JPS6345725B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a method for producing a photosensitive resin. More specifically, the present invention relates to a method for producing a photosensitive resin by reacting polyvinyl alcohol with a styrylpyridinium salt compound or a styrylquinolinium salt compound. Technical Background The following three methods have been known as methods for producing photosensitive resins by reacting polyvinyl alcohol with styrylpyridinium salt compounds or styrylquinolinium salt compounds. (1) Conventional method 1 Polyvinyl alcohol and a styrylpyridinium salt compound or a styrylquinolinium salt compound are dissolved in water, and the two are subjected to a condensation reaction under an acidic catalyst. After the reaction is completed, the reaction solution is neutralized with an alkaline aqueous solution to obtain a photosensitive resin. According to this method, the sensitivity of the obtained photosensitive resin decreases due to unreacted styrylpyridinium salt compound or styrylquinolinium salt compound and an inorganic salt consisting of an acidic catalyst and a neutralizing base.
Another disadvantage is that the water resistance of the resin film formed after exposure and water development is reduced. (2) Conventional Method 2 Polyvinyl alcohol and a styrylpyridinium salt compound or a styrylquinolinium salt compound are dissolved in water, and the two are subjected to a condensation reaction under an acidic catalyst. After the reaction is complete, the photosensitive resin produced in a poor solvent is precipitated or treated with an ion exchange resin to remove unreacted styrylpyridinium salt compounds or styrylquinolinium salt compounds and acidic catalysts. get. According to this method, compared to the photosensitive resin produced by Production Method 1, the sensitivity of the photosensitive resin and the water resistance of the resin film formed after exposure and water development are improved. However, this method requires a large amount of organic solvent as a precipitant or a large amount of ion exchange resin, so when this method is put into practical use industrially, it has disadvantages such as complicated steps and increased costs. Therefore, this method is not suitable for practical use. (3) Conventional method 3 A styrylpyridinium salt compound or a styrylquinolinium salt compound and an acidic catalyst,
A photosensitive resin obtained by dissolving in water or a mixed solvent of water and an organic solvent having good compatibility with water, mixing polyvinyl alcohol into this solution, and causing a condensation reaction between the two. is thoroughly washed to remove unreacted styrylpyridinium salt or styrylquinolinium salt and acidic catalyst. According to this method, when unreacted styrylquinolinium salt compounds or styrylpyridinium salt compounds are washed away, a considerable proportion of the photosensitive resin, which is the main product, is also washed away. This results in serious drawbacks such as the resin yield decreasing to 50-70%. In particular, when partially saponified polyvinyl acetate is used as the polyvinyl alcohol, it has a tendency to easily swell in water, so the above-mentioned drawbacks tend to occur strongly. In addition, partially saponified polyvinyl acetate tends to form grains, resulting in additional drawbacks such as significantly reduced workability. Purpose of the Invention The purpose of the present invention is to provide a method for producing a photosensitive resin that has excellent photosensitivity and can form a tough resin film in a high yield, and that is easy to work with. It's about doing. Structure of the Invention The method of the present invention is based on the following general formulas () and (): [However, Y in the above formula is the following general formula () and ():

【formula】

[Formula] (In the above formula, R ₁ represents a member selected from the group consisting of a hydrogen atom, an alkyl group, and an aralkyl group, and the alkyl group and aralkyl group are a hydroxyl group, a carbamoyl group, an ether bond, and an aralkyl group, respectively. _R2 represents a member selected from the group consisting of a hydrogen atom and a lower alkyl group, and X ^- is an anion. ion), m represents an integer from 1 to 6, n represents 0 or 1, and t represents 0 or 1] One type of quaternary ammonium salt compound and polyvinyl alcohol are reacted to form 0.2 to 20 mol% of the following general formula (): and 59.8 to 99.8 mol% of the following general formula (): and 0 to 40 mol% of the following general formula (): When producing a modified polyvinyl alcohol photosensitive resin having a polymer constitutional unit, the above-mentioned quaternary ammonium salt compound is dissolved in water together with an acidic catalyst, and the resulting aqueous solution is mixed with an aromatic hydrocarbon compound, an aliphatic At least one selected from hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, higher alcohols, ketones, esters, and ethers
