JPH09114092A - Polyvinyl alcohol-base photosensitive resin composition and pattern forming method using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. having satisfactory water and heat resistances and sufficiently high water solubility and also having satisfactory miscibility with an anionic additive by incorporating a PVA-base high molecular compd. having specified amts. of plural specified constituent units in a specified molar ratio. SOLUTION: This compsn. contains a PVA-base high molecular compd. obtd. by adding a styryl compd. having a photosensitive quaternized arom. N-contg. hetero ring represented by formula I and a phenyl compd. having a sulfonic acid group represented by formula II in a pendent state so as to regulate the content of the styryl compd. to 0.5-10mol%, that of the phenyl compd. to 0.6-20mol% and the molar ratio of the styryl compd. to the phenyl compd. to <1. In the formula, I, R1 is the residue of a quaternized arom. N-contg. hetero ring, R2 is H or lower alkoxyl, (m) is 0 or 1 and (n) is an integer of 1-6. In the formula II, X is Na, K, ammonium, an org. amine, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyvinyl alcohol-based photosensitive resin composition and a pattern forming method using the same, and more specifically, it has good compatibility with an anionic additive, and water resistance and heat resistance. And a pattern forming method using the same.

[0002]

2. Description of the Related Art Conventionally, as water-soluble polyvinyl alcohol-based photosensitive resins, Japanese Patent Publication No. 56-5761, Japanese Patent Publication No. 56-5762, Japanese Patent Publication No. 56-11906, and Japanese Patent Publication No. 59-17550. Japanese Patent Laid-Open No. 2-11
Known are polyvinyl alcohol-based photosensitive resins in which a styryl derivative having a quaternized aromatic nitrogen-containing heterocycle is pendant, which is disclosed in Japanese Patent No. 8575, Japanese Patent Publication No. 2-276806, Japanese Patent Application Laid-Open No. 6-43645 and the like. Has been. Although these photosensitive resins have high sensitivity, they have a drawback that they are poor in water resistance and swell during development, so that sufficient resolution cannot be obtained. Furthermore, since these photosensitive resins are cationic, they have the drawback that they thicken or gel when mixed with an anionic additive such as an anionic surfactant or emulsion. Further, when a pattern is formed on a substrate having an anionic surface by using these photosensitive resins, there is a problem that scum is generated due to ionic interaction.

On the other hand, as a solution to such a problem, there is a polyvinyl alcohol in which a styryl derivative having a quaternized aromatic nitrogen-containing heterocycle having a betaine structure is pendant as a polyvinyl alcohol photosensitive resin. -160807 gazette. However, this photosensitive resin has drawbacks such as insufficient water solubility and slightly low sensitivity.

[0004]

The above-mentioned conventional polyvinyl alcohol-based photosensitive resins have, for example, poor water resistance, poor heat resistance, insufficient water solubility, and poor miscibility with anionic additives. It has drawbacks such as

In view of the above circumstances, the present invention uses a photosensitive resin composition having good water resistance and heat resistance, sufficient water solubility, and good miscibility with an anionic additive, and the same. It is an object to provide a pattern forming method.

[0006]

A first aspect of the present invention for achieving the above object is a polyvinyl alcohol polymer compound having constitutional units represented by the following general formulas (I) and (II): ,

[0007]

Embedded image (R ₁ is a quaternized aromatic-containing nitrogen heterocyclic residue, R ₂ is a hydrogen atom or a lower alkoxyl group, m is 0 or 1,
n represents an integer of 1 to 6)

[0008]

Embedded image (X represents hydrogen, Na, K, ammonium, organic amine or organic quaternary ammonium) The content of the general formula (I) is 0.5 to 10 mol%,
The content of the general formula (II) is 0.6 to 20 mol%,
A polyvinyl alcohol-based photosensitive resin composition comprising a polyvinyl alcohol-based polymer compound having a molar ratio of less than 1 represented by the general formula (I) / general formula (II).

