JP2001051416A - Photosensitive composition based on saponified product of polyvinyl acetate and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive composition soluble in a high boiling point organic solvent such as propylene glycol, developable with water, excellent in safety and having high sensitivity, high adhesiveness to a substrate and good suitability to patterning by dissolving a derivative of a saponified product of polyvinyl acetate having specified constituent units in at least one organic solvent selected from a specified group. SOLUTION: A derivative of a saponified product of polyvinyl acetate having constituent units of formulae I, II, etc., is dissolved in at least one organic solvent selected from the group comprising solvents of formulae III, IV, etc., to obtain the objective photosensitive composition. In the formulae I-IV, (k) and (l) are each an arbitrary natural number, (l) may be 0, R1 is H or methyl, R5 and R6 are each H, methyl, ethyl or acetyl, R7 and R8 are each H, methyl or ethyl, (s) is an integer of 1-4 and (t) is an integer of 1-2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyvinyl acetate saponified photosensitive resin composition, and more particularly to a resin composition which is dissolved in a relatively non-toxic high-boiling organic solvent such as propylene glycol. The present invention relates to a polyvinyl acetate saponified photosensitive resin composition which is developable, has high sensitivity, has high adhesion to a substrate, and has good patterning properties, and a pattern forming method.

[0002]

2. Description of the Related Art Conventionally, water-soluble polyvinyl alcohol-based photosensitive resins have been disclosed in JP-B-56-5761, JP-B-56-5762, JP-A-56-11906, and JP-A-59-17550. Bulletin, Tokuhei 2-27
There is known a polyvinyl alcohol-based photosensitive resin in which a styryl derivative having a quaternized aromatic nitrogen-containing heterocycle disclosed in JP-A-6806 and JP-A-6-43645 is pendant. These photosensitive resins are
It is widely used as a material for screen printing plates, other printing and plate making materials, biocatalyst fixing materials, and electronic materials.

[0003] A quaternary product of styrylpyridinium or styrylquinolium is one of the few photosensitive materials that undergo photodimerization through a singlet state, and has an excellent property of being free from oxygen inhibition.

[0004]

However, a photosensitive resin having a styrylpyridinium or styrylquinolium group and a derivative thereof dissolved in an aqueous solvent are mixed with an inorganic material or the like to form a paste, which is applied to a substrate by screen printing. In this case, the plate is dried and it is difficult to print repeatedly. Also, the coating film after printing is easy to dry,
Poor smoothness and defoaming properties make it difficult to obtain a uniform coating film.

Further, photosensitive resins having styrylpyridinium or styrylquinolium groups and derivatives thereof are soluble in highly polar solvents such as dimethylsulfoxide, but these solvents are highly toxic and have odor and corrosive properties. May not be available depending on the work process.

On the other hand, if polyvinyl alcohol having a low degree of saponification is used, it can be dissolved in some organic solvents but cannot be developed with water.

In view of such circumstances, the present invention pendants styrylpyridinium or styrylquinolium quaternary compound and its derivative which can be dissolved in a relatively safe high-boiling organic solvent such as propylene glycol and developed with water. It is an object to provide a polyvinyl acetate saponified photosensitive composition and a pattern forming method.

[0008]

Means for Solving the Problems A first aspect of the present invention to solve the above-mentioned problem is to provide a polyvinyl acetate saponified derivative having a structural unit represented by the following general formulas (1) to (4): A saponified polyvinyl acetate photosensitive composition characterized by being dissolved in at least one organic solvent selected from the group represented by formulas (5), (6) and (7).

