JP2000039512A - Photosensitive resin composition for color filter and production of color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin compsn. for color filters which does not deteriorate the performance of the performance of the color filters and capable of decreasing the quantity of exposure and improving working efficiency at the time of pattern formation at the time of producing the color filters using a photolithography method and a process for producing the color filters using the same. SOLUTION: The photosensitive resin compsn. for production of the color filters having plural groups of filter pixels having different spectral characteristics on a substrate contains a high-polymer binder, coloring agents incorporated therein, a photoinitiator for forming active species to initiate photo-reaction by photoirradiation and a sensitizing agent which sensitizes this photoinitiator and is decolored by an external stimulus, such as light or heat.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition for a color filter and a method for producing a color filter using the same, and more particularly to an improvement in the sensitivity of a resist in which a colorant is dispersed in a resin. is there.

[0002]

2. Description of the Related Art As a conventional method for producing a color filter, for example, a dyeing method, an ink jet method, a printing method, a photoresist method and the like are known. The dyeing method is a technology of manufacturing a color filter by repeating a process of dyeing in an appropriate dyeing bath and a dye-proofing process for each of three colors of red, green and blue after forming a predetermined pattern. is there.

[0003] This method is disadvantageous in that the steps are complicated and the total number of steps is large. On the other hand, an efficient method of manufacturing a color filter with a smaller number of steps has been proposed. For example, using an ink jet device,
This applies to technologies such as an ink jet method in which ink is ejected and fixed on a transparent substrate serving as a substrate for coloring, and a printing method in which ink is transferred to a transparent substrate serving as a substrate using a printing machine. . In these systems, the alignment of the position is performed by an ink jet head or a printing press and a printing plate, so that a step of patterning the colored layer by light irradiation is not required. However, it is difficult to form high-definition pixels by these methods.

[0004] On the other hand, the photolithography method uses a coloring liquid containing a coloring agent and a polymer conjugate, coats it on a substrate, forms a film, and then patterns and develops the coloring layer by photolithography to obtain one color. Is formed. In this method, this step is repeated for each color, as in the dyeing method. However, since the dyeing step and the anti-dyeing treatment are not required, the number of steps is not only simpler than that of the dyeing method but also the spectral characteristics Control and reproducibility can be easily obtained. Furthermore, since photolithography is used, it is possible to produce higher-resolution color filters that have higher resolution and are difficult with printing and ink-jet methods. This is the mainstream method.

In the photolithography method, a coloring liquid in which a coloring agent is previously mixed in a resin is used. However, in order to function as a color filter in a thin film, it is necessary to considerably increase the concentration of the coloring agent. On the other hand, in the photolithography method, since a pattern is formed by light irradiation and development through a photomask, it is preferable that a substantially uniform photoreaction occurs in the thickness direction of the resist film. However, since a high-concentration colorant is used as described above, the light transmittance of each color other than the specific wavelength region is almost at 0%. In addition, if it does not have such spectral characteristics, it does not function as a good color filter. The specific wavelength in each color, that is, the region having a high transmittance is, for example, 600 to 700 nm for red,
500 to 600 nm for green and 400 to 5 for blue
It corresponds to 00 nm. In addition, when a high concentration of a colorant of any hue is used, it has considerable absorption in the ultraviolet region.

On the other hand, in order for a photoreaction to occur, an active species for inducing the photoreaction is required. What generates this active species by light is called a photoinitiator. This photoinitiator absorbs light to generate radical species, generates an acid, or undergoes physical or chemical change due to decomposition or isomerization, and has high solubility in an organic solvent or water. Things that change are known. Most of these photoinitiators generally have absorption from ultraviolet to near ultraviolet.

Therefore, in the photolithography method using these photoinitiators, the light intensity decreases due to the absorption of the coloring agent in the depth direction of the coating film, and the photoreaction rate deteriorates. If you don't have enough light for the photoreaction,
The formed pattern causes a defect during development. That is, in order to form a good pattern, the amount of exposure required to cause a photoreaction to the deepest part is large, and there is a problem that a long exposure time is required.

[Problems to be solved by the invention]

An object of the present invention is to provide a color filter using a photolithography method, which does not degrade the performance of the color filter, which is the original purpose, reduces the exposure amount at the time of pattern formation, and improves the working efficiency. Provided are a photosensitive resin composition for a filter and a method for producing a color filter using the same.

[0009]

In order to solve the above-mentioned problems, the present inventors have solved the above-mentioned problems in a specific wavelength region for colorants of each color, that is, 600 to 700 nm for red and 500 to 600 n for green.
m, and blue having a transmittance of about 400 to 500 nm, and nearly 100% at blue, and as a result of intensive studies, the present invention has been achieved.