A second aspect of the present invention is characterized in that, in the first aspect, the molar ratio represented by the general formula (I) / the general formula (II) is 0.3 to 0.8. It is in a polyvinyl alcohol-based photosensitive resin composition.

A third aspect of the present invention is the polyvinyl alcohol-based photosensitive resin composition according to the first or second aspect, which further contains an anionic additive.

In a fourth aspect of the present invention according to the third aspect, the anionic additive is an anionic hydrophobic polymer emulsion, an anionic surfactant, an anionic dye, an anionic pigment or an anionic pigment. The polyvinyl alcohol-based photosensitive resin composition is characterized by being at least one selected from the group consisting of the water-soluble polymer compound and the anionic photosensitizer.

A fifth aspect of the present invention is a step of forming a photosensitive resin layer by coating the polyvinyl alcohol-based photosensitive resin composition according to any one of the first to fourth aspects on a substrate, and the step of forming the photosensitive resin layer. And a step of developing the resin layer by pattern exposure and subsequently developing the resin layer.

A sixth aspect of the present invention is the pattern forming method according to the fifth aspect, wherein the surface of the substrate is anionic.

A seventh aspect of the present invention is the phosphor according to the sixth aspect, wherein the substrate is a substrate on which a black matrix is formed, and the photosensitive resin composition contains a phosphor. A pattern forming method is characterized by forming a pattern.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted intensive research to develop a photosensitive resin composition having excellent properties that achieves the above-mentioned objects, and as a result, a photosensitive quaternized fragrance was obtained. A composition containing a polyvinyl alcohol-based polymer compound obtained by pendant of a styryl compound having a group nitrogen-containing heterocycle and a phenyl compound having a sulfonic acid group at a specific molar ratio achieves the above object. They found out the present invention.

The polyvinyl alcohol polymer compound contained in the composition of the present invention is represented by the following general formula (III) in a saponified polyvinyl acetate or a water-soluble copolymer of vinyl alcohol and another vinyl compound. Aldehyde or an acetal represented by the following general formula (IV), and the following general formula
It can be easily obtained by reacting the aldehyde represented by (V) in an aqueous solvent in the presence of an acid catalyst.

[0017]

Embedded image

[0018]

[Chemical 6] (R ₃ and R ₄ are lower alkylene groups, and R ₃
And R ₄ together form an alkylene group)

[0019]

Embedded image

[0020] R ₁ in the general formula (III) and (IV) represents an aromatic nitrogen-containing heterocyclic residue quaternized, such R ₁
The following examples can be given as examples.

[0021]

Embedded image

Here, R ₅ represents a lower alkyl group, a lower alkoxyl group, a lower alkoxyl carbonylalkyl group, or a benzyl group, and Y ⁻ is, for example, chloride ion, bromide ion, iodide ion, lower alkoxysulfate. Ion, an anion such as p-toluenesulfonate ion, Z is O, S, Se, or NR ₆ (R ₆
Represents a lower alkyl group).

The acid catalyst used in the reaction for synthesizing the polyvinyl alcohol polymer compound used in the composition of the present invention is, for example, phosphoric acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, or an acidic ion exchange resin. Can be used, or X in the general formula (V) can be used.
When is hydrogen, it can be used as the catalyst itself.

The reaction is carried out in an aqueous medium, preferably water. The reaction conditions are not particularly limited, but in general,
It can be carried out in a temperature range from room temperature to 100 ° C. for 2 to 72 hours, preferably at 30 to 70 ° C. for 3 to 8 hours, and subsequently at 10 to 30 ° C. for 5 to 20 hours. Good.

After the reaction, the reaction mixture is poured into a large amount of a poor solvent such as acetone, ethanol or dioxane to precipitate a target polymer compound, which is separated, washed with methanol or the like and dried according to the present invention. It is possible to obtain the polyvinyl alcohol polymer compound used in. Alternatively, after the reaction, by neutralizing with an alkaline aqueous solution, for example, an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, aqueous ammonia, or the like, or after neutralizing with a basic ion-exchange resin, the ion-exchange resin is filtered to obtain the purpose. An aqueous solution of the polymer compound can be obtained.

