JPH1184655A - Pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a pattern having high resolution, high sensitivity, excellent adhesion property to a substrate, coating property and storage stability without causing environmental pollution by forming a photoset pattern in a process including a step of applying a photosensitive resin compsn. which contains a photosensitive resin having specified structural unit on a substrate to form a photosensitive resin compsn. coating film. SOLUTION: In this pattern forming method, a photosensitive resin compsn. which contains a photosensitive resin having a structural unit expressed by formula I is applied on a substrate to form a photosensitive compsn. coating film. The photosensitive compsn. is exposed to light according to a desired pattern. and the exposed photosensitive compsn. coating film according to the pattern is developed with water or a water-based developer to form a photoset pattern. In formula I, n is 1, 2, or 3, and Ar is selected from formula II. In formula II, X is lithium, sodium, potassium, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pattern forming method using a novel photosensitive resin composition, and more particularly to a pattern forming method having high sensitivity, good storage stability and good resolution.

[0002]

2. Description of the Related Art Conventionally, as a negative type photoresist used for forming a black matrix such as a color CRT or a phosphor pattern, a resist (PVA-ADC) comprising a water-soluble polymer such as polyvinyl alcohol and a dichromate is used. However, this type of photoresist has a basic problem that special processing equipment is required for the purpose of preventing environmental pollution since it contains dichromate.

On the other hand, photoresists free from such problems include water-soluble diazides as photocrosslinking agents, for example,
There is known a photosensitive composition in which sodium 4,4'-diazidostilbene-2,2'-disulfonate (hereinafter, abbreviated as DAS) is combined with a water-soluble polymer which can be photocrosslinked thereby. For example, a polymer using a vinyl alcohol-maleic acid copolymer or a salt thereof as a photocrosslinkable water-soluble polymer (Japanese Patent Application Laid-Open No. 48-97602).
JP-A-48-97603), those using a vinyl alcohol-acrylamide copolymer (JP-A-48-97603) and those using water-soluble polyvinyl butyral (JP-A-48-98).
No. 905) have been proposed, but these cannot be practically used because of their low sensitivity. Further, as a material having a sensitivity that can be actually used, polyvinyl pyrrolidone (hereinafter abbreviated as PVP) to which a water-soluble bisazide is added (hereinafter referred to as a PVP-DAS-based resist; see, for example, JP-A-48-90185) ), Acrylamide-diacetone acrylamide copolymer (hereinafter abbreviated as PAD) to which water-soluble bisazide is added (hereinafter referred to as PA)
Referred to as D-DAS-based resist;
No. 0225) is known.

[0004] Considering the case where it is used for forming a black matrix for a color CRT, PVA-
In addition to the above-mentioned pollution problems, ADC-based resists have low oxygen permeability and no reciprocity failure characteristics, and thus have a problem of poor resolution. Further, the PVP-DAS-based resist has a problem that the oxygen permeability is too high, so that it is necessary to increase the coating film thickness in order to obtain an appropriate sensitivity, thereby lowering the resolution. Also, PAD-DAS
Although the system resist has good sensitivity and resolution, it has a problem that the etching property after forming a resist pattern and applying graphite is not good and cannot be etched depending on the type of graphite.

Considering the use of forming a phosphor pattern, the PVA-ADC resist is not sufficient in terms of sensitivity, in addition to the problem of pollution, and the chromium oxide remains after firing, so that the phosphor is difficult to use. There is a problem that the brightness of the image is reduced. In addition, PVP-DAS resist and P
AD-DAS resists have a problem in sensitivity and cannot be used.

On the other hand, as a non-chromium resist particularly for use in forming a phosphor pattern, as a photosensitive unit, a polyvinyl alcohol is subjected to a condensation reaction with a quaternary ammonium salt such as a styrylpyridium salt compound or a styrylquinolium salt compound. (Japanese Patent Publication No. 56-5761 and Japanese Patent Publication No.
6-5762, JP-A-56-11906). However, these resists are not satisfactory in terms of resolution.

As a method of forming a color filter for a color cathode ray tube, Japanese Patent Application Laid-Open Nos. 5-26695, 8-87962, 8-185799, and the like have been proposed. There are problems such as environmental pollution, low sensitivity, and complicated processes for using dichromate as a solvent, and it is not satisfactory.

