a compound obtained by reacting urea or melamine with formaldehyde or an alkyl-modified compound thereof is preferable, and a melamine derivative having an alkoxymethyl group is particularly preferable. next,
Specific examples of the infrared absorbing dye (c) having an absorption in the near infrared wavelength region used in the present invention include the following.

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

Of these, cyanine dyes are more preferred. Further, an indole type cyanine (indocyanine) or a thiazole type cyanine (thiocyanine) dye is particularly preferable. Next, the photoacid generator (d) used in the present invention includes, for example, 1) S.I. I. Schlesinger, Photog
r. Sci. Eng. , 18, 387 (1974),
T. S. Bal et al, Polymer, 21,
423 (1980); 2) U.S. Pat. Nos. 4,069,055 and 4,069,
No. 056, Re27,992, Japanese Patent Application No. 3-1401
Ammonium salt described in the specification of No. 40, etc.,

3) D. C. Necker et al,
Macromolecules, 17, 2468 (19
84), C.I. S. Wen et al, Teh. Pro
c. Conf. Rad. Curing ASIA, p4
78, Tokyo, Oct (1988); U.S. Pat. Nos. 4,069,055 and 4,069,056;

4) J. V. Crivello et a
1, Macromolecules, 10 (6), 13
07 (1977), Chem. & Eng. News,
Nov. 28, p31 (1988), European Patent No. 10
No. 4,143, U.S. Pat. Nos. 339,049, 41
0,201, JP-A-2-150848, JP-A-2-150848
Iodonium salts described in the specification or publication of 296514,

5) J. V. Crivello et a
1, Polymer J. 17, 73 (1985),
J. V. Crivello et al, J. Mol. Org.
Chem. 43, 3055 (1978); R. W
att et al, J.A. Polymer Sci. ,
Polymer Chem. Ed. , 22,1789
(1984); V. Crivello et a
1, Polymer Bull. , 14, 279 (19
88); V. Crivello et al, Ma
cromolecules, 14 (5), 1141 (1
981); V. Crivello et al,
J. Polymer Sci. PolymerChe
m. Ed. , 17, 2877 (1979), European Patent Nos. 370,693, 3,902,114 and 23.
No. 3,567, No. 297,443, No. 297,442
No. 4,933,377, 161 and 81
Nos. 1, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827 and German Patent 2,904,626
Nos. 3,604,580 and 3,604,581, and the sulfonium salts described in the publications and the like.

6) J. V. Crivello et a
1, Macromolecules, 10 (6), 13
07 (1977); V. Crivello et
al, J. et al. Polymer Sci. , Polymer
Chem. Ed. , 17, 1047 (1979) and the like,

7) C.I. S. Wen et al, Te
h. Proc. Conf. Rad. Curing AS
IA, p478, Tokyo, Oct (1988), etc .; onium salts such as arsonium salts; 8) U.S. Pat. No. 3,905,815, JP-B-46-4.
605, JP-A-48-36281, JP-A-55-3
2070, JP-A-60-239736, JP-A-61-61736
-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401,
JP-A-63-70243, JP-A-63-298339
Organic halogen compounds described in the specification or publication of the issue,

9) K. Meier et al, J. Mol. R
ad. Curing, 13 (4), 26 (1986),
T. P. Gill et al, Inorg. Che
m. , 19, 3007 (1980); Astru
c, Acc. Chem. Res. , 19 (12), 37
7 (1896), JP-A-2-161445, etc., organometallic / organic halides,