The saponified polyvinyl acetate used in such a reaction has, for example, an average degree of polymerization of 200 to 5,000,
Preferably 300 to 3000, saponification degree 60 to 100
%, Preferably 70 to 99% is suitable.

Here, the average degree of polymerization is set to 200 to 5,000, when the degree of polymerization is less than 200, sufficient sensitivity cannot be obtained. On the other hand, when the degree of polymerization is more than 5,000, the composition is a photosensitive composition. This is because the solution has an excessively high viscosity, resulting in poor coatability or poor water developability, whichever is preferred.

The saponification degree is set to 60 to 100% because if the saponification degree is lower than 60%, sufficient water solubility and water developability cannot be obtained.

As the saponified product of polyvinyl acetate, for example, a modified product of saponified polyvinyl acetate such as hydrophilic group-modified, lipophilic group-modified, anion-modified, cation-modified or reactive group-modified acetoacetyl group may be used. it can.

As described above, a water-soluble copolymer obtained by copolymerizing vinyl alcohol and another vinyl compound can be used in place of the polyvinyl acetate saponified product. Examples of such other vinyl compound include: Examples thereof include N-vinylpyrrolidone and acrylamide.

With such saponified polyvinyl acetate,
When the compound of the general formula (III) or (IV) and the compound of the general formula (V) are reacted in the presence of an acid catalyst, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, and other aldehydes are used. It is also possible to simultaneously react these compounds or these acetals.

General Formula for Saponified Polyvinyl Acetate
The introduction rate of the compound (III) or (IV) is 0.5 to 10 mol%, preferably 0.8 to 7 mol% per monomer unit.
It is. Here, the introduction rate is set to 0.5 to 10 mol% because the sensitivity is low and not practical when it is less than 0.5 mol% and the water solubility is insufficient when it is more than 10 mol%. Generally, if the degree of polymerization of the polyvinyl acetate saponified product used is low, sufficient sensitivity cannot be obtained unless the introduction rate is high, and if the degree of polymerization is high, sufficient sensitivity can be obtained even if the introduction rate is low. Tends to.

General Formula for Saponified Polyvinyl Acetate
The introduction rate of the compound (V) is from 0.6 to 100 per monomer unit.
It is 20 mol%, preferably 0.9 to 20 mol%. Further, the ratio A / B of the introduction rate (denoted as A) of the compound of the general formula (III) or (IV) and the introduction rate (denoted as B) of the compound of the general formula (V) is less than 1, preferably 0. It is 0.8-0.3. A composition using a polymer compound having this ratio of 1 or more cannot achieve the object of the present invention. If this ratio is more than 0.8 and less than 1, the water solubility tends to be insufficient and 0.3
If it is smaller, the water resistance tends to deteriorate.

When the ratio of the above introduction ratio is around 1, the water solubility decreases, and as described in the synthesis example (1) described later, when the obtained high molecular compound is analyzed by ion chromatography, the catalyst acid and methylsulfuric acid are used. Since almost no roots are detected, it is considered that the polyvinyl alcohol-based polymer compound contained in the composition of the present invention has a structure represented by the following formula (VII). Further, it is presumed that the solution obtained by neutralizing the reaction solution is in equilibrium with the following formula (VI) and formula (VII).

[0035]

Embedded image

Incidentally, Japanese Patent Publication No. 3-61939 discloses that
A modified polyvinyl alcohol photosensitive resin having the same constituents as the polymer compound used in the present invention is disclosed. However, this photosensitive resin is A / B> 1 from the description in the specification.
Furthermore, the polarity of such a polymer compound does not change due to the introduction of an acidic group. Therefore, the photosensitive resin disclosed in this publication is different from the object of the present invention. Further, there is no description in this publication regarding the ionicity of the polymer compound.

The composition of the present invention contains the polyvinyl alcohol polymer compound as described above, but preferably further contains an anionic additive.