That is, the present invention provides a photosensitive resin composition for producing a color filter having a plurality of groups of filter pixels having different spectral characteristics on a substrate; A colorant mixed therein, a photoinitiator that generates an active species that initiates a photoreaction by light irradiation, and a sensitizer that sensitizes the photoinitiator and decolorizes by external stimulus such as light or heat And a photosensitive resin composition for a color filter.

A second aspect of the present invention is based on the first aspect, wherein the absorption spectrum of the sensitizer exists in a wavelength region where the transmittance of the colorant is 50% or more. The present invention relates to the photosensitive resin composition for a color filter according to claim 1.

The invention described in claim 3 is the first or second invention.
3. A color filter according to claim 1, wherein the photoinitiator is a radical generator and contains a photopolymerizable monomer having at least one ethylenically unsaturated bond in the molecule. The present invention relates to a photosensitive resin composition for use.

The invention according to claim 4 is the first or second invention.
3. The method according to claim 1, wherein the photoinitiator is an acid generator or a base generator and contains a photopolymerizable monomer having at least one oxirane group or oxetane group in the molecule. The present invention relates to the photosensitive resin composition for a color filter described above.

According to a fifth aspect of the present invention, there is provided a color filter according to the first aspect, wherein the sensitizer is a cyanine or merocyanine dye. The present invention relates to a photosensitive resin composition for use.

According to a sixth aspect of the present invention, based on the first to fifth aspects, the polymer conjugate is soluble in an organic solvent or water. And a photosensitive resin composition for a color filter.

According to a seventh aspect of the present invention, there is provided a polymer conjugate, a colorant mixed therein, a photoinitiator for generating an active species for initiating a photoreaction by light irradiation, and the photoinitiator. After applying a photosensitive resin composition containing a sensitizer that sensitizes the composition and decolorizes by an external stimulus such as light or heat onto a substrate, forms a film, and then exposes and develops the resultant by photolithography. A process of forming a single-color pattern is repeated for three colors of red, green, and blue, and a color filter is manufactured by decolorizing, thereby manufacturing a color filter.

[0017]

In the method for producing a color filter using the photosensitive resin composition for a color filter of the present invention, a sensitizer having absorption in a wavelength region where transmittance is high in a colorant of each color is used. A uniform and efficient photoreaction can be caused in the thickness direction. Further, the present sensitizer can be decolorized by an external stimulus such as light or heat after pattern formation.

That is, the present photosensitive resin composition for a color filter can achieve a reduction in the manufacturing time and a corresponding improvement in work efficiency and yield without changing the original hue of the color filter.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The polymer conjugate used in the present invention includes:
Light irradiation part or light shielding part is organic solvent, alkaline aqueous solution,
It is not particularly limited as long as it can be dissolved in water or a commercially available developer. However, considering that the working environment and environmental problems at the global level are being taken up, those having a composition capable of developing with water or alkali are more desirable. Such a resin generally includes a hydrophilic monomer represented by (meth) acrylic acid, a monomer having 2-hydroxyethyl, acrylamide, N-vinylpyrrolidone and an ammonium salt, and a (meth) acrylic acid ester, acetic acid Vinyl, styrene,
A polymer conjugate is known in which a lipophilic monomer such as N-vinylcarbazole is copolymerized at a proper mixing ratio by a known method. Specific examples are described in JP-A-57-16408 and JP-A-2009-2009.
JP, JP-A-2-181704, JP-A-2-1-1
Examples thereof include, but are not limited to, those disclosed in Japanese Patent Application No. 99403 and the like. These polymer conjugates are a negative type, that is, a combination of a radical polymerizable monomer having an ethylenically unsaturated group or a cationic polymerizable monomer having an oxirane group, a radical generator, an acid generator or a base generator. The light-shielding portion can be used as a type of resist that is removed by development. Further, a polymer conjugate represented by t-butyl carbonate, t-butyl ester, tetrahydroxypyranyl ester or tetrahydroxypyranyl ether of polyhydroxystyrene can also be used. This kind of polymer conjugate is
It can be used as a positive type resist, that is, a type in which a light-irradiated portion is removed by development by combination with an acid generator.

As the colorant used in the present invention, a dye or a pigment or a mixture thereof can be used so as to obtain a desired hue. These may be dispersed and kneaded in the polymer binder, or may be used by dispersing or dissolving with a suitable solvent.

Specific examples of the dye include Acid Red 52,
87, 92, 122, 486, Solvent Red 8, 83,
109, 125, 132, Disperse Red 60, 72,
88, 206, Basic Red 12, 27, Acid Blue 9,
40, 83, 129, 249, Solvent Blue 25, 3
5, 36, 55, 67, 70, Disperse Blue 56, 8
1, 60, 87, 149, 197, 211, 214, Ba
sic Blue 1, 7, 26, 77, Acid Green 18, Solv
ent Green3, Basic Green1, Acid Yellow38, 9
9, Solvent Yellow 25, 88, 89, 146, Dispe
rse Yellow, 42, 60, 87, 198, Basic Yell
ow21 and the like, but are not limited thereto.