10) S. Hayase et al,
J. Polymer Sci. , 25, 753 (198
7), E. Reichmanis et al. P
polymer Sci. , Polymer Chem.
Ed. 23, 1 (1985); Q. Zhu et
al, J. et al. Photochem. , 36, 85, 39,
317 (1987); Amit et al, Te
trahedron Lett. , (24) 2205
(1973); H. R. Barton etal,
J. Chem Soc. , 3571 (1965);
M. Collins et al, J. Mol. Chem. So
c. , Perkin I, 1695 (1975);
Rudinstein et al, Tetrahed
ron Lett. , (17), 1445 (197
5). W. Walker et al, J.A. Am.
Chem. Soc. , 110, 7170 (1988),
S. C. Busman et al, J. M .; Imagin
gTechnol. , 11 (4), 191 (198
5), H. M. Houlihan et al, Mac
romolecules, 21, 2001 (198
8), p. M. Collinset al, J. et al. Che
m. Soc. Chem. Commun. , 532 (1
972); Hayase et al, Macro
moleculars, 18, 1799 (1985),
E. FIG. Reichmanis et al. Elec
trochem. Soc. , Solid State
Sci. Technol. , 130 (6); M. H
oulihan et al, Macromolecu
les, 21, 2001 (1988), EP 02
90,750, 046,083, 156,53
No. 5, No. 271, 851, No. 0, 388, 343,
U.S. Pat. Nos. 3,901,710 and 4,181,53
No. 1, JP-A-60-198538, JP-A-53-13
3022, a photoacid generator having an o-nitrobenzyl-type protecting group,

11) M. Tuooka et al,
Polymer Preprints Japan, 3
8 (8); Berner et al, J. Mol. Ra
d. Curing, 13 (4); J. Mijs e
tal, Coating Technology. , 55
(697), 45 (1983); Akzo, H .; Ada
chi et al, Polymer Preprin
ts, Japan, 37 (3), EP 0199,
672, 84515, 199,672, 0
44,115, 0101,122, U.S. Patent Nos. 4,618,564, 4,371,605, 4,431,774, JP-A-64-18143, and JP-A-2-245756. Compounds, such as iminosulfonates, which generate sulfonic acid upon photodecomposition, described in JP-A No. 3-140109 or in Japanese Patent Application No. 61-166544. The disulfone compound of the above can be mentioned.

Compounds in which an acid-generating group or compound is introduced into the main chain or side chain of a polymer, such as M.P. E. FIG. Woodhouse et a
1, J .; Am. Chem. Soc. , 104, 5586
(1982); P. Pappas et al,
J. Imaging Sci. , 30 (5), 218
(1986); Kondo et al. Macr
omol. Chem. Rapid Commun. ,
9, 625 (1988); Yamada eta
1, Makromol. Chem. , 152, 153,
163 (1972); V. Crivello et
al, J. et al. Polymer Sci. , Polyme
r Chem. Ed. , 17, 3845 (1979),
U.S. Pat. No. 3,849,137, German Patent No. 3,91
4,407, JP-A-63-26653, JP-A-55-266.
No. 164824, JP-A-62-69263, JP-A-6-69263
3-140387, JP-A-63-163452, JP-A-62-153853, JP-A-63-14629
Compounds described in the specification or publication of the above-mentioned publications can be used.

Further, V.I. N. R. Pilai, Syn
thesis, (1), 1 (1980); Abad
et al, Tetrahedron Lett. ,
(47) 4555 (1971); H. R. Bart
on et al, J.A. Chem. Soc. , (C),
329 (1970); U.S. Pat. No. 3,779,778.
And compounds capable of generating an acid by light as described in JP-A No. 126,712 and the like. More specifically, for example, compounds represented by the following formulas T-1 to T-15 can be mentioned.

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

Of these, more preferred are s-triazine compounds having two or more trihalomethyl groups, and particularly preferred is tris (trichloromethyl) -s-
Triazine. Specific examples of the (e) pigment used in the present invention include inorganic pigments such as barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, chromium oxide, and carbon black, anthraquinone pigments, berylene pigments, and disazo pigments. Organic pigments such as pigments, phthalocyanine pigments, isoindoline pigments, dioxazine pigments, quinacridone pigments, verinone pigments, triphenylmethane pigments, and thioindigo pigments.

These can be used alone or in combination. Among them, especially phthalocyanine pigments,
Dioxazine pigments, anthraquinone pigments, disazo pigments, isoindoline pigments, and carbon black are preferred in terms of color reproducibility, light resistance, and heat resistance. It is specifically shown by a color index (CI) number.