Examples of the anionic additives include anionic hydrophobic polymer emulsions, anionic surfactants, anionic dyes, anionic pigments, anionic water-soluble polymer compounds, and anionic photosensitizers. Can be mentioned.

Examples of the anionic hydrophobic polymer emulsion include the following (1) to (3).

(1) Hydrophobic polymer emulsion using an anion activator as an emulsifier; examples of anion activators include higher fatty acid salts, higher alkyl dicarboxylic acid salts, higher alcohol sulfate ester salts, alkyl sulfonates,
Higher alkyl disulfonate, sulfated fat and fatty acid salt, sulfonated higher fatty acid salt, higher alkyl phosphate ester salt, higher fatty acid ester sulfate ester salt or sulfonate, higher alcohol ether ether sulfate ester salt or sulfonic acid Salts, condensates of higher fatty acids and amino acids, alkylolated sulfates of higher fatty acid amides, alkylated sulfonates of higher fatty acid amides, alkylcarboxylates of higher alkylsulfonamides, sulfosuccinate ester salts, alkylbenzene sulfones Acid salt, alkylphenol sulfonate, alkylnaphthalene sulfonate, formalin condensate of alkylnaphthalene sulfonate, alkyltetraline sulfonate,
Examples thereof include alkylbenzimidazole sulfonate, naphthenate, and naphthenyl alcohol sulfate ester salt.

(2) Hydrophobic polymer emulsion using anionic protective colloid as an emulsifier; examples of the anionic protective colloid include carboxyl- or sulfonic acid-modified polyvinyl alcohol, polyacrylic acid salt, and polymethacrylic acid salt. it can.

(3) In addition, a hydrophobic polymer emulsion containing an unsaturated compound such as acrylic acid, methacrylic acid, itaconic acid or 2-sulfoethyl methacrylate salt as a copolymerization component.

Examples of the anionic surfactant include those mentioned in the description of the anionic hydrophobic polymer emulsion.

Examples of anionic dyes include direct dyes and acid dyes.

Examples of the anionic pigment include pigments having a carboxylic acid group and a sulfonic acid group, and pigments treated with an anionic polymer.

Examples of the anionic water-soluble polymer include a water-soluble polymer having a carboxyl group or a sulfonic acid.

One of the characteristics of the composition of the present invention is that it can be used in combination with other anionic photosensitizers. Examples of the anionic photosensitizer include 4,4′-diazidostilbene-2,2′-disulfonic acid, 4,4′-diazidodibenzalacetone-2,2′-disulfonic acid and 2,5-bis (4'-Azido-2'-sulfobenzylidene) cyclopentanone, 2,6-bis (4'-azido-2'-sulfobenzylidene) cyclohexanone and their alkali metal salts, ammonium salts, organic amine salts, organic groups Examples thereof include quaternary ammonium salts.

When the composition of the present invention contains the above-mentioned anionic azide-based photosensitizer, it is particularly preferable to further add a water-soluble polymer having a good reactivity with the photoreactive intermediate of the azide group. As such a water-soluble polymer, for example,
Examples include polyvinylpyrrolidone, polyacrylamide, poly (N, N-dimethylacrylamide), copolymers of acrylamide and diacetone acrylamide, copolymers of acrylamide and N, N-dimethylacrylamide, cationized cellulose, and the like. .

The characteristics of the composition of the present invention can be improved by further adding at least one photopolymerizable unsaturated compound and a photopolymerization initiator system.

The photopolymerizable unsaturated compound may be either hydrophobic or hydrophilic, and examples thereof include polymerizable unsaturated unsaturated groups such as acryl group, methacryl group, allyl group, vinyl ether group, vinyl group and acrylamide group. Mention may be made of unsaturated monomers or unsaturated prepolymers having at least one group.