Examples of pigments include Pigment R
ed9, 19, 38, 43, 97, 122, 123, 14
4, 149, 166, 168, 177, 179, 18
0, 192, 215, 216, 208, 216, 21
7, 220, 223, 224, 226, 227, 22
8, 240, Pigment Blue 15, 15: 6, 16, 2
2, 29, 60, 64, Pigment Green 7, 36, Pigm
ent Yellow 20, 24, 86, 81, 83, 93, 1
08, 109, 110, 117, 125, 137, 13
8, 139, 147, 148, 153, 154, 16
6, 168, 185, Pigment Orange 36, Pigment
Violet 23 and the like can be mentioned, but not limited to these. Further, these dyes and pigments may be used as a mixture of two or more in order to obtain a desired hue.

The photoinitiator used in the present invention to generate an active species that initiates a photoreaction by light irradiation includes:
Examples of the initiator include a radical initiator, an acid generator, and quinonediazide that absorb light and change its physical properties, but are not limited thereto.

Specific examples of the radical initiator include Mac
romolecules, 10 , 1307 (197
7). And diphenyliodonium, ditolyliodonium, phenyl (p-anisyl)
Iodonium, bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium,
Chloride, bromide or borofluoride of iodonium such as bis (p-chlorophenyl) iodonium,
In addition to iodonium salts such as hexafluorophosphate salts and hexafluoroarsenate salts, triarylsulfonium salts, triarylphosphonium salts, and iron arene complexes, tert-butyl peroxy-iso-
Butarate, 2,5-dimethyl-2,5-bis (benzoyldioxy) hexane, 1,4-bis [α- (tert-butyldioxy) -iso-propoxy] benzene, di-te
rt-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butyldioxy) hexene hydroperoxide, α- (iso-propylphenyl) -iso-propyl hydroperoxide, 2,5-bis (hydroperoxy)- 2,5-dimethylhexane, tert-butyl hydroperoxide, 1,1-bis (tert-butyldioxy) -3,3,5-trimethylcyclohexane, butyl-4,
4-bis (t-butyldioxy) valerate, cyclohexanone peroxide, 2,2 ′, 5,5′-tetra (tert
-Butylperoxycarbonyl) benzophenone, 3,
3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (ter
(t-amylperoxycarbonyl) benzophenone, 3,
3 ′, 4,4′-tetra (tert-hexylperoxycarbonyl) benzophenone, 3,3′-bis (tert-butylperoxycarbonyl) -4,4′-dicarboxybenzophenone, tert-butylperoxybenzoate,
Organic peroxides such as di-tert-butyldiperoxyisophthalate, 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, and 1,2-benzanthraquinone And benzoin derivatives such as benzoin methyl, benzoin ethyl ether, α-methyl benzoin and α-phenyl benzoin.

Specific examples of the acid generator include, among the above-mentioned radical generators, diaryl iodonium salts, triaryl sulfonium salts, triaryl phosphonium salts, iron arene complexes, and the like. However, the present invention is not limited to these.

Specific examples of diaryliodonium salts include diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium mesylate, and diphenyliodonium mesylate. -Donium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis (p -
Tert-butylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium mesylate, bis (p-tert-butylphenyl) iodide Nickel tosylate, bis (p
-Tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium tetrafluoroborate, bis (p-tert-butylphenyl) iodo Donium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate and the like can be mentioned.

Examples of triarylsulfonium salts include triphenylsulfonium chloride, triphenylsulfonium bromide, tri (4-methoxyphenyl)
Sulfonium tetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphone-
And tri (4-ethoxyphenyl) sulfonium tetrafluoroborate.

Examples of triarylphosphonium salts include triphenylphosphonium chloride, triphenylphosphonium bromide, tri (4-methoxyphenyl) phosphonium tetrafluoroborate, and tri (p-
Methoxyphenyl) phosphonium hexafluorophosphonate, tri (4-ethoxyphenyl) phosphonium tetrafluoroborate and the like. Of these, diaryliodonium salts are particularly preferred. Specific examples of the photogroup generator include bis ((2-nitrobenzyl) oxy) carbonylhexane-1,6-diamine, nitrobenzylcyclohexylcarbamate, di (methoxybenzyl) hexamethylenedicarbamate, and the following chemicals. Compounds of structural formulas are mentioned.

[0030]

Embedded image (Wherein R is a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted phenyl group. )

[0031]

Embedded image (Wherein R is a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted phenyl group. )

[0032]

Embedded image (Wherein R is a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted phenyl group. )

[0033]

Embedded image

As the sensitizer that sensitizes the photoinitiator and decolorizes by external stimulus such as light or heat, any sensitizer that can be used for such a purpose can be used. Yes, "Dye Handbook (Nobu Okawara,
Teijiro Kitao, Tsuneaki Hirashima, Ken Matsuoka, Ed., Kodansha) "
The dye compounds having a large number of amino groups described in (1) can be used in the present invention. Particularly preferred are cyanine dyes and merocyanine dyes.