[0008]

As described above, no conventional photoresist is satisfactory in all of the pollution problems, sensitivity, and resolution, so that it has high sensitivity, high adhesiveness to a substrate, The emergence of a pattern forming method using a composition having excellent coatability and storage stability has been desired. Especially,
A photosensitive composition with high sensitivity, excellent adhesion to substrates, applicability, storage stability, etc., while maintaining the advantages of reciprocity failure when using a water-soluble polymer and a water-soluble azide. The emergence of patterning methods is eagerly desired.

In view of such circumstances, the present invention is free from concerns about pollution, has high resolution, has sufficient sensitivity, and has excellent photosensitivity such as adhesion to substrates, coating properties, and storage stability. It is an object to provide a pattern forming method using a resin composition.

[0010]

According to the present invention, there is provided a pattern forming method comprising the steps of: applying a photosensitive resin composition containing a photosensitive resin having a structural unit represented by the following general formula onto a substrate; A coating film forming step of forming a photosensitive composition coating film, an exposure step of subjecting the photosensitive composition coating film to a desired pattern exposure, and applying the pattern-exposed photosensitive composition coating film to water or an aqueous developer. And a developing step of forming a photo-cured pattern by developing the photo-cured pattern.

[0011]

Embedded image

Here, n is 1, 2 or 3. Also,
Ar is selected from the following, and the following X represents lithium, sodium, potassium, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium, or tetraalkylammonium.

[0013]

Embedded image

Here, the photosensitive resin composition may further contain, for example, a water-soluble polymer.

The photosensitive resin composition may be, for example,
Further, it may contain a water-soluble azide compound.

The substrate is, for example, an inner surface of a face plate of a color CRT.

Further, after the developing step, a step of applying a graphite slurry to the entire surface of the photocurable pattern and drying the same to form a graphite coating film; Forming a matrix.

Further, for example, the photosensitive resin composition may further include a phosphor, and a phosphor pattern may be formed by the developing step.

Further, the photosensitive resin composition may further contain a pigment, and a color filter may be formed by the developing step.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be achieved by using a polyvinyl acetate saponified by introducing a photosensitive group having a special long-wavelength azide. And completed the present invention.

The photosensitive resin represented by the general formula (I) used in the present invention is obtained by reacting a photosensitive compound represented by the following formula (1) with a saponified polyvinyl acetate in the presence of an acid catalyst. be able to.

[0022]

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Here, R is an alkyl group up to C6 and-(CH ₂ ) _m- (m
Is selected from 2 or 3). N is 1, 2 or 3. Ar and X are as described above.

Such a photosensitive compound can be obtained by condensing a rhodanine compound represented by the following formula (2) with an aldehyde compound having an azido group-containing aromatic ring represented by the following formula (3).

[0025]

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The rhodanine compound is prepared, for example, by converting an acetal compound having an amino group into carbon disulfide in the presence of a base such as ammonia, triethylamine, NaOH or KOH to synthesize a dithiocarbamate,
It can be obtained by reacting with ethyl chloroacetate. In this case, the reaction solvent can be selected from water, ether, DMF and the like depending on the amine compound used, but is not limited thereto.

The aromatic aldehyde having an azide group condensable with the rhodanine compound or the aldehyde compound having an aromatic ring having an azide group is represented by the following formula (3)
Indicated by

[0028]

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Here, in the formula (3), Ar is as described above.

The saponified polyvinyl acetate used in the present invention means polyvinyl alcohol or a water-soluble copolymer of vinyl alcohol and another vinyl compound.
For example, those containing a modified vinyl acetate saponified by modification with a hydrophilic group, modification with a hydrophobic group, modification with an anion, modification with a cation, modification with an amide group, or modification with a reactive group such as an acetoacetyl group.

The polyvinyl alcohol used here has, for example, an average degree of polymerization of 200 to 5000 and a degree of saponification of 6
Those with 0 to 100% are preferred. Average degree of polymerization is 200
If it is smaller, it is difficult to obtain sufficient sensitivity.
If the average degree of polymerization is larger than 5000, the viscosity of the solution of the photosensitive resin becomes high, so that the problem that the coating property is deteriorated is apt to occur. It is difficult to obtain the thickness. On the other hand, if the saponification degree is lower than 60%, it is difficult to obtain sufficient water solubility and water developability.