emulsifying the seed in a solvent consisting of a water-insoluble organic compound and dispersing the polyvinyl alcohol powder particles in the resulting emulsion, thereby dispersing the quaternary ammonium salt in the dispersed polyvinyl alcohol powder particles. This is a method for producing a modified polyvinyl alcohol photosensitive resin, which is characterized by absorbing an aqueous compound solution and reacting the two. Detailed Description of the Invention In the method of the present invention, the following general formulas () and (): [However, Y in the above formula is the following general formula () and ():

【formula】

At least one quaternary ammonium salt compound, that is, a styrylpyridinium salt compound and/or a styrylquinolinium salt compound, represented by: By reacting polyvinyl alcohol in the presence of an acidic catalyst, 0.2 to 20 mol% of the following general formula (): and 59.8 to 99.8 mol% of the following general formula (): and 0 to 40 mol% of the following general formula (): A modified polyvinyl alcohol photosensitive resin having a polymer constitutional unit of 1 is produced. In the above general formulas () and (), R ₁ is a hydrogen atom or an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl group, and aralkyl groups such as benzyl, phenylethyl, methylbenzyl, and naphthylmethyl groups. These alkyl groups and aralkyl groups may be unsubstituted, or may contain one or more selected from hydroxyl groups, carbamoyl groups, ether bonds, unsaturated double bonds, and the like. Also
R ₂ is selected from hydrogen atoms and lower alkyl groups, preferably those containing 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, pertyl, and hexyl groups. Furthermore, X ^- represents an anion, such as chloride ion, bromide ion, sulfate ion, methoxysulfate ion, phosphate ion, perchlorate ion, hydroborate ion, methanesulfonate ion, p-toluenesulfonate ion, etc. selected from. Compounds of general formula () and/or () are:
It is generally used in a proportion of 0.25 to 100 parts by weight, preferably 0.5 to 50 parts by weight, based on 100 parts by weight of polyvinyl alcohol. Acidic catalysts used for the reaction between the compound of general formula () and polyvinyl alcohol include hydrochloric acid, sulfuric acid,
It is selected from phosphoric acid, perchloric acid, hydroborofluoric acid, p-toluenesulfonic acid, acetic acid, citric acid, etc., and is generally used in a proportion of 0.01 to 10% by weight based on the reaction mixture. In the method of the present invention, the compound of general formula () and or () and the required amount of the acidic catalyst are dissolved in water, and this aqueous solution is mixed with stirring in an organic solvent that is incompatible with water, Emulsify this.
Next, a required amount of polyvinyl alcohol powder is dispersed in the obtained emulsion, and an aqueous solution containing the compound of the general formula () and/or () and an acidic catalyst is absorbed into the dispersed polyvinyl alcohol powder particles, In this state, polyvinyl alcohol and the compound of general formula () and/or () are reacted. In the method of the present invention, when preparing an aqueous solution containing the compound of general formula () and/or () and an acidic catalyst, the amount of water used is such that the polyvinyl alcohol is uniformly swollen at the reaction temperature;
The amount is preferably such that it does not dissolve. Generally, the ratio of the weight of water to the weight of polyvinyl alcohol is preferably in the range of 0.2 to 10;
It is more preferably within the range of 0.5 to 5. The aqueous solution prepared as described above is dispersed in an organic solvent that is incompatible with water. Such organic solvents include aromatic hydrocarbon compounds, aliphatic hydrocarbons,
It is composed of at least one selected from alicyclic hydrocarbons, halogenated hydrocarbons, higher alcohols, ketone compounds, ester compounds, and ether compounds. The aromatic hydrocarbon compound used in the method of the present invention has the following general formula: [However, in the above formula, R ₃ and R ₄ each represent a hydrogen atom or an alkyl group, preferably an alkyl group containing 1 to 3 carbon atoms, such as methyl, ethyl, and propyl group, Z represents a hydrogen atom or a halogen atom, such as a chlorine atom or a bromine atom, and l represents an integer of 1 to 4, preferably 1 to 3.] For example, benzene, Selected from toluene, xylene, chlorobenzene, dichlorobenzene, chlorotoluene, cyclotoluene, etc. The aliphatic hydrocarbon is preferably represented by the following general formula: C _a H _{2 (a+1)} [wherein a represents an integer of 5 to 10], and includes pentane, hexane, heptane, Selected from octane, nonane, decane, isopentane, etc. The alicyclic hydrocarbon is preferably one represented by the following general formula C _a H _2a [where a represents an integer of 5 to 10], for example,
Selected from cyclohexane, cyclopentane, methylcyclohexane, dimethylcyclohexane, etc. The halogenated hydrocarbon has the following general formula C _b A _d H _2(b+1)-d [However, in the above formula, b represents an integer from 1 to 3, and d