[0009]

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[0010]

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(Where k, l, m, and n represent arbitrary natural numbers, and l may be 0. However, (k + 1 + m / 2 +
n / 2) = 200-4500. R ¹ represents a hydrogen atom or a methyl group. R ² is represented by the following general formula (8),
(9), at least one selected from the group represented by (10) and (11), wherein R ³ and R ⁹ each independently represent a hydrogen atom, an alkyl group or an alkoxy group, and R ⁴ represents A hydrogen atom, a C1-C8 chain hydrocarbon group, an aryl group, an aralkyl group or a heterocyclic group,
p represents an integer in the range of 1 to 6, and q represents 0 or 1. R ⁵ and R ⁶ are each independently a hydrogen atom, a methyl group,
Represents an ethyl group or an acetyl group; R ⁷ and R ⁸ each independently represent a hydrogen atom, a methyl group or an ethyl group; s represents an integer in the range of 1 to 4; R ¹⁰ represents a member selected from the group consisting of a hydrogen atom, an alkyl group or an aralkyl group and a mixture thereof, and the alkyl group or the aralkyl group is a hydroxyl group, a carbamoyl group, an ether bond, an ester bond, and an unsaturated bond, respectively. And at least one member selected from the group consisting of
R ¹¹ represents an alkylene group, X ⁻ represents a cobasic ion of an acid, and Y ⁻ represents SO ₃ ^— or CO ₂ ^— . )

[0012]

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According to a second aspect of the present invention, in the first aspect, (k + 1 + m / 2 + n) of the general formulas (1) to (4) is used.
/ 2) = 300-3000, and (k + 1 + m / 2 +
n / 2), wherein the ratio of l to be 50% or less is the photosensitive polyvinyl acetate saponified photosensitive composition.

According to a third aspect of the present invention, in the first or second aspect, (k + 1 + m) of the general formulas (1) to (4) is used.
/ 2 + n / 2), wherein the proportion of m is in the range of 0.5 to 5% and the proportion of n is in the range of 3 to 25%.

In a fourth aspect of the present invention, in any one of the first to third aspects, R ^{4 in the} general formula (4) is C ² to C
5. A polyvinyl acetate saponified photosensitive composition, which is a chain hydrocarbon of No. 5.

According to a fifth aspect of the present invention, there is provided a polyvinyl acetate saponified photosensitive composition according to any one of the first to fourth aspects, further comprising at least one of an inorganic powder and an organic powder dispersed therein. In the composition.

According to a sixth aspect of the present invention, a polyvinyl acetate saponified photosensitive composition according to any one of the first to fifth aspects is applied to a substrate and dried, followed by pattern exposure, and a developer mainly composed of water. And a pattern forming method characterized by developing.

According to a seventh aspect of the present invention, there is provided a pattern forming method according to the sixth aspect, wherein the polyvinyl acetate saponified photosensitive composition is applied to a substrate by a screen printing method or a blade coating method. In the way.

As a result of intensive studies to solve the above-mentioned problems, a photosensitive resin having styryl pyridinium or styryl quinolium quaternized polyvinyl acetate and a derivative thereof have a hydrophobic group at a specific ratio. To improve the hydrophobicity of the resin itself until it is dissolved in a high-boiling organic solvent such as propylene glycol, and found that development with water is possible without lowering favorable performance such as sensitivity and adhesion. Thus, the present invention has been achieved.

Here, in the photosensitive composition of the present invention, it is preferable to use an organic solvent represented by the above general formula (5), (6) or (7), and these are used in combination of two or more kinds. You can also. As an example, ethylene glycol, diethylene glycol, triethylene glycol,
Ethylene glycols such as tetraethylene glycol,
Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Glycol ether acetates such as diethylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate; propylene glycols such as propylene glycol and dipropylene glycol; propylene glycol monomethyl ether; propylene glycol monoethyl ether Le, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, propylene glycol ethers such as dipropylene glycol diethyl ether, triethylene glycol, and the like.

Among the above-mentioned organic solvents, propylene glycol and dipropylene glycol are particularly preferable in consideration of the effect on the human body and the solubility.

Further, other solvents can be mixed as long as the solubility of the photosensitive resin used in the present invention is not impaired. If there is no practical problem, water can be used in combination.

