JPH0361939B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a photosensitive resin and a method for producing the same, and more specifically, it relates to a modified polyvinyl alcohol photosensitive resin containing acid groups and a method for producing the same. [Prior Art] A method of condensing unmodified polyvinyl alcohol with a quaternary ammonium salt compound such as a styrylpyridinium salt compound or a styrylquinolinium salt compound, and the photosensitive resin obtained thereby, are disclosed in Japanese Patent Publication No. 1983 -5761 and 56-5762, and JP-A-56-11906. In these methods, the condensation reaction between polyvinyl alcohol and a quaternary ammonium base-containing compound is carried out in the presence of an acidic catalyst such as sulfuric acid, phosphoric acid, or hydrochloric acid, and after the condensation reaction, the resulting reaction mixture is Neutralized with aqueous alkaline solution. However, in these methods, inorganic salts tend to be included in the resulting photosensitive resin, and for this reason, the image obtained by exposing a photosensitive material made from this photosensitive resin and developing with water. The water resistance of the photocurable resin that forms the part is insufficient,
In addition, drawbacks have been recognized, such as the surface of the image area becoming rough. In order to eliminate the above drawbacks, conventionally,
After completion of the condensation reaction, the resulting reaction mixture is subjected to steps such as ion exchange treatment or precipitation purification of the resulting resin to remove unreacted quaternary ammonium salt compounds,
The acidic catalyst and salts generated by neutralization were removed. However, such a purification process is complicated and increases the cost of the product. Therefore, there has been a long-awaited need for a new photosensitive resin and a method for producing the same that can overcome the above-mentioned drawbacks of conventional methods. [Problems to be Solved by the Invention] An object of the present invention is to provide a photosensitive resin that can provide good water resistance and a smooth surface. [Means and effects for solving the problems] The present invention involves introducing an acidic side chain-containing copolymer unit and a specific quaternary ammonium base side chain-containing group copolymer unit into the main chain of polyvinyl alcohol. As a result, we succeeded in solving the above problem. That is, the modified polyvinyl alcohol photosensitive resin according to the present invention has the general formula (A): Acidic side group-containing copolymer unit represented by (B) general formula (): [However, in the above formula, Y is the following general formula () and (): (In the above formula, R ₁ represents an alkyl group and X ^- represents an anion) represents one member selected from the quaternary ammonium base represented by 0 or 1] At least one basic side chain group-containing copolymer unit represented by (C) the following general formula: vinyl acetate copolymerized unit, and (D) the following general formula: A polyvinyl alcohol modified product consisting of vinyl alcohol copolymerized units and having a degree of polymerization of 300 to 4000, wherein the content of the vinyl acetate unit (C) is 40 mol% or less, and the acidic side The total content (N) of the chain group-containing copolymer unit (A), the basic side chain group-containing copolymer unit (B), and the vinyl alcohol copolymer unit (D) is 60 mol% or more, and the copolymer component The content of (A) is 0.01 to 10% with respect to the total content (N), and the content of the copolymerization component (B) is with respect to the total content (N), It is characterized by being 0.2 to 30%. The modified polyvinyl alcohol photosensitive resin of the present invention has a polyvinyl alcohol main chain component in its polymer structure and a modified copolymer component bonded and copolymerized with the polyvinyl alcohol main chain component. Among the modified copolymer components, the basic side chain group-containing copolymer unit has the following general formula (): This is shown in . In the above general formula (), m represents an integer of 1 to 6, n represents 0 or 1, and Y represents the following general formulas () and (): represents a quaternary ammonium salt residue selected from pyridinium salt residues and quinolinium salt residues shown in In the above formula () (), R ₁ is an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms,
For example, methyl, ethyl, propyl, butyl, pentyl and hexyl groups, etc., and X ^- represents an anion, such as chloride, bromide, sulfate, phosphate, perchlorate, methoxysulfate, methanesulfone It represents one member of acid ion, p-toluenesulfonic acid ion, etc. The content of basic side group-containing copolymerized units (B) of the general formula () in the modified polyvinyl alcohol of the present invention is the vinyl alcohol unit of the raw material polyvinyl alcohol, that is, the acidic side chain group in the corresponding modified polyvinyl alcohol. Containing copolymer unit
0.2 to the total amount (N) of (A), basic side chain group-containing copolymer unit (B), and vinyl alcohol unit (D)
30 mol%, preferably within the range of 0.2 to 20 mol%. The acidic side group-containing copolymer unit contained in the modified polyvinyl alcohol photosensitive resin of the present invention is It is an organic sulfonic acid side chain group-containing unit represented by The content of the acidic side group-containing copolymer unit (A) is the vinyl alcohol unit of the raw material polyvinyl alcohol,
That is, 0.01 for the total amount (N) of acidic side group-containing copolymer units (A), basic side chain group-containing copolymer units (B), and vinyl alcohol units (D) in the corresponding modified polyvinyl alcohol. ~10 mol%. Furthermore, the polyvinyl alcohol main chain in the modified polyvinyl alcohol copolymer of the present invention is
It has a degree of polymerization of 300 to 4000, and a degree of saponification of 60% or more. The organic sulfonic acid group may be neutralized. The modified polyvinyl alcohol copolymer of the present invention contains both an acidic group having an organic sulfonic acid group and a basic group having a pyridinium base and/or a quinolinium base in its molecule. The ionic bonding force between
Therefore, the photosensitive resin of the present invention has high apparent sensitivity, and the image area obtained by exposing the photosensitive material made therefrom and developing it with water exhibits excellent water resistance. The modified polyvinyl alcohol photosensitive resin of the present invention has the general formula () or (): [In the above formula, Y, m, and n are the same as defined above, and t represents 0 or 1. ] A quaternary ammonium salt compound (styryl pyridinium salt compound or styryl quinolinium salt compound) represented by Obtained by condensation reaction. This condensation reaction is characterized in that it is carried out without the addition of an acidic catalyst, or even when it is added, a very small amount is sufficient; therefore, it is necessary to subject the product to a purification process to remove the acidic catalyst. There is no. Since the polyvinyl alcohol copolymer used in the above reaction has an acid group, the polyvinyl alcohol copolymer can be expressed by the general formula ( ) or () can undergo a condensation reaction with a quaternary ammonium salt compound. The introduction of the organic sulfonic acid group into polyvinyl alcohol may be carried out simultaneously with the condensation reaction with the quaternary ammonium salt compound in the same step. The quaternary ammonium salt compounds represented by general formulas () and () are, for example, 1-methyl-
4-{2-[4-(2,2-dimethoxyethoxy)
phenyl]ethyl}-pyridinium methosulfate,
N-methyl-4-(p-formylstyryl)-pyridinium methosulfate, and N-methyl-2-
styrylpyridinium salt compounds such as (p-formylstyryl)-pyridinium hydrochloride, and 1-methyl-4-{2-[4-(2,2-dimethoxyethoxy)phenyl]ethyl}-quinolinium methosulfate, N -methyl-4-(p-formylstyryl)-quinolinium methosulfate, and N
selected from styrylquinolinium salt compounds such as -methyl-2-(p-formylstyryl)-quinolinium sulfate and the like. The reaction between the quaternary ammonium salt compound of general formula () or () and the acid group-containing polyvinyl alcohol derivative is preferably carried out in an aqueous medium,
The reaction mixture then usually exhibits a pH of 1 to 3.
Although there is no particular limitation on the temperature of this condensation reaction, it is generally heated at 50 to 80°C for 3 to 6 hours, and then
It is preferable to heat at 10 to 30° C., for example, at room temperature for 10 to 20 hours, for example, for one day and night. Once the condensation reaction is complete, add an alkaline aqueous solution, such as a sodium hydroxide aqueous solution, to the reaction mixture.
Alternatively, an ammonia aqueous solution is added to neutralize this. As a result, an aqueous solution of the modified polyvinyl alcohol photosensitive resin is obtained. At this time, since the alkali is absorbed by the acid groups of the modified polyvinyl alcohol, the aqueous solution does not substantially contain free salt. Therefore, this aqueous solution can be used as it is as a photosensitive resin aqueous solution without being subjected to ion exchange treatment or other purification steps. [Example] The present invention will be explained below using Examples. Example 1 Polyvinyl alcohol (polymerization degree 2000, saponification degree
88 mol%) was dissolved in 900 g of water. Then add 1.9 o-benzaldehyde sulfonic acid to this aqueous solution.
g (equivalent to 0.5 mol% per vinyl alcohol unit)
and N-methyl-4-(p-formylstyryl)
When 10g of quinolinium methosulfate was dissolved,
Its pH became 2.2. This aqueous solution was stirred at 60° C. for 4 hours, and then stirred at room temperature for another day and night. After the condensation reaction, the reaction solution was adjusted to pH6 with aqueous ammonia solution.
When neutralized to 7 to 7, an aqueous photosensitive resin solution (A) in which a sulfone group and a styrylquinolinium salt were introduced into the same polyvinyl alcohol was obtained. The structural units and their content of this photosensitive resin were as follows.