On the other hand, as a copolymer of vinyl alcohol and another vinyl compound, for example, an average degree of polymerization of 200 to 200
5000 can be used. In addition, as a vinyl monomer copolymerizable with vinyl alcohol, for example, N
-Vinylpyrrolidone, acrylamide and the like.

Such saponified polyvinyl acetates,
When the photosensitive compound represented by the above formula (1) is reacted with the photosensitive compound represented by the above formula (1) in the presence of an acid catalyst to obtain a photosensitive resin represented by the above formula (I), for example, formaldehyde, acetaldehyde,
Aliphatic aldehydes such as propionaldehyde, butyraldehyde, crotonaldehyde, benzaldehyde,
Sulfonate, benzaldehyde disulfonic acid salt, aromatic aldehydes such as sodium 4-azido-2-sulfobenzaldehyde, carboxybenzaldehyde, hydroxybenzaldehyde, formylstyrylpyridinium salt or ketones such as acetals thereof, acetone and methyl ethyl ketone. They can be reacted simultaneously.

The introduction ratio of the photosensitive compound of the formula (1) to the saponified polyvinyl acetate is preferably about 0.3 to 50 mol% per monomer unit.

The pattern forming method of the present invention is carried out using a photosensitive resin composition containing the above-mentioned photosensitive resin of the general formula (I).

The photosensitive resin may be used together with a water-soluble polymer as described above. Examples of the water-soluble polymer include natural polymers such as saponified polyvinyl acetate, gelatin, cellulose derivatives, and casein; It is a polymer or copolymer composed of a functional vinyl monomer.
Here, as the water-soluble vinyl monomer, N-vinylformamide, N-vinylacetamide, vinylpyrrolidone, acrylamide, diacetoneacrylamide, N,
Examples include N-dimethylacrylamide, vinylpyridine, methacrylamide, allylthiourea and the like. The content of the resin of the formula (1) with respect to the total water-soluble polymer is preferably 0.5% or more.

The photosensitive resin may be used together with the water-soluble azide compound as described above. Such water-soluble azide compounds include, for example, 4,4'-diazidostilbene 2,2'-disulfonic acid, 4,4'-diazidobenzalacetophenone-2-sulfonic acid, 4,4'-diazidostilbene -Α-carboxylic acids and their alkali metal salts, ammonium salts, organic amine salts and the like. Furthermore, Japanese Patent Publication No. 50-27404,
JP-A-50-141403, JP-A-2-2047
No. 50, JP-A-4-26849, JP-A-5-268
Water-soluble azide compounds described in JP-A No. 11442, JP-A-5-113661, JP-A-6-239930 and the like can be suitably used.

The photosensitive resin composition used in the present invention may contain, for example, ethylene glycol, sorbitol or a surfactant, if necessary, for improving coating properties and moisture retention properties. A so-called silane coupling agent, which is an adhesion promoter, can be added to the photosensitive composition of the present invention as needed to improve the adhesion to the substrate. As these adhesion promoters, water-soluble adhesion promoters such as N-β (aminoethyl) -aminopropylmethyldimethoxysilane and N-β (aminoethyl) -γ-aminopropyltrimethoxysilane are used. .

If necessary, for example, a preservative, an antifoaming agent, and a pH adjuster can be added to the photosensitive resin composition used in the present invention.

Further, if necessary, a hydrophobic polymer emulsion is added to the photosensitive resin composition used in the present invention, for example, to improve film strength, water resistance, and adhesion to various substrates. be able to. Here, examples of the hydrophobic emulsion include a polyvinyl acetate emulsion, a polyacrylate emulsion, and a urethane emulsion. Pattern formation using the composition containing the hydrophobic polymer emulsion can be suitably used, for example, for a screen printing plate.

Further, a coloring agent such as a pigment or a dye may be added to the photosensitive resin composition used in the present invention in order to prevent halation due to exposure or to obtain a colored image.

In particular, a colored image obtained by dispersing a pigment in the photosensitive resin composition used in the present invention includes, for example, a color filter for a liquid crystal display, a color filter for a color CRT, a color filter for a plasma display, a color proof for printing, It can be applied to the second original drawing, etc.