In the general formulas (1) to (4) of the present invention, (k + 1
+ M / 2 + n / 2) is preferably in the range of 200 to 4500, more preferably 300 to 3000. If it is smaller than this range, the film will not have sufficient strength even when cured with light, and the pattern will be lost due to development. Also,
When it is larger than this range, a hydrogen-bonding gel tends to be formed.

Further, (k + 1 +) of the general formulas (1) to (4)
It is preferable that the ratio of l to be (m / 2 + n / 2) is 50% or less. When 1 is larger than 50, the developability with water is reduced, and a residue is generated in an unexposed portion.

In the present invention, the ratio of m represented by (k + 1 + m / 2 + n / 2) in the general formulas (1) to (4) is 0.1.
It is preferably in the range of 5 to 5%, more preferably 0.8 to 4%. Below this range, the sensitivity is insufficient, and above this range, the developability with water decreases.

In the present invention, the ratio of n represented by (k + 1 + m / 2 + n / 2) in the general formulas (1) to (4) is 3 to 2
Preferably it is in the range of 5%. Below this range,
Poor hydrophobicity and easy to gel. Above this range, development residues are likely to occur, and the adhesion to the substrate is also reduced. Further, R ⁴ in the general formula (4) is C2 to C
It is preferably a chain hydrocarbon of No. 5. This is for imparting appropriate hydrophobicity.

The photosensitive composition of the present invention can be prepared in an aqueous solution or a mixed solution of water and an organic solvent by the following general formula (12)
Or after introducing an aldehyde or acetal of styrylpyridinium or styrylquinolium quaternary represented by (13) and an aldehyde or an acetal of the general formula (4) into a saponified polyvinyl acetate,
It is achieved by dehydrating and dissolving in an organic solvent. The dehydration is performed by a method such as heat distillation, vacuum distillation, azeotropic dehydration, etc., and these may be used in combination. Alternatively, it can be prepared by pouring a polymer synthesized in water into a poor solvent, taking out the polymer, and dissolving the polymer in an organic solvent.

[0028]

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(R ² and R ³ are the same as in the above formula (3).)

The above-mentioned saponified polyvinyl acetate is obtained by copolymerizing another vinyl monomer for the purpose of controlling the developing property and improving the properties of the resist, modifying the hydrophilic group, modifying the lipophilic group, modifying the terminal, modifying the cation, and modifying the anion. A modified polyvinyl acetate saponified product such as a modified product is also applicable.

Compounds to be introduced into the saponified polyvinyl acetate to form the general formula (4) include formaldehyde, acetaldehyde, propionaldehyde, n-
Butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, pivalinaldehyde,
C1-C9 such as capronaldehyde and heptaldehyde
Aliphatic unsaturated aldehydes such as C1-C9 such as aliphatic saturated aldehydes, acrolein, crotonaldehyde, and propioaldehyde, benzaldehyde, orthotolualdehyde, metatolualdehyde, aromatic aldehydes such as paratolualdehyde, and furfural. Heterocyclic aldehydes and their acetalized products can be mentioned. These can be used alone or in combination of two or more.

Examples of the catalyst used for the acetalization include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid; organic acids such as oxalic acid, methanesulfonic acid and dodecylbenzenesulfonic acid;
And an acidic ion exchange resin. These are desirably neutralized or removed after the reaction.

At the time of the synthesis, the addition of the aldehyde or acetal compound of the general formula (4) or the aldehyde compound or acetal compound of styrylpyridinium or styrylquinolium quaternary compound to the reaction system may be carried out simultaneously. Since the aldehyde forming the formula (4) or the acetalized product thereof prevents the introduction of styrylpyridinium or styrylquinolium quaternary compound, it is more preferable to provide a time lag between the additions.

The solvent used for the azeotropic dehydration includes aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene.

Further, an aldehyde or an acetalized product thereof which forms the general formula (4) is introduced, and a saponified polyvinyl acetate previously dissolved in an organic solvent is dissolved in the organic solvent. It is also possible to introduce quaternaries of pyridinium or styrylquinolium.

