JP3004044B2 - Photosensitive colored resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a photosensitive colored resin composition for forming a colored image, and is particularly suitable for use in producing a color filter.

<Related Art> Generally, a color filter used for a solid-state imaging device, a liquid crystal display device, or the like is one in which, for example, mosaic, stripe, or triangle color elements are arranged on the surface of a transparent substrate.

At present, these color filters are mainly manufactured by a dyeing method.

The dyeing method is to impart photosensitivity to soluble water-soluble polymers such as gelatin, fish glue, casein, and polyacrylamide by adding a dichromate or a water-soluble azide compound, and then exposing through a photomask. Then, after developing with water to obtain a relief pattern, the relief pattern is dyed to form a colored image. By repeating such a process three times,
The red, green, and blue filters are formed. Between each color process, for example, anti-staining treatment with tannic acid is performed, or an intermediate layer of urethane resin or acrylic resin is provided. Prevents color mixing.

By the way, such conventional dyeing methods involve complicated processes, difficult control of the dyeing bath, poor heat resistance of the dyeing medium (water-soluble polymer), poor heat resistance and poor weather resistance of the dye, and the like. There are drawbacks.

Therefore, in order to overcome the above-mentioned drawbacks, recently, a color filter has been actively developed by, for example, a printing method or a pigment dispersion method.

This printing method is a method in which a colored image is formed by sequentially printing on a transparent substrate using an ink in which a pigment is dispersed in an organic vehicle. This method is selected for its simple process, cost, and durability, in addition to the fact that film formation and patterning can be performed at the same time. However, it has new problems such as fringes having poor dimensional accuracy and poor surface smoothness.

On the other hand, the pigment dispersion method is a method in which the above-mentioned problems are improved. In this method, a pigment is dispersed in a photosensitive resin,
A colored image is formed by coating, drying, exposing and developing on a transparent substrate, and has the advantage that a simple process color filter can be manufactured as compared with the dyeing method. As the photosensitive resin used in the pigment dispersion method, for example, a stilbazolium-based pendant polyvinyl alcohol disclosed in JP-A-60-124736, JP-A-60-237403 and JP-A-62-212603 are disclosed. Photosensitive polyimide and polyamide disclosed in, such as a photosensitive resin comprising an acrylic polymer and a bisdiazide compound disclosed in JP-A-1-200353,
Various radically polymerizable photosensitive resins comprising a polyfunctional acrylate monomer, an organic polymer binder and a photopolymerization initiator disclosed in JP-A-1-152449 and the like have been proposed.

<Problems to be solved by the invention> However, in the photosensitive resin according to the pigment dispersion method,
Stilbazolium-based pendant polyvinyl alcohol has a drawback of low heat resistance. To improve this, a stilbazolium-based pendant polyvinyl alcohol having a betaine structure disclosed in JP-A-2-160807 has been proposed, but the heat resistance is also insufficient.

Further, those using photosensitive polyimide or polyamide have high heat resistance, but have problems such as development with an organic solvent having low sensitivity in which the resin is colored. On the other hand, systems using bisazide compounds as photosensitizers
There is a problem that the exposure is affected by oxygen at the time of low sensitivity exposure. A system using radical polymerization has high sensitivity, but has a problem that it is affected by oxygen during exposure. To avoid this, it is necessary to perform exposure in an inert gas atmosphere or to provide an oxygen barrier film,
For this reason, there are problems such as an increase in the cost of the apparatus or a complicated process.

The present invention is highly sensitive in view of the circumstances described above,
Excellent heat resistance without changing even under the influence of oxygen,
Another object of the present invention is to provide a photosensitive colored resin composition having various properties such as that the development is aqueous.

<Means for Solving the Problems> A photosensitive resin composition according to the present invention for achieving the above object is a photosensitive colored resin composition for forming a colored pattern, and is cured by (a) acid (B) a photoacid generator, and (c) a pigment. Characterized in that it is contained at a ratio of

 Hereinafter, the contents of the present invention will be described in detail.