C. I. Red; 9, 97, 122, 123,
149, 168, 177, 180, 192, 215, 2
16, 217, 220, 223, 224, 226, 22
7, 228, 240 C.I. I. Blue; 15, 15; 6, 22, 60, 64 C.I. I. Green; 7, 36 C.I. I. Black; 7 C.I. I. Yellow; 20, 24, 86, 93, 109, 11
0, 117, 125, 137, 138, 147, 14
8, 153, 154, 166, 168 C.I. I. Orange; 36, 43, 51, 55, 59, 6
1 C. I. Violet; 19, 23, 29, 30, 3
7, 40, 50 C.I. I. Tea; 23, 25, 26

The preferred mixing ratio of these light-sensitive materials is as follows: (a) 15-70 wt.
%, More preferably 20 to 65 wt%, (b) 5 to 40 wt% of the crosslinking agent, more preferably 10 to 35 wt%, and (c) 0.1 to 30 wt% of the infrared absorbing dye, more preferably 0.1 to 30 wt%.
5 to 25 wt%, (d) 0.1 to 30 wt% photoacid generator
%, More preferably 0.5 to 25 wt%, and (e) the pigment is 5 to 60%, more preferably 10 to 55 wt%.

(A) If the amount of the binder resin is less than the above range, the ability to form a coating film is reduced, so that a uniform film cannot be obtained, and pinholes and striations are easily generated. Also,
If it exceeds the above range, it is difficult to obtain a sufficient crosslinked structure, and the image forming function is reduced. (B) If the amount of the crosslinking agent is below the above range, the crosslinking reactivity decreases, and if the amount exceeds the above range, the coating film becomes sticky and the workability decreases.

(C) If the infrared absorbing dye is below the above range, it becomes difficult to obtain sufficient sensitivity, and if it exceeds the above range, the color reproducibility decreases. (D) When the photoacid generator falls below the above range, it becomes difficult to obtain sufficient sensitivity as in the case of the infrared absorbing dye, and when the photoacid generator exceeds the above range, component precipitation occurs on the coating film surface and a uniform coating film is formed. No longer available. (E) If the pigment is below the above range, the color density and color reproduction area required for the color filter are narrowed, and if it exceeds the above range, sufficient sensitivity cannot be obtained.

The light-sensitive material used in the present invention is usually used by dissolving the above components in an organic solvent. As the organic solvent, specifically, diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate,
n-octane, Valsol # 2, Apco # 18 Solvent, diisobutylene, amyl acetate, butyl butyrate, apco thinner, butyl ether, diisobutyl ketone, methyl cyclohexene, methyl nonyl ketone,
Propyl ether, dodecane, Social solvent
nt No1 and No2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 1
50, (n, sec, t) -butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether, ethyl orthoformate, methoxymethyl pentanone, methyl butyl Ketone, methylhexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, Dipentene, methoxymethylpentanol, methylamylketone, methylisopropylketone, propylpropionate, propyleneglycol Tert-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl Ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, methylethyl 3-ethoxypropionate, Methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, 3-ethoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, dipropylene glycol monomethyl ether, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether, Propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol,
Organic solvents such as tripropylene glycol methyl ether and 3-methyl-3-methoxybutyl acetate are exemplified.

It is also possible to use a mixture of two or more of the above solvents. The solvent has a boiling point of 10
It is preferable to select one in the range of 0 ° C to 200 ° C. More preferably, it has a boiling point of 120 ° C to 170 ° C. Further, the compounding amount of the organic solvent has a solid content concentration of 5 to 5.
It is preferable to adjust so as to be in the range of 50 wt%, more preferably in the range of 10 to 45 wt%. If the solid content is less than the above range, it is difficult to obtain a sufficient resist film thickness, and the color reproducibility becomes poor. On the other hand, if the ratio exceeds the above range, the viscosity of the photosensitive solution becomes high, so that it is difficult to control the uniformity and thickness of the coating film.

In the present invention, in addition to these essential components, a coating improver, a polymerization inhibitor, a plasticizer, a flame retardant, an antifoaming agent and the like can be suitably added. These can be used alone or in combination of several kinds. In the present invention, a color filter red, blue, green, black, etc. of a color filter on a transparent substrate is obtained by repeating the steps of substrate coating, coating film drying, laser exposure, and development of the color resist photosensitive solution obtained as described above as many times as necessary. Is formed.