Further, the photopolymerization initiator system may be a system which produces photopolymerization active radicals upon irradiation with light, and examples thereof include benzoin ether, hydroxyalkyl ketone, dialkoxyacetophenone, benzoylphosphine oxide, and benzoin oxime. Α-cleavage type initiators such as ketones, aromatic ketones such as benzophenone, benzyl, thioxanthone and ketocoumarin, and systems of these aromatic ketones and hydrogen donors such as amines, organic peroxides, onium salts, triphenyl Examples thereof include a system of alkyl boric acid or iron-arene complex and an electron donor such as a thioxanthene dye or ketocoumarin, a system of N-arylglycine and an electron attractor, and a polyhalogen compound.

Further, it is usually desirable to add a thermal polymerization inhibitor to these photopolymerization systems.

The composition of the present invention also contains a nonionic hydrophobic polymer emulsion other than the above components, a surfactant, a dye, a pigment, an inorganic filler, an emulsion stabilizer, a plasticizer, a leveling agent and the like. be able to. Further, it is possible to include a cationic additive to the extent that the composition solution does not thicken or gel, and further, various phosphors for forming a phosphor pattern, graphite for forming a black matrix, etc. A light absorbing substance can be included.

The composition of the present invention is prepared by adding the above cationic additive and, if necessary, various additives to the above polyvinyl alcohol polymer compound, and dissolving or dispersing it in a solvent mainly containing water. Can be prepared by

As the solvent used in this case, water is generally used, and a solvent soluble in water at a ratio of 50% by weight or less, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, tetrahydrofuran, A water-soluble agent such as dioxane, dimethylformamide, N-methylpyrrolidinone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc. can be added.

The photosensitive resin composition of the present invention obtained as described above is used on a metal plate such as aluminum or stainless steel, a screen mesh, paper, a glass plate, a semiconductor substrate, or any other substrate depending on the application. For example, 0.5 to 10
It is used by coating and drying so as to have a dry thickness of 00 μm.

These coatings have ultraviolet rays, for example, a wavelength of 3
After irradiating the irradiated part with an actinic ray such as 0 to 500 nm to cure the irradiated part, the non-irradiated part is removed with water or the like to obtain a pattern image. It can be used as body pattern formation, color filter for CCD and LCD, color proof for printing and various etching resists.

A particularly advantageous use in patterning with the compositions of the invention is when patterning on a substrate having an anionic surface. When a pattern is formed on a substrate having an anionic surface by using a conventionally known cationic polyvinyl alcohol-based photosensitive resin, scum remains on the non-exposed portion. When a pattern is formed on such a substrate, a clean pattern without scum is formed.

Next, specific examples of pattern formation using the present composition on a substrate having an anionic surface will be described. The color CRT is red on the inside of the face plate,
A structure consisting of a stripe or dot pattern made of green and blue phosphors and a non-emissive light absorbing substance made of graphite etc. filled in the voids, and the non-emissive light filling the voids in the phosphor pattern. The absorption part is called a black matrix. The manufacturing method is to first form a black matrix and then form phosphor patterns of each color, and a liquid in which graphite is dispersed is used for the black matrix. Examples of the dispersant for graphite include sodium salt of carboxymethyl cellulose (Japanese Patent Publication No. 46-2
18), lithium salt of carboxymethyl cellulose (JP-A-4-82140), and anionic compounds such as β-naphthalene sulfonate. Therefore, the surface of the black matrix is anionic.
A photosensitive composition having a phosphor dispersed therein is applied, and after exposure, development is carried out. However, if the photosensitive composition is cationic, it is not completely developed and scum remains, resulting in unexposed areas. The phosphor on the black matrix remains. When the anionic composition of the present invention is used in the photosensitive composition in which the phosphor is dispersed, a completely developed and clean color-free phosphor pattern can be obtained.