[Table] Comparative example 1 Polyvinyl alcohol (polymerization degree 2000, saponification degree
88%) was dissolved in 900 g of water. Dissolve 10 g of N-methyl-4-(p-formylstyryl)pyridinium methosulfate in this aqueous solution, adjust the pH of this aqueous solution to 2.7 with an aqueous phosphoric acid solution, stir at 60°C for 4 hours, and then stir at room temperature overnight. continued. After the condensation reaction was completed, the reaction solution was neutralized to pH 6 to 7 with an ammonia aqueous solution to prepare a comparative photosensitive resin aqueous solution (1). Comparative example 2 Polyvinyl alcohol (degree of polymerization 800, degree of saponification
99%) was dissolved in 900 g of water. Dissolve 30 g of N-methyl-4-(p-formylstyryl)pyridinium methosulfate in this aqueous solution, adjust the pH of this aqueous solution to 2.2 with an aqueous phosphoric acid solution, stir at 60°C for 4 hours, and then stir at room temperature overnight. continued. After the condensation reaction is completed, the reaction solution is neutralized to pH 6 to 7 with an ammonia aqueous solution to obtain a comparative photosensitive resin aqueous solution (2). Comparative example 3 Polyvinyl alcohol (polymerization degree 2000, saponification degree
88%) was dissolved in 900 g of water. Dissolve 10 g of N-methyl-4-(p-formylstyryl)quinolinium methosulfate in this aqueous solution, adjust the pH of this aqueous solution to 2.2 with an aqueous phosphoric acid solution, stir at 60°C for 4 hours, and then stir at room temperature overnight. continued. After the condensation reaction is complete, the resulting reaction solution is PHed with aqueous ammonia solution.
6 to 7 to prepare a photosensitive resin aqueous solution (3). Example 2 In Example 2, 60 g of the photosensitive resin aqueous solution (A) prepared in Example 1 and 18% polyvinyl acetate emulsion (solid content concentration 50%) were mixed and printed on a screen printing plate (nylon 200 mesh). It was applied to a film thickness of 15 μm and dried. A negative film was placed on the resulting photosensitive plate and irradiated for 4 minutes from a height of 1 m using a 2 kW ultra-high pressure mercury lamp. Thereafter, when the photosensitive plate was developed with water, the exposed areas remained and the unexposed areas were washed away, forming an image. Regarding the above-mentioned photosensitive plate, the water resistance and resolution of the exposed area, the number of remaining stages, the gloss of the image area, etc. were measured using Kodatsu Step Bullet No. 2,
The results are shown in Table 1. Comparative Examples 4, 5, 6 In Comparative Example 4, the same exposure and development operations as in Example 2 were carried out, except that 60 g of the photosensitive resin aqueous solution (1) of Comparative Example 1 was used and the irradiation time was 6 minutes. The results shown in Table 1 were obtained. In Comparative Example 5, the photosensitive resin aqueous solutions (1) and (2) of Comparative Examples 1 and 2 were mixed in the proportions listed in Table 1, and in Comparative Example 6, the photosensitive resin of Comparative Example 3 was used. Exposure and development operations similar to those in Comparative Example 4 were performed using aqueous solution (3). The results are shown in Table 1.