In the present invention, the resin-based material (a) curable by an acid is, for example, a crosslinking agent having an N-methylol structure such as an amino resin such as urea resin or melamine resin and a phenolic hydroxyl group or a carboxyl group. Resin-based material with group-containing resin, resin-based material with epoxy resin and phenolic resin, or J.Photopolym.Sci.Technol.V
ol3 No.3 (1990) p235-247
-Hydroxystyrene and a copolymer of p-acetoxymethylstyreene containing a hydroxystyrene structure, etc., which have the property of being cured by an acid.

In the above resin-based material, examples of the crosslinking agent having an N-methylol structure include methylolated urea, urea resin, methylolated melamine, methylolated guanamine,
Methylolated glyoxal diurein, methylolated uron, methylolated tetrahydropyrimidone derivative,
Methylolated triazones or their alkyl ethers can be mentioned. Among them, it is preferable to use an alkyl ether because of high storage stability.
The alkyl group of this alkyl ether has 1 carbon atom.
Particularly preferred are alkyl groups of 5 to 5.

In the resin-based material, as the resin having a phenolic hydroxyl group, for example, an alkali-soluble phenol resin, a novolak resin, a polymer having a hydroxystyrene structure, a polymer having a structure represented by the following general formula (I), Examples thereof include alkali-soluble polyimides having a phenolic hydroxyl group.

(Wherein, R ₁ represents hydrogen, an alkino group or an aryl group, R ₂ represents a hydrogen, a halogen, an alkyl group or an alkoxy group, and n represents an integer of 0 to 6). And a ketone in the presence of an acid catalyst. Phenols used at this time include, for example, phenol,
Cresol, ethylphenol, butylphenol, xylenol, phenylphenol, hydroquinone, catechol, resorcinol, pyrogallol, naphthol,
Bisphenol A and the like can be mentioned. These phenols are used alone or in combination of two or more. Examples of the ketones include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, acetone, and methyl ethyl ketone.

In the above resin-based material, the polymer having a hydroxystyrene structure can be obtained, for example, by copolymerizing hydroxystyrene or α-methyl-hydroxystyrene alone, two or more kinds, or styrene or an acrylic monomer. Examples of the acrylic monomer as the copolymerization component include acrylic ester, methacrylic ester, acrylamide, methacrylamide, and acrylonitrile.

Examples of the polymer containing the maleimide derivative structure represented by the above general formula (I) include, for example, JP-A-61-162039.
And Japanese Patent Application Laid-Open Nos. Sho 62-151408 and 62-151409.

As an alkali-soluble polyimide having a phenolic hydroxyl group, for example, J. Photopolym.Sci.Technol.Vol3N
o.3 (1990) pp. 275-280.

In the above resin-based material, the resin having a carboxyl group may be, for example, an unsaturated organic acid compound such as acrylic acid, methacrylic acid, or vinylbenzoic acid, and an unsaturated compound such as acrylic acid ester, methacrylic acid ester, or acrylonitrile. And the like.

In the resin-based material, examples of the epoxy resin include a novolak type epoxy resin, a bisphenol A type epoxy resin, a brominated bisphenol A type epoxy resin, and an alicyclic epoxy resin.

On the other hand, the photoacid generator (b) in the present invention refers to a compound that generates an acid upon irradiation with light, and many known compounds and mixtures thereof may be used. ^{_{-, BF 4 -, PF 6}} -, AsF 6 -, SbF 6 -, SiF 6 -, ClO 4
^-, CF ₃ SO ₄ ^- salts such as; (ii) organic halogen compounds; (ii
i) naphthoquinonediazidesulfonic acid compound and (iv)
Light sulfonic acid generating compounds and the like are suitable.