[0060]

【Example】

[Synthesis Example (1)] Polyvinyl alcohol (PVA) GM
-14 L (manufactured by Nippon Synthetic Chemical Industry, degree of polymerization 1200, saponification rate 88%) 10 gr was dissolved in pure water 90 gr. 0.792 gr of N-methyl-4-formylstyrylpyridinium methosulfate (hereinafter abbreviated as SbQ;
1.16 mol% with respect to the unit mol of PVА), and 0.25 gr of phosphoric acid were added, and the mixture was stirred at 30 ° C for 3 hours. Subsequently, 0.772 gr of sodium o-benzaldehyde sulfonate (hereinafter abbreviated as B? S; Sb
(1.57 times mol of Q) was added, and the mixture was stirred at 30 ° C. for 20 hours. The reaction solution was poured into a large amount of acetone to cause a white polymer to break out. The polymer was washed thoroughly with methanol and dried in vacuum to obtain 9.5 gr of polyvinyl alcohol derivative.

SbQ and BAS by UV spectrophotometry
When the binding rate of polyvinyl alcohol to was measured,
It was 1.0 mol% and 1.1 mol%, respectively. In addition, when methyl sulfate radicals derived from SbQ and phosphate radicals derived from the catalyst were measured by ion chromatography analysis, both trace levels were detected. The results of this analysis supported the above-mentioned internal salt structure, and as a result it became clear that this polymer was anionic.

[Synthesis Example (2)] Synthesis Example (1) Amberlite ΙR was added to the reaction solution prepared under the same preparation and reaction conditions.
-45 (Ion exchange resin manufactured by Rohm & Haas) 2.5
gr was added and stirred for 2 hours. After the pH was measured and confirmed to be neutral, the mixture was filtered through 400 mesh mesh.
The product obtained is 1 equivalent to the aqueous polymer solution of Synthesis Example (1).
It showed stability over the years.

[Comparative Synthesis Example (1)] In Synthesis Example (1),
By the same method as in Synthesis Example (1) except that B? S was 0.246 gr (0.5 times mol of SbQ), 1.0 mol% of SbQ and 0.
A 4 mol% bonded polyvinyl alcohol derivative was obtained.

By the same ion chromatographic analysis as in Synthesis Example (1), it was revealed that some SbQ did not form an internal salt because methyl sulfate and phosphate were detected, and as a result, it was a cationic polymer. Became.

[Comparative Synthesis Example (2)] JP-A-55-231
According to the method disclosed in Japanese Patent Laid-Open No. 63-63, the PV PV (GM-
A polyvinyl alcohol derivative having 1.0 mol% of SbQ bonded to 14 L) was obtained. Since this product contains no anion component, it is a completely cationic polymer.

Example (1) The polymer of Synthesis Example (1) was dissolved in pure water to prepare a 10 wt% aqueous solution. Finetex ΕS- which is an anionic emulsion in this aqueous solution
650 (manufactured by Dainippon Ink and Chemicals; polyester emulsion, solid content 29% by weight) was mixed at a solid content ratio of 1: 2. Although a small amount of thickening was observed, a clean photosensitive composition was obtained.

Using the photosensitive composition, a coating film having a thickness of 15 μm was formed on a screen mesh on a 250 mesh screen plate, exposed with a 2 kW ultra-high pressure mercury lamp from a distance of 60 cm for 90 seconds, and developed with water spray. went. When the obtained pattern was observed, swelling was small and the resolution was good.

[Example (2)] When the same test as in Example (1) was conducted using the polymer aqueous solution of Synthesis Example (2), the same result as in Example (1) was obtained with an exposure time of 100 seconds. was gotten.

[Comparative Examples (1) and (2)] As in Example (1), the polymers obtained in Comparative Synthesis Examples (1) and (2) were dissolved in pure water to prepare a 10% by weight aqueous solution. Got When ES-520 was mixed with this aqueous solution at a solid content ratio of 1: 2 in the same manner as in Example (1), an extreme thickening was observed, and a test on a screen similar to that in Example (1) could be performed. There wasn't.

[Example (3)] Polyvinylidone and 4, 4 were placed on a 10 cm square soda glass plate by a general method described in JP-A-48-90815.
Photosensitizing solution containing 4'-diazidostilbene-2,2'-sodium disulfonate, Electroduck 1530
A black matrix for a cathode ray tube having a hole diameter of 105 μm was prepared as follows by using (Achison Japan Ltd .; graphite dispersion) and a shadow mask having a hole diameter of 135 μm.