Specific examples of the cyanine dye or the merocyanine dye include 2-[[3-allyl-5- [2- (5,6-dimethyl-3-propyl-2 (3H) -benzothiazolylidene) ethylidene] -4-oxo-2 -Thiazolidinylidene] methyl] -3-ethyl-4,5-diphenylthiazolium iodide, 3-ethyl-2-[[3-ethyl-5- [2- (1-ethyl-4 (1H)
-Quinolinylidene) ethylidene] -4-oxo-2-thiazolidinylidene] methyl] benzoxazolium bromide, 3-ethyl-2-[[3-ethyl-5- [2- (1-ethyl-2 (1H) -quinolinylidene) ethylidene] -4-oxo2 -Thiazolidinylidene] methyl]
Benzothiazolium iodide, 2-[[3-allyl-5- [2- (1-ethyl-4 (1H) -quinolinylidene) ethylidene] -4-oxo-2-thiazolidinylidene] methyl] -3-ethyl-4,5-diphenylthiazo Lium bromide and the like can be mentioned.

Further, 3-ethyl-2-[(3-ethyl-
2-benzothiazolinylidene) methyl] benzothiazolium, 1,3,3-trimethyl-2-[(1,3,3-
Trimethyl-2-indolinylidene) methyl] -3H-
Indolium, 3-ethyl-2-[(1-ethyl-2
(1H) -quinolylidene) methyl] benzothiazolium, 3-ethyl-2-[(1-ethyl-2 (1H) -quinolylidene) methyl] benzoselazolium, 1-ethyl-2-[(1-ethyl -2 (1H) -quinolyliden)
Methyl] quinolinium, 1-ethyl-2-[(1-ethyl-4 (1H) -quinolylidene) methyl] quinolinium, 1-ethyl-4-[(1-ethyl-4 (1H) -quinolylidene) methyl] quinolinium, 3-ethyl-2-
[3- (3-ethyl-2-thiazolidinylidene) -1-
Propenyl] thiazolinium, 3-ethyl-2- [3-
(3-ethyl-2-benzoxazolinylidene) -1-propenyl] benzoxazolium and

3-ethyl-2- {2-[(3- (3-ethyl-5-phenyl-2-benzoxazolinylidene) methyl] -1-butenyl} -5-phenylbenzoxazolium, , 6-Dichloro-1,3-diethyl-2-
[3- (5,6-Dichloro-1,3-diethylbenzimidazolinylidene) -1-propenyl] benzimidazolium, 1,3,3-trimethyl-2- [3- (1,
3,3-trimethyl-2-indolinylidene) -1-propenyl] -3H-indolium, 3-ethyl-2 ｛2
-[(3-ethyl-2-benzothiazolinylidene) methyl] -1-butenyl {benzothiazolium, 3-ethyl-2- [3- (3-ethyl-2-benzothiazolinylidene)- 2-methyl-1-propenyl] benzothiazolium, 2- {2-methyl-3- [3- (3-sulfopropyl) -2-benzoselenazolinylidene] -1-propenyl} -3- (3 -Sulfopropyl) benzoselenazolium

3-ethyl-4-methyl-2- [3- (3
-Ethyl-4-methyl-2-thiazolinylidene) -1-
Propenylthiazolium iodide, 3-ethyl-2
-[3- (3-ethyl-2-benzothiazolinylidene)
-1-propenyl] benzothiazolium, 3- (3-sulfopropyl) -2- {3- [3- (3-sulfopropyl) -2-benzothiazolinylidene] -1-propenyl} benzothiazo Lium, 3-ethyl-2- [3- (3
-Ethyl-2-benzoselenazolinylidene) -1-propenyl] benzoselenazolium, 2- {2-methyl-3
-[3- (3-sulfopropyl) -2-naphtho [1,2
-D] thiazolinylidene] -1-propenyl} -3-
(3-sulfopropyl) naphtho [1,2-d] thiazolium, 3-ethyl-2- [3- (3-ethyl-2-naphtho [2,1-d] thiazolinylidene) -2-methyl-1
-Propenyl] naphtho [2,1-d] thiazolium and