It is possible to disperse in the photosensitive resin of the present invention.
The inorganic powder that can be used is ZnO: Zn, Zn
_Three(PO_Four)_Two: Mn, Y_TwoSiO_Five: Ce, CaWO_Four: P
b, BaMgAl₁₄O_{twenty three}: Eu, ZnS: (Ag, C
d), Y_TwoO_Three: Eu, Y_TwoSiO_Five: Eu, Y_ThreeAl
_FiveO₁₂: Eu, YBO_Three: Eu, (Y, Gd) BO_Three: E
u, GdBO_Three: Eu, ScBO_Three: Eu, LuBO_Three:
Eu, Zn_TwoSiO_Four: Mn, BaAl₁₂O₁₉: Mn, S
rAl₁₃O₁₉: Mn, CaAl₁₂O₁₉: Mn, YB
O_Three: Tb, BaMgAl₁₄O_{twenty three}: Mn, LuBO_Three: T
b, GdBO_Three: Tb, ScBO _Three: Tb, Sr₆Si_ThreeO
_ThreeC₁₄: Eu, ZnS: (Cu, Al), ZnS: A
g, Y_TwoO_TwoS: Eu, ZnS: Zn, (Y, Cd) BO
_Three: Eu, BaMgAl_TenO_{1 7}: Phosphor powder such as Eu,
PbO-SiO_TwoSystem, PBO-B_TwoO_Three-SiO_TwoSystem, Zn
O-SiO_TwoSystem, ZnO-B_TwoO_Three-SiO_TwoSystem, BiO-
SiO_TwoSystem, BiO-B_TwoO_Three-SiO_TwoLead borosilicate gas
Glass, zinc borosilicate glass, bismuth borosilicate glass, etc.
Glass powder, cobalt oxide, iron oxide, chromium oxide, acid
Nickel oxide, copper oxide, manganese oxide, neodymium oxide,
Vanadium oxide, cerium chippek yellow, oxidation
Cadmium, alumina, silica, magnesia, spinel
Na, K, Mg, Ca, Ba, Ti, Zr, Al, etc.
Oxides, iron, nickel, copper, aluminum, silver, gold
And the like. These can be used alone or
Alternatively, two or more kinds can be used in combination.

The organic powder that can be dispersed in the photosensitive composition of the present invention includes azo pigments, phthalocyanine pigments, indigo pigments, anthraquinone pigments, perylene pigments, perinone pigments, dioxazine pigments. Organic pigments such as quinacridone pigments, isoindolinone pigments, phthalone pigments, and methine / azomethine pigments are applicable.

These inorganic powders and organic powders can be used singly or in combination of two or more kinds, and 50 to 240 parts by weight based on 100 parts by weight of the total of the photosensitive resin composition.
It is preferable to mix in a range of 0 parts by weight. If the amount is more than 2400 parts by weight, the photocurability may be reduced and the pattern may be missing. If the amount is less than 50 parts by weight, when the photosensitive material needs to be removed by baking, problems such as contraction of the pattern may occur.

In the photosensitive composition of the present invention, conventionally known components such as a plasticizer, a pigment, a dye, an antifoaming agent, a coupling agent and a leveling agent can be added as necessary.

The photosensitive composition of the present invention may be a solution or
It is applied as a paste. The application method is not particularly limited, but screen printing, curtain coating, blade coating, spin coating, spray coating, dip coating,
A slit coat or the like is applied.

After the applied solution or paste has passed through a drying step, it is exposed through a predetermined mask. The photosensitive wavelength is 300 to 450 nm, and a high-pressure mercury lamp, arc lamp, chemical lamp, metal halide lamp, xenon lamp, or the like can be used. The exposed coating film is developed by a wet process to form a pattern.

The developing method can be any of a spray type, a paddle type, and an immersion type, but a spray type with little residue is preferable. Ultrasonic waves or the like can be applied as needed.

The developer is preferably neutral water. It is also possible to add an organic solvent, a surfactant, an antifoaming agent and the like for the purpose of assisting the developing property.