More specifically, (i) examples of ammonium salts as onium salts are described in U.S. Pat. Nos. 4,069,055 and 4,069,056; examples of diazonium salts include Photogr. Sci. Eng., 18 , 387 (1974), J.Macrom
ol. Sci., Chem., A21 , 1695 (1984), and Polymer. 21 , 423.
(1980); Examples of iodonium salts include Macromol
ecules, 10 , 1307 (1977). Chem., & Eng. News, Nov. 28, P3
1 (1988), and EP 0,104,143; examples of sulfonium salts include Polymer J., 17 , 73.
(1985), Polymer Bull., 14 , 279 (1985), J. Polymer Sc
i., 17 , 977 (1979), J. Org. Chem., 43 , 3055 (1978).
g. Chem., 50 , 4360 (1985), JP-A-57-18723, JP-A-56-8428, U.S. Patent No. 4,760,013, U.S. Patent No. 4,139,655, U.S. Patent No. 4,734,444 And EP 0297,433; examples of phosphonium salts include US Pat. Nos. 4,069,055,
4,069,056 and Macromolecules, 17 , 2469 (1984)
Examples of selenonium salts include Macromolecules, 10 ,
1307 (1977) and J. Polymer Sci., Polymer Chem. Ed., 1
7, 1047 (1979); examples of arsonium salts include Pr.
oc. Conf. Rad. Curing ASIA p478 Tokyo. Oct. (1988).

Examples of (ii) organic halogen compounds capable of generating an acid upon irradiation with light include carbon tetrabromide, iodoform, tribromoacetophenone, a phenyltrihalomethylsulfone compound described in JP-B-46-4605, and the like. JP-B-48-36281, JP-A-53-133428, JP-A-Sho-6
No. 0-105667, JP-A-60-239736, halomethyl-S-triazine compounds, Angew. Physik.
24 , 381 (1918); J. Phys. Chem, 66 , 2449 (1962);
JP-A-54-74728, JP-A-55-77742, JP-A-59-77742
148784, JP-A-60-3626, JP-A-60-1385
And halomethyloxadiazole compounds described in JP-A-39-239 and JP-A-60-239473.

(Iii) Examples of the naphthoquinonediazide compound include:
1,2-naphthoquinonediad- (2) -4-sulfonyl chloride can be mentioned.

(Iv) Examples of the photosulfonic acid generating compound include 1,2-
Naphthoquinonediazide- (2) -4-sulfonic acid ester or amide compound, Polymer Preprints.Japan
35 , 2406 (1986), β-ketosulfone compound, M
acromolecules, 21, 2001 (1988), JP-A-64-18143, an ester compound of nitrobenzyl alcohol and an arylsulfonic acid, EP 0,044,155.
No. 0,199,672, an ester compound of an oxime and an arylsulfonic acid described in U.S. Pat.
No. 1,371,605, No. 4,618,564, ester compounds of N-hydroxyamide or imide and sulfonic acid, European Patent No. 84515, benzoin and sulfone described in No. 199,672. Examples thereof include an ester compound with an acid.

Among these photoacid generators, the organic halogen compound (ii), particularly the halomethyl-S-triazine compound, the halomethyloxadiazole compound and the photosulfonic acid generating compound (iv) are preferred because of their good crosslinking efficiency.

These photoacid generators may be used alone or as a mixture. The amount of the photoacid generator is 0.1 to 50% by weight based on the solid content of the resin-based material curable by the acid (a). Preferably, it is 0.5 to 30% by weight. This is 0.1
If the amount is less than 50% by weight, the amount of generated acid is so small that a crosslinking reaction hardly occurs. Also, if the amount exceeds 50% by weight, a further effect of increasing the amount cannot be expected, and the developability deteriorates, and both are not preferred.

The photoacid generator can be used in combination with a sensitizer for increasing the acid generation efficiency as required.