3-ethyl-2- {2-[(3-ethyl-
2-naphtho [2,1-d] thiazolinylidene) methyl]
-1-butenyl @ naphtho [2,1-d] thiazolium,
3-ethyl-2- {2-[(3-ethyl-2-naphtho [1,2-d] thiazolinylidene) methyl] -1-butenyl} naphtho [1,2-d] thiazolium, 1,1,3
-Trimethyl-2- [3- (1,1,3-trimethylbenzindoline-2-ylidene) -1-propenyl]-
1H-benzindolium, 3-ethyl-2- [3-
(3-ethyl-2-naphtho [2,1-d] thiazolinylidene) -1-propenyl] naphtho [2,1-d] thiazolium, 3-ethyl-2- [3- (1-ethyl-4 (1
H) -Quinolylidene) -1-propenyl] benzoxazolium, 3-ethyl-2- [3- (3-ethyl-2-naphtho [1,2-d] thiazolinylidene) -1-propenyl] naphtho [1, 2-d] thiazolium, 1-ethyl-
2- [3- (1-ethyl-2 (1H) -quinolylidene)
-1-propenyl] quinolinium and

3-ethyl-2- [3- (1-ethyl-4
(1H) -quinolylidene) -1-propenyl] benzothiazolium, 1-ethyl-2- [3- (1-ethyl-4)
(1H) -quinolylidene) -1-propenyl] quinolinium, 1-ethyl-4- [3- (1-ethyl-4 (1
H) -quinolinylidene) -1-propenyl] quinolinium, 3-ethyl-2- [5- (3-ethyl-2-benzoxazolinylidene) -1,3-pentadienyl] benzoxazolium, 1,3, 3-trimethyl-2- [5
-(1,3,3-trimethyl-2-indolinylidene)
-1,3-pentadienyl] -3H-indolium, 3
-Ethyl-2- [5- (3-ethyl-2-benzothiazolinylidene) -1,3-pentadienyl] benzothiazolium, 3-ethyl-2-{[3- (3-ethyl-2-
Benzothiazolinylidene) methyl] -5,5-dimethyl-2-cyclohexene-1-ylidene] methyl {benzothiazolium, 3-ethyl-2- [5- (3-ethyl-2)
-Benzoselenazolinylidene) -1,3-pentadienyl] benzoselenazolium, 1,1,3-trimethyl-
2- [5- (1,1,3-trimethylbenzindoline-2-ylidene) -1,3-pentadienyl] -1H-
Benzindolium, 3-ethyl-2- [5- (3-ethyl-2-naphtho [2,1-d] thiazolinylidene)-
1,3-pentadienyl] naphtho [2,1-d] thiazolium, 3-ethyl-2- [5- (3-ethyl-2-naphtho [1,2-d] thiazolinylidene) -1,3-pentadienyl] naphtho [1,2-d] thiazolium and

1-ethyl-2- [3-chloro-5- (1
-Ethyl-2 (1H) -quinolilidene) -1,3-pentadienyl] quinolinium, 1-ethyl-2- [5-
(1-ethyl-2 (1H) -quinolylidene) -1,3-
Pentadienyl] quinolinium, 1-ethyl-4- [3
-Chloro-5- (1-ethyl-4 (1H) -quinolylidene) -1,3-pentadienyl] quinolinium, 1-ethyl-4- [5- (1-ethyl-4 (1H) -quinolylidene) -1, 3-pentadienyl] quinolinium, 3-
Ethyl-2- [7- (3-ethyl-2-benzoxazolinylidene) -1,3,5-heptatrienyl] benzoxazolium, 1,3,3-trimethyl-2- [7-
(1,3,3-trimethyl-2-indolinylidene)-
1,3,5-heptatrienyl] -3H-indolium, 3,3-dimethyl-2- [7- (3,3-dimethyl-1- (3-sulfopropyl) -2-indolinylidene] -1, 3,5-heptatrienyl] -1- (3-sulfopropyl) -3H-indolium, 3-ethyl-2
-[7- (3-ethyl-2-benzazolinylidene)-
1,3,5-heptatrienyl] benzothiazolium and

3-ethyl-2- [7- (3-ethyl-2
-Benzothiazolinylidene) -1,3,5-heptatrienyl] benzothiazolium, 3-ethyl-2- [7-
(3-ethyl-2-benzoselenazolinylidene) -1,
3,5-heptatrienyl] benzoselenazolium,
1,1,3-trimethyl-2- [7- (1,1,3-trimethylzensindoline-2-ylidene) -1,3,3
5-heptatrienyl] -1H-zensindolinium,
3-ethyl-2- [7- (3-ethyl-2-naphtho [1,2-d] thiazolinylidene) -1,3,5-heptatrienyl] naphtho [1,2-d] thiazolium,
-Ethyl-2- [7- (1-ethyl-2 (1H) -quinolylidene) -1,3,5-heptatrienyl] quinolinium, 1-ethyl-4- [7- (1-ethyl-4 (1
H) -Quinolylidene) -1,3,5-heptatrienyl] quinolinium, 2-{[3-allyl-5- [2-
(5,6- {methyl-3-n-propyl-2-benzothiazolinylidene) ethylidene] -4-exo-2-thiazolidibilidene] methyl} -3-ethyl-4,5-diphenylthiazolium, 3-ethyl-2-{[3-ethyl-
5- [2- (1-ethyl-4 (1H) -quinolylidene)
Ethylidene] -4-exo-2-thiazolidinylidene]
Methyl {benzoxazolium, 3-ethyl-2-} [3
Iodides and bromides such as -ethyl-5- [2- (1-ethyl-4 (1H) -quinolylidene) ethylidene] -4-exo-2-thiazolidinylidene] methyl} -4,5-diphenylthiazolium , Chloride, hexafluoroantimonate, hexafluorophosphate, tetrafluoroborate, hexafluoroarsenate,
Examples thereof include p-toluenesulfonate, trifluoromethanesulfonate, methanesulfonate, and perchlorate salt.