Examples of the organic solvent which can be added to the developer include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol,
Alcohols such as butanol and tert-butanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, glycols such as trimethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl Glycos such as ether, diethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, etc. Ethers, N- methylpyrrolidone, N, N- dimethylformamide, N, N- dimethylacetamide and the like.

The amount of the organic solvent added to the developer is
It is preferably 100 parts by weight or less with respect to 00 parts by weight, and more preferably 20 parts by weight or less in consideration of the safety of the working environment.

Examples of the surfactant that can be added to the developer include aliphatic carboxylic acid salts such as sodium laurate and sodium oleate, and higher alcohol sulfates such as sodium lauryl sulfate and castor oil sulfate sodium. Ester salts, sodium polyoxyethylene lauryl ether sulfate, polyoxyethylene lauryl ether sulfate triethanolamine, etc., polyoxyethylene alkyl ether sulfate salts, sodium polyoxyethylene octyl phenyl ether sulfate, polyoxyethylene octyl phenyl ether sulfate Polyoxyethylene alkyl allyl ether such as ester triethanolamine, sodium polyoxyethylene nonyl phenyl ether sulfate Acid ester salts, alkyl diphenyl ether disulfonates, alkyl disulfonates, alkyl allyl sulfonates such as sodium dodecylbenzene sulfonate, sodium dibutyl naphthalene sulfonate, sodium triisopropyl naphthalene sulfonate, and higher alcohols such as sodium lauryl phosphate diester Phosphate salts, polyoxyethylene lauryl ether phosphate monoester disodium,
Polyoxyethylene alkyl ether phosphate salts such as sodium polyoxyethylene lauryl ether phosphate, sorbitan fatty acid esters such as sorbitan monostearate, sorbitan monooleate and sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, poly Polyoxyethylene sorbitan fatty acid esters such as oxyethylene coconut oil fatty acid sorbitan, polyoxyethylene sorbitan monopalmitate, alkyl betaines such as acetylene glycols and lauryl dimethyl amino acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxy And alkylimidazolines such as ethylimidazolinium betaine. These can be used alone or in combination of two or more. The addition amount is neutral water 1
0.01 to 15 parts by weight is preferable with respect to 00 parts by weight,
0.01 to 10 parts by weight is more preferable.

For the purpose of suppressing foaming at the time of development, for example, silicone resin-based antifoaming agents such as silicone resin, fluorine silicone resin, and an inorganic powder compound of silicone resin, castor oil, sesame oil, linseed oil, etc. Fatty acids, higher fatty acids such as stearic acid, oleic acid, palmitic acid, etc., fatty acid esters such as isoamyl stearic acid, diglycol lauric acid, distearyl succinic acid, sorbitan monolauric acid, polyoxyethylene sorbitan, polyoxyalkylene glycol, poly Oxyalkylene glycol derivatives, alcohols such as methanol, ethanol, isopropanol, sec-butanol, n-butanol, 3-heptal, 2-ethylhexanol, di-tert-aminophenoxyethanol, di-tert
Ethers such as aminophenoxyethanol, 3-heptylcellosolve and nonylcellosolve-3-heptylcarbitol, phosphates such as tributylphosphate, sodium octylphosphate, and tris (butoxyethyl) phosphate; amines such as diamylamine; Amides such as polyalkylene amide, acylate polyamine, dioctadecanoylpiperidine, metal soaps such as A1-stearic acid, Ca-stearic acid, K-oleic acid, Na-dodecylsulfonic acid, Na-laurylsulfonic acid, etc. Can be added. The addition amount is 0.01 to 10 with respect to the total developer.
% By weight is preferred.

[0048]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, examples of the present invention will be described. However, since the examples differ according to the type and purpose of use of the photosensitive composition constituted by using this polymer compound, the present invention is merely an example. It does not limit the range of.