The pattern forming method using the photosensitive resin composition described above includes, for example, a step of forming a photosensitive composition coating film by coating on a substrate and a step of forming a desired film on the photosensitive composition coating film. Pattern exposure; and developing the pattern-exposed photosensitive composition coating film with water or an aqueous developer.

The substrate may be an inner surface of a face plate of a color cathode ray tube. Therefore, specifically, a black matrix, a phosphor pattern, a color filter, and the like of a color CRT can be formed.

Hereinafter, the pattern forming method according to the present invention will be further described.

(1) Step of Forming Coating Film of Photosensitive Composition on Substrate As the substrate, any substrate to which the photosensitive composition of the present invention can adhere can be used. Specific examples of the substrate used in the present invention are shown below, but the substrate that can be used in the present invention is not limited thereto. That is, specific examples of the substrate include, for example, glass, SiO ₂ treated glass, glasses such as ITO-attached glass, polyester films, polyamide films, polyvinyl chloride films, various plastic films such as polypropylene films and plates, Examples include various metal substrates, plastic plates and plastic films in which metals are laminated, meshes, silicon wafers, and the like.

Examples of the method for applying the photosensitive composition of the present invention include a spin coating method, a roll coater method, a curtain coating method, an applicator method and the like which have been conventionally used. After the application, the coating film is obtained by drying at a predetermined temperature according to a conventional method.

(2) Pattern Exposure Step The exposure light source for the coating film of the photosensitive composition may be an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a chemical lamp, or the like. Any general light source that emits light having a wavelength sensitive to the photosensitive resin can be used. Also, as the exposure method,
All general exposure methods such as a reduced projection exposure method, a contact exposure method, and a purity exposure method can be used.

(3) Developing Step The coating film of the photosensitive composition which has been subjected to the pattern exposure is formed of water, water-
It can be developed with an aqueous solution in which a mixed solvent of a water-soluble solvent, an acid, an alkali, a pH adjuster, a surfactant and the like are dissolved. As the developing method, development can be performed by a general method such as spray development, dipping development, and paddle development.

As described above, the pattern forming method of the present invention is particularly preferably applied to the inner surface of the face plate of a color CRT. When the above-described pattern forming method of the present invention is applied to the inner surface of the face plate of the color cathode ray tube, the productivity is good because of high sensitivity and high resolution.

For example, in the case of forming a black matrix for a color cathode ray tube, after forming the above-mentioned pattern, graphite is applied and treated with a stripping solution (etching). In this case, the pattern formed according to the present invention can be etched well, so that a clean black matrix can be formed.

Examples of the stripping solution include an oxidizing compound such as periodic acid and hydrogen peroxide, an acid such as sulfuric acid, sulfamic acid, nitric acid and dodecylbenzenesulfonic acid, and an aqueous solution such as a mixture thereof. be able to.

In the case of forming a phosphor pattern, the photosensitive composition of the present invention containing the phosphor is applied to an object on which the phosphor pattern is to be formed, for example, on the black matrix on the inner surface of the face plate of a color CRT. And dry it. After exposing it to ultraviolet light through a mask having a predetermined pattern, only the portion exposed by water development is left. Red (R), green (G), blue (B)
When the three types of phosphors are used, the above process is repeated three times to complete the phosphor screen.

In the case of forming a color filter of a color cathode ray tube, for example, the photosensitive composition containing the pigment of the present invention may be applied on the surface on which the color filter is to be formed, on the face plate on which the black matrix of the color cathode ray tube is formed. And uniformly dried. After exposing it to ultraviolet light through a mask having a predetermined pattern, only the portion exposed by water development is left. When three kinds of inorganic pigments of red (R), green (G), and blue (B) are used, the above process is repeated three times to complete a color filter.

[0055]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments.

(Production Example 1 of Photosensitive Resin) (1) [Preparation of Aqueous Dispersion of 3- (2 ′, 2′-Dimethoxyethyl) rhodanine] 53 g of aminoacetaldehyde dimethyl acetal and 20 g of sodium hydroxide were added to 200 g of water. Disperse and dissolve, 10
Cooled to ° C. Under stirring, 38 g of carbon disulfide was added dropwise over 30 minutes, followed by a reaction at 20 ° C. for 24 hours. next,
Ethyl chloroacetate (81 g) was added dropwise over 15 minutes, and then reacted at room temperature for 24 hours to obtain an aqueous dispersion of the target compound represented by the following formula.