Further, many cyanine dyes or merocyanine dyes including those described above can be obtained from Japan Photographic Dye Laboratories Co., Ltd. under the following names. N
K-4, NK-5, NK-6, NK-33, NK-55,
NK56, NK-76, NK-85, NK-125, N
K-126, NK-138, NK-322, NK-38
2, NK-616, NK-716, NK-719, NK-7
23, NK-734, NK-741, NK-747, NK
-863, NK-1046, NK-1056, NK-1
210, NK-1252, NK-1414, NK-14
20, NK-1531, NK-1533, NK-153
8, NK-1666, NK-1836, NK-195
2, NK-1954, NK-1958, NK-195
7, NK-1967, NK-2037, NK-204
0, NK-2041, NK-2043, NK-204
9, NK-2090, NK-2150, NK-220
3, NK-2273, NK-2279, NK-228
2, NK-2301, NK-2351, NK-241
3, NK-2558, NK-2565, NK-260
6, NK-2610, NK-2686, NK-277
2, NK-2754, NK-2825, NK-284
1, NK-2844, NK-2850, NK-2882
And

NK-2883, NK-2885, NK-
2886, NK-2888, NK-2890, NK-2
901, NK-2906, NK-2908, NK-29
36, NK-2957, NK-2958, NK-297
2, NK-2977, NK-2977, NK-297
8, NK-2997, NK-3004, NK-300
5, NK-3006, NK-3007, NK-302
0, NK-3036, NK-3078, NK-308
0, NK-3099, NK-3100, NK-310
6, NK-3114, NK-3125, NK-314
6, NK-3150, NK-3151, NK-315
8, NK-3159, NK-3167, NK-318
3, NK-3186, NK-3187, NK-319
4, NK-3203, NK-3205, NK-321
1, NK-3239, NK-3243, NK-325
7, NK-3261, NK-3274, NK-3285
And

NK-3289, NK-3291, NK-
3292, NK-3293, NK-3294, NK-3
306, NK-3335, NK-3341, NK-33
53, NK-3356, NK-3358, NK-336
3, NK-3368, NK-3370, NK-337
3, NK-3410, NK-3422, NK-343
0, NK-3444, NK-3451, NK-345
2, NK-3486, NK-3525, NK-361
8, NK-3620, NK-3624, NK-362
8, NK-3644, NK-367, NK-373
7, NK-3736, NK-3744, NK-374
5, NK-3813, NK-3868, NK-387
8, NK-3879, NK-3944, NK-394
9, NK-3962, NK-3966, NK-398
8, NK-3988, NK-4006, NK-411
2, NK-4116, NK-4141, NK-416
3, NK-4164, NK-4173, NK-417
6, NK-4278, NK-4281, NK-428
5, MK-4286, NK-4288, NK-430
8, NK-4351, NK-4352, NK-437
1, NK-4374, NK-4378, NK-438
4, NK-4385, NK-4405, NK-440
8, NK-4413, NK-4424, NK-443
7, NK-4448, NK-4463, NK-447
5, NK-4485 and the like.

If necessary, two or more sensitizers may be used in combination. In addition, sensitizers that further improve sensitivity by using an amino compound such as N-phenylglycine or a borate compound as an auxiliary agent of the sensitizer have been reported.However, if necessary, these auxiliary agents may be used. It may be added.