Known sensitizers can be used as such a sensitizer,
For example, anthracene, phenanthrene, perylene, pyrene, chrysene, 1,2-benzoanthracene, coronene, 1,6-diphenyl-1,3,5-hexatriene, 1,1,4,
4-tetraphenyl-1,3-butadiene, 2,3,4,5-tetraphenylfuran, 2,5-diphenylthiophene, thioxanthone, 2-chlorothioxanthone, phenothiazine, 1,3-diphenylpyrazoline, 1,3 -Diphenylisobenzofuran, xanthone, benzophenone, 4-hydroxybenzophenone, anthrone, ninhydrin, 9
-Fluorenone, nitropyrene, 2,4,7-trinitrofluorenone, indanone, phenanthraquinone, tetralone, 7-methoxy-4-methylcoumarin, 3-keto-
Bis (7-diethylaminocoumarin), fluorocene,
Sensitizers such as eosin, rhodamine S and triphenylpyrylium perchlorate can be mentioned.

The ratio between these sensitizers and the compound capable of generating the acid is 0.01 / 1 to 10/1 by mole, preferably 0.1 / 1 to 5%.
/ 1.

The sensitivity of the composition of the present invention can be enhanced by selecting the type of such a sensitizer according to the pigment used.

The pigment (c) in the present invention means a colored powder that is hardly soluble in water or an organic solvent, and is preferably one having excellent heat resistance, light resistance and solvent resistance. Such pigments include, for example, azo, anthraquinone, isoindolinone, indigo, indathrone, xanthene, quinacridone, quinophthalone, dioxazine, thioindigo, pyranthrone, phthalocyanine, perinone, perylene-based pigments. , Benzoindazolone-based organic pigments and inorganic pigments such as Miroli blue, ultramarine blue, cobalt blue, emerald green, carbon, titanium carbon, iron oxide, and the like. Can be

When the above pigment is used for a color filter or the like,
From the viewpoints of light transmittance, uniformity of the formed film, and the like, the particle size is preferably 1 μm or less.

The weight ratio of the following formula (1) in the present invention is: 95/5 to 10/90, preferably 90/10 to 40/60. This is because when the weight ratio is less than 95/5, the film thickness for obtaining a desired color density becomes too thick, and
If the ratio exceeds 10/90, the dispersion stability of the pigment and the film-forming ability are impaired, which are both undesirable.

In the photosensitive colored resin composition of the present invention, the component (a) of the resin-based material curable by the acid and the component (b) of the photoacid generator are dissolved in a solvent capable of dissolving, and the pigment is dispersed. It is used as a solution that has been made to fall.

Examples of such solvents include ethers such as dioxane, diethoxyethane, diethylene glycol dimethyl ether, methyl cellosolve, ethyl cellosolve, ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dimethyl oxalate, methyl lactate, ethyl lactate Esters, such as N, N-dimethylformamide, N, N-dimethylacetamide, etc. S, pyrrolidones such as N- methylpyrrolidone, lactones such as γ- butyrolactone, and the like sulfoxides such as dimethyl sulfoxide. These solvents may be used alone or in combination of two or more.
And the concentration in the above components (total solids including additives)
It is suitably from 2 to 70% by weight, more preferably from 5 to 50% by weight.

In the photosensitive colored resin composition of the present invention, if necessary, the viscosity of the composition is adjusted, the dispersion stability of the pigment is improved, the coating property is improved, the adhesion of the coating film to the substrate is improved, and the coating film is flattened. Other additives can be added for the purpose of improving the developing property and the developing characteristics.

Next, examples of use of the photosensitive colored resin composition of the present invention will be described.

After coating the photosensitive colored resin composition of the present invention on a substrate and drying to form a colored resin layer, the layer is irradiated with light according to a predetermined pattern, and the layer is irradiated at about 50-200 ° C., preferably 70-1 ° C.
Heat in the range of 50 ° C. and then develop with a developer to form a colored pattern.

As the substrate on which the coating film is formed, for example, soda glass, pyrex glass, quartz glass used for a liquid crystal display device or the like, a glass obtained by attaching a transparent conductive film to these glasses, or a solid-state imaging device is used. A photoelectric conversion element substrate, such as a silicon substrate, may be used.

Examples of the coating method include conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating, and screen printing coating.