Known methods such as spin coater, roll coater, curtain coater, screen printing, and dipping can be used for coating the substrate. A glass substrate is generally used as the substrate, but a plastic transparent substrate such as PMMA or polycarbonate can also be used. The coating thickness is 0.2μ
m to 10 μm are preferred. More preferably 0.3-5μ
It is. If the coating film thickness is below the above range, sufficient color density will not be obtained, and if it exceeds the above range, the flatness of the colored pattern will be lost.

In order to dry the coating film, a convection oven or a hot plate is used. The drying temperature is preferably from 50C to 150C, and the drying time is preferably from 30 seconds to 60 minutes. 700 to 110 as a light source for performing image exposure
A light source that emits a near-infrared laser beam of 0 nm, for example, a solid-state laser such as a ruby laser or a YAG laser;
A semiconductor laser and the like can be mentioned, and a semiconductor laser having a small size and a long life is particularly preferable.

The color filter pattern forms a latent image by directly scanning and exposing the resist film with laser light based on digital information of the pattern. Although development can be performed immediately after exposure, it is desirable to include a heating step (PEB post-exposure bake) after exposure to improve sensitivity. For the PEB, a convection oven or a hot plate used for drying a coating film can be used. PEB temperature is 50 ° C to 150 ° C, more preferably 6 ° C.
It is in the range of 0 ° C to 140 ° C. The PEB time is 30
A range from seconds to 60 minutes is preferred. If the PEB temperature and the time are below the above ranges, the effect of improving sensitivity is not seen, and if the PEB temperature and the time are beyond the above ranges, the resolution may be lowered.

The development is performed with a developing solution such as an organic solvent or an aqueous alkali solution. Acetone, toluene, ME
When developing with organic solvents such as K, environmental problems, harm,
An alkaline aqueous solution is more preferable as the developing solution because of problems such as explosion hazard. Examples include aqueous sodium hydroxide, aqueous potassium hydroxide, aqueous sodium carbonate, potassium carbonate, aqueous ammonia, aqueous tetramethylammonium hydroxide, and the like.

Further, a surfactant, an antifoaming agent and the like may be added to the developer. The developing method is not particularly limited, and can be performed by a known method such as a paddle method, a dipping method, and a spray method. Also, pre-wet may be adopted. A single-color pattern is formed in a series of steps from the above coating to development. In the production of a color filter, these series of steps are repeated for the required number of colors.However, before the next color patterning step, heat-curing or photo-curing is added after development to increase the film strength of the colored resist pattern formed on the image. Is desirable. In the case of thermosetting, use a convection oven or hot plate at 150 ° C to 25
In the case of photo-curing, it is desirable to irradiate with ultraviolet light such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a carbon arc lamp in the range of 10 to 10,000 mj at 0 ° C. for 30 seconds to 60 minutes.

[0057]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. Example-1 m-cresol novolak resin (Mw = 3000) 70 wt% Cymel 300 15 wt% (Methoxymethylmelamine manufactured by Mitsui Cyanamid Co.) Infrared absorbing dye CY-10 (Nippon Kayaku Co., S-1) 2.5 wt% 2,4,6-tris (trichloromethyl) -s-triazine 2.5 wt% (T-1) Anthraquinone Red (C.I.177) 10 wt% or more of the solid component concentration in cyclohexanone 20wt
% To prepare a color resist photosensitive solution.

Next, the above-mentioned resist photosensitive solution was applied to a 7059 glass substrate (manufactured by Corning) using a spin coater, and the resist film was dried on a hot plate at 80 ° C. for 1 minute. Α step of resist film thickness (manufactured by Tencor)
Was 2 μm. When the surface of the resist film was visually observed, there was no coating unevenness such as a pinhole, and a good coating film was obtained.

This was scanned and exposed with a semiconductor laser (830 nm, manufactured by Applied Techno). 3 for resist film
Irradiation was performed at 00 mj / cm ² . PEB was performed on a hot plate at 100 ° C. for 3 minutes. Development is performed using an aqueous solution of tetramethylammonium hydroxide (TMAH) at 25 ° C.
For 1 minute. Through the above operation, a red resist pattern was formed on the glass substrate that was scanned and exposed by the laser. The pattern edge was good.