Further, specific examples of the photopolymerizable monomer having one or more ethylenically unsaturated bonds in a molecule to be added when a radical generator is used as a photoinitiator in the present invention include an ethylenically unsaturated bond in a structural unit. And a polyfunctional vinyl monomer in addition to a monofunctional vinyl monomer, or a mixture thereof. Specifically, high-boiling vinyl monomers such as (meth) acrylic acid, itaconic acid, maleic acid, (meth) acrylamide, diacetone acrylamide, and 2-hydroxyethyl (meth) acrylate;
Further, aliphatic polyhydroxy compounds, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, neopentyl glycol, 1,3- Di or poly such as propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol and mannitol Alicyclic monomers such as (meth) acrylates, dimethylol tricyclodecane monoacrylate and dimethylol tricyclodecane diacrylate, and aromatic polyhydroxy Compounds, such as hydroquinone, resorcinol, catechol, pyrogallol, bisphenol A
Di- or poly (meth) acrylates, ethylene oxide-modified (meth) acrylates of isocyanuric acid, etc., as well as 2-phenoxyethyl acrylate;
Examples include, but are not limited to, 2-phenoxyethyl methacrylate, phenol ethoxylate monoacrylate, p-chlorophenyl acrylate, KAYARAD-R551 (manufactured by Nippon Kayaku Co., Ltd.). Among them, those which are liquid at normal temperature and normal pressure and have a boiling point of 100 ° C. or higher at normal pressure are more preferable. These may be used as a mixture of two or more as necessary.

Further, specific examples of the photopolymerizable monomer having at least one oxirane group or oxetane group in the molecule to be added when an acid generator is used as a photoinitiator in the present invention include Adeka.RTM. Resin EP-4900,
EP4080, EP-4000ED-505, ED-5
06, Epicron S-129, 43 manufactured by Dainippon Ink and Chemicals, Inc.
0, 430-L, 725, 720, 705, 707, 1
600, Etoto YDF-170, 17 manufactured by Toto Kasei
5, 2001, 2004, YH-434, YH-434
L, ST-3000, YD-716, YD-300, P
G-202, PG-207, YD-171, YD17
2. Araldite PY-306, MY-720, XN1034, DY02 manufactured by Ciba Specialty Chemicals
2, CY184, CY192, CY179, CY17
7, CY175, PT810, Yuko Shell Epoxy Epicoat 807, 1031, YX-4000, 604,
YDE205, 191P, 190P, 871, 872,
RXE15, Sumitomo Chemical Sumiepoxy ELM-434,
ELM-434HV, ELM-120, EP made by Mitsui Chemicals
OMIKR 710, R540, R508, R531, Nippon Kayaku GAN, GOT, AK-601, Toagosei Chemicals 3-ethyl-3-hydroxymethyloxetane, 1,
4-bis ((3-ethyl-3-oxetanylmethoxy)
Methyl) benzene and the like, but are not limited thereto.

In the production of a color filter using the photosensitive resin composition of the present invention, the photosensitive resin composition is coated on a substrate and then formed by a photolithography method. For the substrate, any substrate can be used as long as it is transparent and does not suffer from the strength and the coloring liquid to a certain extent. Specifically,
Examples thereof include a glass plate, a polycarbonate plate, a polymethyl methacrylate plate, and a polyester film, but are not limited thereto. Further, when applying the coloring liquid to the substrate, it can be performed using a spin coater, a roll coater, a bar coater, or the like.

When the coloring liquid is applied, it may be diluted with an appropriate solvent if necessary, but in that case, it is necessary to apply the solvent on the substrate and then dry it. Solvents that can be used when preparing the coloring liquid, the substrate to be dissolved is dissolved, swelling,
Any organic solvent that is not affected by cloudiness and erosion can be used, and most of commonly used organic solvents can be used. Specifically, water, methanol, ethanol, propanol, isopropyl alcohol, n-
Butanol, t-butanol, 2-methylpropyl alcohol, chloroform, dichloromethane, carbon tetrachloride,
1,4-dioxane, tetrahydrofuran, acetone,
Ethyl methyl ketone, ethyl acetate, acetonitrile, toluene, xylene, cyclohexane, cyclohexanone, n-pentane, n-heptane, n-hexane, 2-
Methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethoxyethyl acetate, 2
-Butoxyethyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl ether, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethyl acetate, 2- Examples thereof include (2-butoxyethoxy) ethyl acetate, 2-phenoxyethanol, and diethylene glycol dimethyl ether, but are not limited thereto, and any solvent that satisfies the above requirements can be used. Further, two or more solvents may be mixed and used as necessary.

[0051]

The present invention will be described in more detail with reference to the following examples, but it should not be construed that the invention is limited thereto.

2-hydroxyethyl methacrylate 2
0 parts by weight, 50 parts by weight of methyl methacrylate, and 15 parts by weight of methacrylic acid were dissolved in 300 parts by weight of cyclohexanone, and 0.5 part by weight of azoisobutyronitrile was added. The mixture was reacted at 60 ° C. for 10 hours under a nitrogen atmosphere. The solution of the polymer conjugate was purified by precipitation in n-hexane and dried under reduced pressure.
An original copolymer was obtained. Dissolve 20 parts by weight of this polymer conjugate in 100 parts by weight of cyclohexanone.
68, 15 parts by weight, Pigment Orange 36, 5 parts by weight,
One part by weight of the dispersant was added and kneaded sufficiently with three rolls. Thereafter, 1 part by weight of diphenyliodonium hexafluorophosphate and 0.2 part by weight of a sensitizer NK-4163 were added, and the mixture was stirred well to prepare a colored liquid for red.