That is, a so-called phosphor slurry having the following formulation was applied to the above glass plate, dried and applied to a thickness of 8 to 10 μm, and a phosphor pattern was prepared under the following conditions.
When the obtained pattern was observed, the filling degree of the phosphor was good, the resolution was excellent, and there was no remaining phosphor on the black matrix.

(Composition of phosphor slurry) Green phosphor 10 gr 10 wt% polymer aqueous solution of Synthesis Example (1) 10 gr Pure water 15 gr 5% Tamol 731 aqueous solution 1 gr (Rohm & Haas Co .; anionic surfactant) 10% LT-221 aqueous solution 0.05 gr

(Pattern forming conditions) Shadow mask: Hole diameter 135 μm Shadow mask-Glass plate distance: 10 mm Light source-Glass plate distance: 30 cm Light source: Ultra-high pressure mercury, 350 nm, illuminance 0.15 mw / c
m ² exposure time: 40 seconds Development: water spray development

[Comparative Examples (3) and (4)] Similar evaluations were carried out using the polymers of Comparative Synthesis Examples (1) and (2).
However, since neither polymer is sufficiently miscible with tamol 731 which is an anionic surfactant, a phosphor slurry was prepared by removing tamol 731 from the formulation of Example (2).

When these phosphor slurries were used to form a phosphor pattern under the same conditions as in Example (3), the filling degree and resolution of the phosphor were almost the same as in Example (3). A large amount of undeveloped phosphor was observed on the black matrix.

From these results, the polymers of Comparative Synthesis Examples (1) and (2) are cationic polymers, so they tend to remain on the surface of the anionic black matrix due to ionic bonds, and therefore the phosphor is also black. It is presumed that they tend to remain on the matrix surface.

[0077]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, a styryl compound having a photosensitive quaternized aromatic nitrogen-containing heterocycle and a phenyl compound having a sulfonic acid group are pendant in a specific molar ratio. Since it is a photosensitive resin composition using a polyvinyl alcohol-based polymer obtained by doing so, water resistance and heat resistance are good, water solubility is also sufficient, good miscibility with anionic additives Produce an effect.

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Claims (7)

[Claims] 1. A polyvinyl alcohol-based polymer compound having structural units represented by the following general formulas (I) and (II): (R ₁ is a quaternized aromatic-containing nitrogen heterocyclic residue, R ₂ is a hydrogen atom or a lower alkoxyl group, m is 0 or 1,
n represents an integer of 1 to 6) (X represents hydrogen, Na, K, ammonium, organic amine or organic quaternary ammonium) The content of the general formula (I) is 0.5 to 10 mol%,
The content of the general formula (II) is 0.6 to 20 mol%,
A polyvinyl alcohol-based photosensitive resin composition comprising a polyvinyl alcohol-based polymer compound having a molar ratio of less than 1 represented by the general formula (I) / general formula (II). 2. The polyvinyl alcohol-based photosensitive resin composition according to claim 1, wherein the molar ratio represented by the general formula (I) / the general formula (II) is 0.3 to 0.8. . 3. The polyvinyl alcohol-based photosensitive resin composition according to claim 1, further comprising an anionic additive. 4. The anionic additive according to claim 3, wherein the anionic hydrophobic polymer emulsion, anionic surfactant, anionic dye, anionic pigment, anionic water-soluble polymer compound and anion. A polyvinyl alcohol-based photosensitive resin composition, which is at least one selected from the group consisting of a photosensitive agent. 5. A step of applying a polyvinyl alcohol-based photosensitive resin composition according to claim 1 on a substrate to form a photosensitive resin layer, and subjecting the photosensitive resin layer to pattern exposure, And a developing step. 6. The pattern forming method according to claim 5, wherein the surface of the substrate is anionic. 7. The phosphor according to claim 6, wherein the substrate is a substrate on which a black matrix is formed, and a phosphor pattern is formed using a composition in which the photosensitive resin composition contains a phosphor. Pattern forming method.