represents an integer of 1 to 4, and A represents a halogen atom, such as a chlorine atom or a bromine atom]. Examples include chloroform, carbon tetrachloride, dichloromethane, trichloroethane, dichloropropane, trichloropropane, Selected from methylene chloride, dichloroethane, dibromoethane, dibromopropane, etc. The higher alcohol is preferably one that is insoluble in water and has 5 to 10 carbon atoms, such as pentanol, hexanol, heptanol, octanol, cyclopentanol, cyclohexanol, cycloheptanol, amyl alcohol. , hexyl alcohol, 2-ethylhexyl alcohol, octanol, nonane alcohol, etc. Ketone compounds are also incompatible with water and are selected from, for example, methyl-ethyl ketone, dibutyl ketone, diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl amyl ketone, cyclohexanone, acetophenone, and the like. Ester compounds are also incompatible with water and are selected from, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, ethyl propionate, butyl propionate, butyl butyrate, ethyl lactate, and the like. Ether compounds are also incompatible with water and are selected from diethyl ether, dipropyl ether, dibutyl ether, anisole, isopropyl ether, dioxane, tetrahydrofuran, and the like. The polyvinyl alcohol used in the method of the present invention is a completely saponified product or a partially saponified product of polyvinyl acetate, and has a degree of saponification of 60 to 100%.
Moreover, those having a degree of polymerization of 300 to 4000 are preferable. When an aqueous solution of the compound of general formula () and/or () and an acidic catalyst is mixed with stirring in an organic solvent that is incompatible with water, the aqueous solution emulsifies (W/O type) in the organic solvent. . When polyvinyl alcohol powder is mixed into this emulsion and stirred, the polyvinyl alcohol powder is dispersed without being dissolved, and the aqueous solution uniformly permeates into the dispersed polyvinyl alcohol particles, uniformly swelling them. Under the above conditions, the dispersion is heated at 20 to 100°C, preferably 10 to 40°C, for 5 to 50 hours (usually overnight).
When stirred, the condensation reaction between polyvinyl alcohol and the compound of general formula () and/or () is completed. After the completion of the reaction, if the solid content in the reaction mixture is excessively separated and this solid content is thoroughly washed with methanol,
Unreacted compounds of general formula () and/or () and acidic catalyst are sufficiently removed from the solid fraction. When the washed polyvinyl alcohol-based photosensitive resin is dried, a fine powder product is obtained. By the method of the present invention, the emulsified aqueous solution containing the compound of general formula () and an acidic catalyst is uniformly absorbed into polyvinyl alcohol, which can be uniformly swollen. Therefore, the solid phase-liquid phase reaction between polyvinyl alcohol and the compound of general formula () and/or () is uniformly carried out, and the resulting photosensitive resin also has a uniform composition. Furthermore, in the method of the present invention, the reaction between polyvinyl alcohol and the compound of general formula () and/or () proceeds quantitatively, and therefore the yield of the photosensitive resin obtained is approximately 100%. If polyvinyl alcohol powder is brought into direct contact with an aqueous solution containing a compound of general formula () and/or () and an acidic catalyst without using an emulsion as in the method of the present invention, the amount of the aqueous solution will be small. Therefore, it is absorbed into a portion of the polyvinyl alcohol powder, and therefore it is impossible to uniformly distribute it in the polyvinyl alcohol powder and swell it uniformly. In order to avoid such problems, increasing the amount of water used may cause the polyvinyl alcohol to dissolve in the aqueous solution or, if the polyvinyl alcohol is a partially saponified product of polyvinyl acetate, to form lumps. This makes the subsequent reaction operations difficult, resulting in a decrease in the yield of the photosensitive resin obtained. Furthermore, when an organic solvent that is not compatible with water is replaced with an organic solvent that is compatible with water, a portion of the resulting reaction product is washed away during the washing process, resulting in a decrease in the yield of the photosensitive resin obtained. This causes the inconvenience of The method of the present invention will be explained below using examples. Example 1 20 g of N-methyl-4-(p-formylstyryl)pyridinium methosulfate and phosphoric acid (content 85
%) in 100 ml of water, and this aqueous solution is mixed in 1 part of toluene. The mixture was stirred vigorously and the aqueous solution was emulsified in toluene. Next, 200 g of polyvinyl alcohol powder with a degree of polymerization of 2000 and a degree of saponification of 88% was added to the emulsion, and the mixture was stirred continuously at room temperature all day and night to react. After the reaction, the condensation reaction resin in the form of solid fine powder is separated and washed with methanol to remove unreacted N-methyl-4-(p
-formylstyryl) pyridinium salt and phosphoric acid were washed away. When the washed solid content is dried, polyvinyl alcohol and N-methyl-4-(p-
218 g of photosensitive resin (yield 100
%) was obtained in a fine powder state. It was confirmed by ultraviolet spectroscopic analysis that this photosensitive resin contained 1.5 mol% of pyridinium base. Example 2 80 g of N-methyl-4-(p-formylstyryl)quinolinium methosulfate and 15 g of phosphoric acid (content)
and to 150 ml of water, and add 1 ml of toluene to this aqueous solution.