20 parts by weight of the above-mentioned polymer conjugate was dissolved in 100 parts by weight of cyclohexanone.
, 15 parts by weight of Pigment Yellow 154, and 1 part by weight of a dispersant, and kneaded sufficiently with a three-roll mill.
Thereafter, 1 part by weight of diphenyliodonium hexafluorophosphate and 0.2 part by weight of a sensitizer NK-3744 were added, and the mixture was stirred well to prepare a green colored liquid.

20 parts by weight of the above-mentioned polymer conjugate was dissolved in 100 parts by weight of cyclohexanone.
, 18 parts by weight of Pigment Violet 23 and 1 part by weight of a dispersant, and kneaded sufficiently with three rolls. Thereafter, 1 part by weight of diphenyliodonium hexafluorophosphate and 0.2 part by weight of a sensitizer NK-1237 were added, and the mixture was stirred well to prepare a colored liquid for blue.

A blue colored liquid was spin-coated (1000 rpm, 60 seconds) on a glass substrate and dried at 80 ° C. for 20 minutes. Using a mask having a pixel size of 30 μm × 100 μm, exposure was performed using a 500 W xenon lamp (30 mJ).
/ Cm ² ). Development was carried out with a 0.1N aqueous sodium hydrogen carbonate solution. Next, baking was performed at 180 ° C. for 1 hour to fix the pattern. After performing the same process using the coloring liquids for green and red, light irradiation of 500 mJ / cm ² was performed with a high-pressure mercury lamp, and the sensitizer was decolorized to produce a color filter. The exposure dose when using a green colorant is 40 mJ /
cm ² . The exposure amount when the red coloring liquid was used was 25 mJ / cm ² .

Comparative Example A color filter was prepared without adding a sensitizer. The sensitivity of the coloring liquid of each color was as follows. Blue 400 mJ / cm ² ; Green; 70
0 mJ / cm ² . Red; 300 mJ / cm ² .

[0057]

The photosensitive resin composition for a color filter and the method for producing a color filter according to the present invention have the above-mentioned effects, and therefore, when producing a color filter using a photolithography method, the color which is the original purpose is obtained. A photosensitive resin composition for a color filter, which can reduce the amount of exposure during pattern formation and improve the working efficiency without deteriorating the performance of the filter, and a method for producing a color filter using the same.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/32 C09D 5/32 F term (Reference) 2H025 AA01 AB13 AC01 AD01 AD03 BC31 BD42 BE01 BE07 BF15 CA01 CA42 CC11 FA03 FA17 2H048 BA45 BA48 BB02 BB41 2H096 AA28 BA05 BA11 CA12 DA01 EA02 EA11 GA08 HA01 4J002 BC041 BF021 BG011 BG031 BG071 BG131 BJ001 EB118 EE038 EE058 EK008 EL026 EL036 EG008 EL0800 018008 ER008

Claims (7)

[Claims] 1. A photosensitive resin composition for producing a color filter having a plurality of groups of filter pixels having different spectral characteristics on a substrate, comprising: a polymer conjugate; a coloring agent mixed therein; It is characterized by containing a photoinitiator that generates an active species that initiates a photoreaction by light irradiation, and a sensitizer that sensitizes the photoinitiator and decolorizes by an external stimulus such as light or heat. Photosensitive resin composition for color filters. 2. The photosensitive resin composition for a color filter according to claim 1, wherein the absorption spectrum of the sensitizer exists in a wavelength region where the transmittance of the colorant is 50% or more. 3. The photo-initiator is a radical generator and contains a photo-polymerizable monomer having at least one ethylenically unsaturated bond in the molecule.
The photosensitive resin composition for a color filter according to the above. 4. The photoinitiator is an acid generator or a base generator, and has an oxirane group or an oxetane group in a molecule.
The photosensitive resin composition for a color filter according to claim 1, further comprising a photopolymerizable monomer having at least one photopolymerizable monomer. 5. The photosensitive resin composition for a color filter according to claim 1, wherein the sensitizer is a cyanine or merocyanine dye. 6. The photosensitive resin composition for a color filter according to claim 1, wherein the polymer conjugate is soluble in an organic solvent or water. 7. A polymer conjugate, a coloring agent mixed therein, a photoinitiator for generating an active species for initiating a photoreaction by light irradiation, a photoinitiator for sensitizing the photoinitiator, and A photosensitive resin composition containing a sensitizer that decolorizes due to an external stimulus such as heat is applied to a substrate, and after forming a film, a single color pattern is formed by exposing and developing by photolithography. A process for producing a color filter, wherein the process is repeated for three colors of red, green and blue, and the sensitizer is decolorized to produce a color filter.