Example 2 m-cresol novolak resin (Mw = 3000) 70 wt% Cymel 300 15 wt% (Methoxymethylmelamine manufactured by Mitsui Cyanamid Co.) Infrared absorbing dye CY-10 (Nippon Kayaku Co., Ltd .; S -1) 2.5 wt% 2,4,6-tris (trichloromethyl) -s-triazine 2.5 wt% (T-1) Phthalocyanine green (CI 6) 10 wt% or more of the components are solidified in cyclohexanone. Component concentration is 20wt
% To prepare a color resist photosensitive solution.

Next, the above-mentioned resist photosensitive solution was applied to a 7059 glass substrate (manufactured by Corning) using a spin coater, and the resist film was dried on a hot plate at 80 ° C. for 1 minute. Α step of resist film thickness (manufactured by Tencor)
Was 2 μm. When the surface of the resist film was visually observed, there was no coating unevenness such as a pinhole, and a good coating film was obtained.

This was scanned and exposed with a semiconductor laser (830 nm, manufactured by Applied Techno). 5 for resist film
Irradiation was performed at 00 mj / cm ² . PEB was performed on a hot plate at 100 ° C. for 3 minutes. Development is performed using an aqueous solution of tetramethylammonium hydroxide (TMAH) at 25 ° C.
For 1 minute. By the above operation, a green resist pattern was formed on the glass substrate which was scanned and exposed by the laser. The pattern edge was good.

Example 3 m-cresol novolak resin (Mw = 3000) 70 wt% Cymel 300 15 wt% (methoxymethylmelamine manufactured by Mitsui Cyanamid Co.) Infrared absorbing dye CY-10 (Nippon Kayaku Co., Ltd .; S -1) 2.5 wt% 2,4,6-tris (trichloromethyl) -s-triazine 2.5 wt% (T-1) Phthalocyanine blue (CI 15; 3) 10 wt% or more components are cyclohexanone 20 wt% solids
% To prepare a color resist photosensitive solution.

Next, the above-described resist photosensitive solution was applied to a 7059 glass substrate (manufactured by Corning) using a spin coater, and the resist film was dried on a hot plate at 80 ° C. for 1 minute. Α step of resist film thickness (manufactured by Tencor)
Was 2 μm. When the surface of the resist film was visually observed, there was no coating unevenness such as a pinhole, and a good coating film was obtained.

This was scanned and exposed with a semiconductor laser (830 nm, manufactured by Applied Techno). 5 for resist film
Irradiation was performed at 00 mj / cm ² . PEB was performed on a hot plate at 100 ° C. for 3 minutes. Development is performed using an aqueous solution of tetramethylammonium hydroxide (TMAH) at 25 ° C.
For 1 minute. Through the above operation, a red resist pattern was formed on the glass substrate that was scanned and exposed by the laser. The pattern edge was good.

[0066]

The present invention provides a high-precision and low-cost color filter by using a specific resist composition for a color filter and a specific production method using the composition and a laser beam. In particular, the present invention provides a novel method for manufacturing a flexible color filter which can significantly reduce the manufacturing process because it is maskless and can cope with the production of a small number of products.

Claims (9)

[Claims] 1. A color comprising (a) a binder resin, (b) a crosslinking agent, (c) an infrared absorbing dye having absorption in a near infrared wavelength region, (d) a photoacid generator, and (e) a pigment. A resist composition for a filter. 2. The resist composition for a color filter according to claim 1, wherein the infrared absorbing dye is a cyanine dye. 3. The resist composition for a color filter according to claim 1, wherein the photoacid generator is an s-triazine compound having two or more trihalomethyl groups. 4. The resist composition for a color filter according to claim 1, wherein the crosslinking agent is a melamine derivative having an alkoxymethyl group. 5. The resist composition for a color filter according to claim 1, wherein the binder resin is a resin having a phenolic hydroxyl group. 6. The resist composition for a color filter according to claim 1, wherein the pigment is at least one selected from anthraquinone, phthalocyanine, isoindolinone, azo, and carbon black. 7. A colored image is formed by applying the resist composition for a color filter according to any one of claims 1 to 6 on a transparent substrate, and directly exposing and developing the photosensitive material with a laser beam. A method for producing a color filter, comprising: 8. The method according to claim 7, wherein the developing solution is an aqueous alkaline solution. 9. The method for producing a color filter according to claim 7, wherein the laser beam is a semiconductor laser.