It got mixed in. The mixture was stirred vigorously and the aqueous solution was emulsified in toluene. This emulsion contains 200% polyvinyl alcohol with a degree of polymerization of 600 and a degree of saponification of 99%.
g was added thereto, and stirring was continued at room temperature all day and night. After the reaction was completed, the condensation reaction product in the form of solid fine powder was separated and washed with methanol to remove unreacted N-methyl-4-(p-formylstyryl)quinolinium salt and phosphoric acid. When the solid content is dried, polyvinyl alcohol and N-methyl-
272g of photosensitive resin which is a condensation reaction resin of 4-(p-formylstyryl)quinolinium methosulfate
(yield 99%) was obtained in the form of a fine powder. It was confirmed by ultraviolet spectroscopic analysis that 4.8 mol% of quinolinium base was present in this resin. Effects of the Invention In the method of the present invention, the aqueous solution containing the compound of the general formula () and/or () is emulsified as minute particles in an organic solvent that is not compatible with water, so that it is uniformly contained in the polyvinyl alcohol powder particles. can be absorbed and react uniformly with this.
Therefore, the photosensitive resin obtained has a uniform composition and quality, and its yield is extremely high.

Claims (1)

[Claims] 1. The following general formulas () and (): [However, in the above formula, Y is the following general formula () and (): [Formula] [Formula] (In the above formula, R ₁ represents a member selected from the group consisting of a hydrogen atom, an alkyl group, and an aralkyl group, The alkyl group and aralkyl group are each selected from those containing at least one member selected from the group consisting of a hydroxyl group, a carbamoyl group, an ether bond, and an unsaturated bond, and R ₂ is a hydrogen atom and represents one member selected from the group consisting of lower alkyl groups, X ^- represents an anion), m represents an integer from 1 to 6, and n represents O or represents 1,
and t represents 0 or 1] At least one quaternary ammonium salt compound represented by the following is reacted with polyvinyl alcohol to form 0.2 to 20 mol% of the following general formula ( and 59.8 to 99.8 mol% of the following general formula (): and 0 to 40 mol% of the following general formula (): When producing a modified polyvinyl alcohol photosensitive resin having a polymer constitutional unit, the above-mentioned quaternary ammonium salt compound is dissolved in water together with an acidic catalyst, and the resulting aqueous solution is mixed with an aromatic hydrocarbon compound, an aliphatic At least one selected from hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, higher alcohols, ketones, esters, and ethers
emulsifying the seed in a solvent consisting of a water-insoluble organic compound and dispersing the polyvinyl alcohol powder particles in the resulting emulsion, thereby dispersing the quaternary ammonium salt in the dispersed polyvinyl alcohol powder particles. A method for producing a modified polyvinyl alcohol photosensitive resin, which comprises absorbing an aqueous compound solution and reacting the two. 2. The method according to claim 1, wherein the polyvinyl alcohol has a degree of saponification of 60 to 100% and a degree of polymerization of 300 to 4000. 3. The weight ratio of water to polyvinyl alcohol in the emulsion reaction system is within the range of 0.5 to 10.
A method according to claim 1.