[0057]

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(2) [5- (Sodium 4'-azido-
Synthesis of 2′-sulfobenzylidene) -3- (2 ″, 2 ″ -dimethoxyethyl) rhodanine] Sodium 4-azido-2-sulfobenzaldehyde 1
An aqueous solution prepared by dissolving 20 g of sodium hydroxide and 30 g of sodium hydroxide in 2500 g of water was prepared, cooled to 10 ° C., and then slowly added to the aqueous dispersion of (1). As the reaction proceeds, the target product precipitates, but the stirring is continued as it is,
The reaction was performed for 24 hours. Add 150 g of NaCl, and add 5 g
After stirring for an hour, the target substance was separated by filtration and washed with acetone.

The product represented by the following formula had a purity of 95% by liquid chromatography. The absorption maximum is 3
It was 88 nm.

[0060]

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(3) [Synthesis of photosensitive resin] Polyvinyl alcohol (GH-17, manufactured by Nippon Gosei) 10
0 g was dissolved in 900 g of water, 13 g of the compound synthesized in (2) and 3 g of phosphoric acid were added thereto, and the mixture was reacted at 80 ° C. for 24 hours. The acetalization rate was 90%. Phosphoric acid is removed by ion exchange treatment, and the photosensitive group is added to PVA in a proportion of 1.
A photosensitive solution into which 3 mol% was introduced was prepared. Thereafter, ion-exchanged water was added to adjust the solid content to 6%.

(Production Example 2 of Photosensitive Resin) (1) [Preparation of Aqueous Dispersion of 3- (4 ′, 4′-dimethoxybutyl) rhodanine] 67 g of aminobutyraldehyde dimethyl acetal and 60 g of aqueous ammonia were dispersed in 200 g of water. Dissolve and cool to 10 ° C. Under stirring, 38 g of carbon disulfide was added dropwise over 30 minutes, followed by a reaction at 20 ° C. for 24 hours. Next, 81 g of ethyl chloroacetate was added dropwise over 15 minutes, and then reacted at room temperature for 24 hours to obtain an aqueous dispersion of the target product represented by the following formula.

[0063]

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(2) [5- (Sodium 4'-azido-
Synthesis of 2′-sulfobenzylidene) -3- (4 ″, 4 ″ -dimethoxybutyl) rhodanine] Sodium 4-azido-2-sulfobenzaldehyde 1
An aqueous solution in which 20 g of sodium hydroxide and 30 g of sodium hydroxide were dissolved in 2500 g of water was cooled to 10 ° C., and this was slowly added to the aqueous dispersion of (1). Although the target product was precipitated as the reaction proceeded, stirring was continued as it was, and the reaction was carried out for 24 hours. Na
150 g of Cl was added, and the mixture was further stirred for 5 hours. The target substance was separated by filtration and washed with acetone.

The product represented by the following formula had a purity of 95% by liquid chromatography. The absorption maximum is 3
It was 88 nm.

[0066]

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(3) [Synthesis of Photosensitive Resin] 100 g of polyvinyl alcohol (GH-17, manufactured by Nippon Synthetic Chemical Industry) was dissolved in 900 g of water. 15 g of the compound of (2) and 3 g of phosphoric acid were added and reacted at 60 ° C. for 24 hours. The acetalization rate was 90%. Phosphoric acid is removed by ion exchange treatment, and the photosensitive group is converted to 1.3 mol% in PVA.
The introduced photosensitive solution was prepared. Thereafter, ion-exchanged water was added to adjust the solid content to 6%.

(Production Example 3 of Photosensitive Resin) 100 g of polyvinyl alcohol (EG-05, manufactured by Nippon Synthetic Chemical Industry) was dissolved in 1800 g of water, and the compound of (2) of Production Example 2 of the photosensitive resin described above was added thereto. 103 g and phosphoric acid 5 g were added, and 6
The reaction was performed at 0 ° C. for 24 hours. Phosphoric acid was removed with an ion exchange resin to prepare a photosensitive solution in which a photosensitive group was introduced into PVA at 10.0 mol%. Ion exchange water was added to adjust the solid content to 6%.