Drying when forming the colored resin layer is about 50 to 150 ° C.
It takes about 30 seconds to 30 minutes. For example, visible light, ultraviolet light, X-rays, and electron beams can be used for the irradiation.

Then, the resin layer is heated. The heat treatment after the exposure causes the resin in the exposed portion to crosslink and harden, so that the resin does not dissolve in the developer.

Examples of the developer include alkaline aqueous solutions such as inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, dibasic sodium phosphate, tertiary sodium phosphate, and ammonia. , Ethylamine, n-propylamine, diethylamine, di-n-propylamine, alkylamines such as triethylamine and methyldiethylamine, alcoholamines such as diethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethyl An aqueous solution of a quaternary ammonium salt such as (2-hydroxyethyl) ammonium hydroxide or a cyclic amine such as pyrrole or piperidine can be used.

If necessary, other additives such as a surfactant, a wetting agent, a stabilizer and a small amount of an organic solvent can be added to the developer.

<Example> Next, the present invention will be described in more detail with reference to an example.

Examples 1 to 6 A resin material curable with an acid (a) and a photoacid generator (b) shown in Table 1 below were dissolved in a solvent, and the pigment (c) was mixed with the solution. After dispersing with a roll, the mixture was diluted to a predetermined concentration with a solvent and then passed through a 1 μm tetron filter to obtain each photosensitive colored resin composition.

These photosensitive coloring resin compositions were applied to a soda glass substrate on which a SiO ₂ film had been formed, using a spinner, and dried at 80 ° C. for 10 minutes. The colored photosensitive resin layer was exposed to an air atmosphere with a metal halide lamp through a mask having a predetermined shape.

Subsequently, the colored photosensitive resin layer subjected to pattern exposure was
After heating at 0 ° C. for 10 minutes, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide to obtain a colored pattern.

The coloring pattern thus obtained is uniform,
The edges were sharp.

Further, the patterns of Examples 1 to 6 were heated at 230 ° C. for 1 hour, and the absorption spectra before and after heating were measured. As a result, no change was observed in all the examples.

Example 7 A composition having the same composition as in Examples 1 to 6 was exposed under an N ₃ gas atmosphere to form a colored pattern. The exposure time was the same as in Examples 1 to 6, and the composition was cured. _No difference between the _two gas atmospheres was observed.

<Effects of the Invention> As described above in detail with the examples, according to the present invention, it has high sensitivity, is not affected by oxygen at the time of exposure, has excellent heat resistance, and can be developed with an aqueous developer. A photosensitive coloring composition can be provided. This photosensitive coloring composition is particularly suitable for use in the production of color filters or black stripes used in liquid crystal display devices.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hideo Kikuchi 563 Yonegasaki-cho, Funabashi-shi, Chiba Pref. Photographic Materials Research Laboratories, Toyo Gosei Kogyo Co., Ltd. (56) References JP-A-60-154248 (JP, A) Hei 2-52348 (JP, A) JP-A-63-313150 (JP, A) JP-A-63-97948 (JP, A) JP-A-60-39642 (JP, A) JP-A-59-113435 (JP, A) JP-A-60-129707 (JP, A) JP-A-60-129739 (JP, A) JP-A-2-804 (JP, A) JP-A-2-144502 (JP, A) 2-191901 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/038 G03F 7/004 G02B 5/20

Claims (4)

(57) [Claims] 1. A photosensitive colored resin composition for forming a colored pattern, comprising: (a) a resin-based material curable by an acid; (b) a photoacid generator; and (c) a pigment. A photosensitive resin composition characterized in that it is contained at a ratio of: 2. The photosensitive resin composition according to claim 1, wherein the pigment has a particle size of 1 μm or less. 3. The photosensitive resin composition according to claim 1, wherein said photoacid generator is contained in an amount of 0.5 to 30% by weight based on an acid-curable resin material. Composition. 4. The photosensitive resin composition according to claim 1, wherein said resin material curable by acid comprises a resin containing phenol and a crosslinking agent having an N-methylol structure. Resin composition.