Example 1 100 g of a vinyl acetate polymer having a degree of polymerization of 600 and a degree of saponification of 70 was dissolved in 535 g of water.
23.3 g of methyl-γ- (p-formylstyryl) pyridinium methosulfate (hereinafter referred to as SbQ), 5 g of phosphoric acid
Was added and stirred at 30 ° C. for 6 hours. Then, 267 g of propylene glycol, 10.4 g of n-butyraldehyde
And further stirred at 30 ° C. for 14 hours.

Add 65 ml of anion exchange resin to this solution.
(Amberlist IRA-4 manufactured by Rohm and Haas
5) was added and neutralized by stirring at 50 ° C. for 4 hours.
The ion exchange resin was separated by filtration.

Further, 628 g of propylene glycol,
After azeotropic dehydration by adding 50 g of cyclohexane, cyclohexane was distilled off to obtain a photosensitive resin solution using propylene glycol as a solvent. The azeotropic dehydration was performed at 74 ° C, and the distillation of cyclohexane was performed at 81 ° C.

SbQ in the resin thus obtained
As a result of nuclear magnetic resonance spectroscopy, the addition amounts of n-butyraldehyde and n-butyraldehyde were 2.7 mol% and 5.5 m, respectively.
ol%.

This photosensitive resin solution was applied on a soda glass plate with a spin coater, dried in a clean oven at 80 ° C. for 30 minutes, cooled to room temperature, and illuminated at 5.0 mW through a mask having a predetermined pattern. It was irradiated with ultraviolet rays of 50 mJ / cm ² by an ultra-high pressure mercury lamp / cm ^2. Subsequently, it was spray-developed with ion-exchanged water for 30 seconds to obtain a desired pattern. The pattern film thickness was 5 μm, and the sensitivity was 10 steps with a Ugra step tablet.

The photosensitive resin solution was stored at 40 ° C., and the change in patterning characteristics was examined. No change was observed in the physical properties even after 2 weeks.

Example 2 100 g of a vinyl acetate polymer having a degree of polymerization of 600 and a degree of saponification of 70 was dissolved in 388 g of water.
15.9 g of methyl-γ- (p-formylstyryl) pyridinium methosulfate and 2 g of methanesulfonic acid were added, and 3
Stirred at 0 ° C. for 6 hours. Next, 259 g of propylene glycol and 13.4 g of benzaldehyde were added, and the mixture was further stirred at 30 ° C. for 14 hours.

To this solution was added 36 ml of anion exchange resin.
(Amberlist IRA-4 manufactured by Rohm and Haas
5) was added and neutralized by stirring at 50 ° C. for 4 hours.
The ion exchange resin was separated by filtration.

Further, 607 g of propylene glycol,
After azeotropic dehydration by adding 50 g of cyclohexane, cyclohexane was distilled off to obtain a photosensitive resin solution using propylene glycol as a solvent. The azeotropic dehydration was performed at 74 ° C, and the distillation of cyclohexane was performed at 81 ° C.

SbQ in the resin thus obtained
And the amount of benzaldehyde added were 2.1 mol% and 5.0 mol, respectively, as a result of nuclear magnetic resonance spectroscopy.
%Met.

This photosensitive resin solution was applied on a soda glass plate with a spin coater, dried in a clean oven at 80 ° C. for 30 minutes, cooled to room temperature, and passed through a mask having a predetermined pattern to obtain an illuminance of 5.0 mW / It was irradiated with ultraviolet rays of 50 mJ / cm ² by an ultra high pressure mercury lamp cm ^2. Subsequently, it was spray-developed with ion-exchanged water for 30 seconds to obtain a desired pattern. The pattern film thickness was 5 μm, and the sensitivity was 8 steps with a Ugra step tablet.

This photosensitive resin solution was stored at 40 ° C., and the change in patterning characteristics was examined. No change was observed in the physical properties even after 2 weeks.

(Example 3) Degree of polymerization 1100, degree of saponification 80
Is dissolved in 676 g of water,
8.3 g of -methyl-γ- (p-formylstyryl) quinolium methosulfate (hereinafter referred to as SQQ), 4 g of oxalic acid
Was added and stirred at 30 ° C. for 6 hours. Then, 477 g of propylene glycol, 11.0 g of n-butyraldehyde
And further stirred at 30 ° C. for 14 hours.