Example 1 Sensitivity Curve The sensitivity curve of a typical photosensitive solution was measured by the following method.

Photosensitive solution A: 6% solids photosensitive solution of Production Example 1 Photosensitive solution B: 6% solids photosensitive solution of Production Example 1: 80 g 6% aqueous solution of polyvinylpyrrolidone: 18.2 g 6% aqueous solution of DAS 1.8 g

The photosensitive solutions A and B were applied to a glass plate of 25 cm ² and dried at 60 ° C. for 5 minutes to obtain a 1 μm photosensitive film. Exposure was performed at 0.15 mW / cm ² (illuminance of 350 nm) for 2 seconds to 50 seconds using an ultra-high pressure mercury lamp, followed by water development for 1 minute and drying. The thickness of the cured film was measured, and the remaining film ratio was obtained.
The results are shown in the following table and graph.

[0072]

[Table 1]

Further, using a photosensitive solution A,
And a super-high pressure mercury lamp of 3 mW / cm ² (350 n
(illuminance of m), a pattern was exposed for 2 seconds through a chrome mask and developed with water to form a clear pattern of 10 μm.

Example 2 20 g of the 6% photosensitive solution obtained in Production Example 1 above, 100 g of an aqueous solution of polyvinylpyrrolidone having a solid content of 6%, and 4,4′-diazidostilbene-2,2 ′ of a 6% aqueous solution -Sodium disulfonate [hereinafter referred to as DAS
10 g). After diluting this mixture to 3%, it was filtered through a 1.0 μm membrane filter.

This photosensitive solution was spin-coated on the inner surface of a color cathode ray tube face plate so that the dried coating film had a thickness of 0.5 μm, and dried at 50 ° C. for 5 minutes to obtain a coating film.

Then, using a shadow mask, an ultra-high pressure mercury lamp was used to emit 0.10 mW / cm ² (illuminance of 350 nm).
For 12 seconds.

Then, the resultant was subjected to water development with warm water of 40 ° C. for 30 seconds to obtain a dot having a well-shaped pattern.

The photosensitive resin composition used exhibited reciprocity failure.

Next, a carbon suspension was applied onto the dots, and the dots and the carbon thereon were removed with a stripper to form a clean black matrix.

Example 3 A black matrix was formed in the same manner as in Example 2 except that the photosensitive solution obtained in Production Example 2 was used instead of the photosensitive solution obtained in Production Example 1.

Example 4 5 g of the 6% photosensitive solution obtained in Production Example 3 above, and an aqueous solution of polyvinylpyrrolidone having a solid content of 6% 10
0 g and 10 g of a 6% aqueous solution of DAS were mixed. Further, 0.07 g of KBM-603 (a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.) was added. After diluting the mixture to 3%, the mixture was filtered through a 1.0 μm membrane filter to prepare a photosensitive solution.

Using this, in the same manner as in Example 2,
A clean black matrix was formed.

(Example 5) 30 g of the 6% photosensitive solution obtained in Production Example 1 above, and an aqueous solution of polyvinylpyrrolidone having a solid content of 6% 7
And 0 g. Further, 0.05 g of KBM-603 (a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.) was added. After diluting the mixture to 3%, the mixture was filtered through a 1.0 μm membrane filter to prepare a photosensitive solution.

Using this photosensitive liquid, a clean black matrix was formed in the same manner as in Example 2.

Example 6 A photosensitive composition having the following formulation was prepared.

A 10 wt% aqueous solution of the photosensitive resin of Production Example (1): 70 gr Red inorganic pigment: 28 gr (iron oxide, average molecular weight 100 nm, manufactured by Ishihara Sangyo) Pure water: 280 gr Silane coupling agent (KBM-603): 0.14 gr 5% Tamol 731 (surfactant manufactured by Rohm & Haas): 1.5 gr

A photosensitive composition having the above-mentioned formulation was prepared by adding 10 cm × 1
It was applied on a 0 cm soda glass by a spin coating method and dried to obtain a coating film of 1.0 μm. Next, the distance 1c between the shadow mask having a pitch of 0.28 mm and the glass plate.
m, the distance between the shadow mask and the ultra-high pressure mercury lamp is 30 cm, and the illuminance at 350 nm on the glass plate surface is 0.20 (mW / c).
m ² ) Exposure was performed for 30 seconds at a position corresponding to red at an exposure illuminance of m ² ).