〔Effect of the invention〕

The modified polyvinyl alcohol photosensitive resin of the present invention has excellent resolution and photosensitivity, and the image area obtained by exposure and development exhibits good water resistance and surface gloss because of the ionic bonding force.

Claims (1)

[Claims] 1. The following copolymerized unit: (A) General formula: Acidic side group-containing copolymer unit represented by (B) general formula (): [However, in the above formula, Y is the following general formula () and (): (In the above formula, R ₁ represents an alkyl group and X ^- represents an anion) represents one member selected from the quaternary ammonium base represented by 0 or 1] At least one basic side chain group-containing copolymer unit represented by (C) the following general formula: vinyl acetate copolymerized unit, and (D) the following general formula: A polyvinyl alcohol modified product consisting of vinyl alcohol copolymerized units and having a degree of polymerization of 300 to 4000, wherein the content of the vinyl acetate unit (C) is 40 mol% or less, and the acidic side The total content (N) of the chain group-containing copolymer unit (A), the basic side chain group-containing copolymer unit (B), and the vinyl alcohol copolymer unit (D) is 60 mol% or more, and the copolymer component The content of (A) is 0.01 to 10 mol% relative to the total content (N), and the content of the copolymer component (B) is relative to the total content (N). , 0.2 to 30 mol% of a modified polyvinyl alcohol photosensitive resin.