To this solution was added 52 ml of anion exchange resin.
(Amberlist IRA-4 manufactured by Rohm and Haas
5) was added and neutralized by stirring at 50 ° C. for 4 hours.
The ion exchange resin was separated by filtration.

Further, 321 g of propylene glycol,
After azeotropic dehydration by adding 50 g of cyclohexane, cyclohexane was distilled off to obtain a photosensitive resin solution using propylene glycol as a solvent. The azeotropic dehydration was performed at 74 ° C, and the distillation of cyclohexane was performed at 81 ° C.

The SQQ of the resin thus obtained was
As a result of nuclear magnetic resonance spectroscopy, the addition amount of n-butyraldehyde was 0.65 mol% and 7.2, respectively.
mol%.

This photosensitive resin solution was applied on a soda glass plate with a spin coater, dried in a clean oven at 80 ° C. for 30 minutes, cooled to room temperature, and passed through a mask having a predetermined pattern to an illuminance of 5.0 mW / It was irradiated with ultraviolet rays of 30 mJ / cm ² by an ultra high pressure mercury lamp cm ^2. Subsequently, it was spray-developed with ion-exchanged water for 30 seconds to obtain a desired pattern. The pattern film thickness was 5 μm, and the sensitivity was 10 steps with a Ugra step tablet.

The photosensitive resin solution was stored at 40 ° C., and the change in patterning characteristics was examined. No change was observed in the physical properties even after 2 weeks.

(Example 4) Degree of polymerization: 2300, degree of saponification: 88
Is dissolved in 713 g of water,
11.7 g of -methyl-γ- (p-formylstyryl) pyridinium methosulfate (hereinafter referred to as SbQ) and 2 g of methanesulfonic acid were added, and the mixture was stirred at 30 ° C for 6 hours. Next, 441 g of propylene glycol and 14.2 g of propionaldehyde were added, and the mixture was further stirred at 30 ° C. for 14 hours.

To this solution was added 26 ml of anion exchange resin.
(Amberlist IRA-4 manufactured by Rohm and Haas
5) was added and neutralized by stirring at 50 ° C. for 4 hours.
The ion exchange resin was separated by filtration.

Further, propylene glycol 1007
g and 70 g of cyclohexane, and azeotropic dehydration was performed. Then, cyclohexane was distilled off to obtain a photosensitive resin solution using propylene glycol as a solvent. Azeotropic dehydration at 74 ° C,
Cyclohexane was distilled off at 81 ° C.

SbQ in the resin thus obtained
The amounts of propionaldehyde and propionaldehyde were determined to be 1.4 mol%, 10.3
mol%.

This photosensitive resin solution was applied on a soda glass plate with a spin coater, dried in a clean oven at 80 ° C. for 30 minutes, cooled to room temperature, and passed through a mask having a predetermined pattern to give an illuminance of 5.0 mW / It was irradiated with ultraviolet rays of 30 mJ / cm ² by an ultra high pressure mercury lamp cm ^2. Subsequently, it was spray-developed with ion-exchanged water for 30 seconds to obtain a desired pattern. The pattern film thickness was 5 μm, and the sensitivity was 10 steps with a Ugra step tablet.

This photosensitive resin solution was stored at 40 ° C., and the change in patterning characteristics was examined. No change was observed in the physical properties even after 2 weeks.

Comparative Example 100 g of a partially saponified polyvinyl acetate saponification having a degree of polymerization of 600 and a degree of saponification of 70 was dissolved in 535 g of water, 23.3 g of SbQ and 5 g of phosphoric acid were added, and the mixture was stirred at 30 ° C. for 6 hours. Then propylene glycol 267
g was added and the mixture was further stirred at 30 ° C. for 14 hours.