Subsequently, spray development was performed with hot water (nozzle: No. 3 manufactured by Spraying System, water pressure:
2.0 kg / cm ² , temperature: 40 ° C., distance 15 cm).

When the obtained pattern is observed with a microscope,
A red pigment layer pattern faithful to the shadow mask was obtained.

Example 7 A 0.1% aqueous solution of polyvinyl alcohol was coated on the inner surface of a color cathode ray tube face plate on which a black matrix was formed by the method of Example 2, dried, and then a phosphor slurry having the following formulation was applied and dried. As a result, a coating film having a thickness of 10 to 12 μm was obtained. continue,
0.12 mW / cm ² (350 nm illuminance) with an ultra-high pressure mercury lamp using a 0.28 mm pitch shadow mask
For 25 seconds. Subsequently, by performing water development with 40 ° C. hot water for 30 seconds, a phosphor pattern sufficiently filled with a green phosphor was formed.

(Composition of Phosphor Slurry) Green phosphor: 100 g Photosensitive solution having a solid content of 2.5% in Production Example 1: 285 g 10% aqueous solution of LT-221 (surfactant manufactured by NOF Corporation): 4.6 g L -62 (BASF surfactant) 10% aqueous solution: 1.8 g

(Example 8) A 0.1% aqueous solution of polyvinyl alcohol was coated on the inner surface of a color cathode ray tube face plate on which a black matrix was formed by the method of Example 2, dried, and then a phosphor slurry having the following formulation was applied. After drying, a phosphor pattern was formed in the same manner as in Example 6 above.

(Composition of Phosphor Slurry) Green phosphor: 100 g Photosensitive solution with 2.5% solid content of Production Example 1: 44 g 2.5% aqueous solution of poly N-vinylformamide: 219 g 2.5% aqueous solution of DAS: 22 g 10% aqueous solution of LT-221 (surfactant manufactured by NOF CORPORATION): 4.6 g 10% aqueous solution of L-62 (surfactant manufactured by BASF): 1.8 g

[0094]

As described above, according to the method of the present invention, there is no need to worry about pollution problems, high resolution, sufficient sensitivity, adhesion to substrates, coating properties, storage stability, etc. It is possible to use a photosensitive resin composition excellent in the above, and to form a high resolution.

[Procedure amendment]

[Submission date] November 21, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Brief description of drawings

[Correction method] Added

[Correction contents]

[Brief description of the drawings]

FIG. 1 is a graph showing the results of Example 1.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/40 G03F 7/40 H01J 9/227 H01J 9/227 D H01L 21/027 H01L 21/30 502R

Claims (7)

[Claims] 1. A coating film forming step of applying a photosensitive resin composition containing a photosensitive resin having a structural unit represented by the following general formula onto a substrate to form a photosensitive composition coating film, An exposure step of subjecting the photosensitive composition coating to a desired pattern exposure, and a developing step of developing the pattern-exposed photosensitive composition coating with water or an aqueous developer to form a photocurable pattern. Characteristic pattern formation method. Embedded image Here, n is 1, 2 or 3. Ar is selected from the following, and the following X represents lithium, sodium, potassium, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium, or tetraalkylammonium. Embedded image 2. The pattern forming method according to claim 1, wherein the photosensitive resin composition further contains a water-soluble polymer. 3. The pattern forming method according to claim 1, wherein the photosensitive resin composition further contains a water-soluble azide compound. 4. The pattern forming method according to claim 1, wherein said substrate is an inner surface of a face plate of a color cathode-ray tube. 5. The method according to claim 4, further comprising, after the developing step, applying a graphite slurry to the entire surface of the photocurable pattern and drying to form a graphite coating film. Forming a black matrix by removing the black matrix. 6. The pattern forming method according to claim 4, wherein the photosensitive resin composition further includes a phosphor, and a phosphor pattern is formed by the developing step. 7. The pattern forming method according to claim 4, wherein the photosensitive resin composition further contains a pigment, and a color filter is formed by the developing step.