To this solution was added 36 ml of anion exchange resin.
(Amberlist IRA-4 manufactured by Rohm and Haas
5) was added and neutralized by stirring at 50 ° C. for 4 hours.
The ion exchange resin was separated by filtration.

Further, 558 g of propylene glycol,
50 g of cyclohexane was added to perform azeotropic dehydration and distillation of cyclohexane, but the solution gelled.

[0076]

As described above, the polyvinyl acetate photosensitive resin of the present invention is soluble in a relatively low toxic high boiling organic solvent such as propylene glycol and can be developed with water. Excellent in nature. Further, since it has high sensitivity, high adhesiveness to a substrate, and good patterning properties, it has a wide range of practical uses and applications, and is of great industrial value.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) (72) Inventor Shinji Sakai 4-2-1 Wakahagi, Inba-mura, Inba-gun, Chiba Prefecture Toyo Gosei Kogyo Co., Ltd. Inside Photosensitive Materials Research Laboratory (72) Inventor Tetsuaki Tochizawa 4-2-1 Wakahagi, Inba-mura, Inba-gun, Chiba Pref.

Claims (7)

[Claims] 1. A structure represented by the following general formulas (1) to (4):
A saponified polyvinyl acetate derivative having a constitutional unit is
Select from groups represented by general formulas (5), (6) and (7)
Dissolved in at least one organic solvent
Characterized by a polyvinyl acetate saponified photosensitive composition. Embedded imageEmbedded image(Where k, l, m, and n represent arbitrary natural numbers, and l is 0
There is a case. However, k + 1 + m / 2 + n / 2 = 200
４4500. R¹Represents a hydrogen atom or a methyl group
You. R^TwoAre the following general formulas (8), (9), (10) and
At least one selected from the group represented by (11)
And R^ThreeAnd R⁹Are independent hydrogen atoms,
Represents an alkyl group or an alkoxy group;^FourIs a hydrogen source
, A C1-C8 chain hydrocarbon group, an aryl group, an arral
Represents a kill group or a heterocyclic group, and p is an integer in the range of 1 to 6.
The number q represents 0 or 1. R^FiveAnd R⁶Are each other
Independently hydrogen, methyl, ethyl or acetyl
R⁷And R⁸Are independent of each other
Represents an atom, a methyl group or an ethyl group, s is 1-4, t
And u represents an integer in the range of 1-2. R^TenIs hydrogen field
Selected from the group consisting of a substituent, an alkyl group or an aralkyl group
Represented by the following formula:
Or an aralkyl group is a hydroxyl group,
Bamoyl group, ether bond, ester bond and unsaturated
Including at least one member selected from the group consisting of bonds
And those not included. R¹¹Is an alkylene group
And X ^-Represents a co-basic ion of an acid;^-Is S
O_Three ^-Or CO_Two ^-Represents ) 2. The method according to claim 1, wherein
In (4), k + 1 + m / 2 + n / 2 = 300 to 3000, and the ratio of l to k + 1 + m / 2 + n / 2 is 50.
% Or less, a photosensitive polyvinyl acetate saponified photosensitive composition. 3. The method according to claim 1, wherein the ratio of m to k + 1 + m / 2 + n / 2 in the general formulas (1) to (4) is 0.5 to 5%, and the ratio of n is 3 to 25%. A saponified photosensitive polyvinyl acetate derivative composition. 4. The photosensitive polyvinyl acetate saponified photosensitive material according to claim 1, wherein R ⁴ in the general formula (4) is a chain hydrocarbon of C2 to C5. Composition. 5. The photosensitive polyvinyl acetate saponified photosensitive composition according to claim 1, further comprising at least one of an inorganic powder and an organic powder dispersed therein. 6. A pattern forming method, comprising applying the photosensitive composition according to any one of claims 1 to 5 to a substrate, drying and applying a pattern, and developing with a developer mainly composed of water. 7. A pattern forming method, comprising applying the photosensitive composition according to claim 1 to a substrate by a screen printing method or a blade coating method.