JPS647649B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photosensitive resin composition. More specifically, the present invention includes two types of modified polyvinyl alcohol containing a photosensitive styrylpyridinium group or a styrylquinolinium group, is easily soluble in water, has excellent sensitivity and resolution, The present invention also relates to a photosensitive resin composition that has excellent adhesive strength in a film formed by exposure and curing. Photosensitive resins that harden or become insoluble when exposed to light can be used as printing plate materials such as letterpress, lithographic, plano-intaglio, and gravure plates, or as photoresists for metal corrosion processing in the production of printed circuit boards, integrated circuits, name plates, etc. It is widely used as. Furthermore, photosensitive resins are also widely used to form image-forming films on substrates such as films, glass plates, screens, and fabrics. Various resins containing azide groups, cinnamoyl groups, etc. are used as photosensitive resins.
These resins: 1. Sensitivity is not necessarily satisfactory. 2. Many of them are insoluble in water, and when an organic solvent or an alkaline aqueous solution is used as a solvent, it is inconvenient to handle the coating and developing steps. There are known problems such as: Water-soluble photosensitive resins include water-soluble resins such as polyvinyl alcohol, gelatin, and glue;
Compositions with dichromate or diazonium salts are known. Among these water-soluble photosensitive resin compositions, the composition containing dichromate has a high stability of the film formed by its aqueous solution and coating,
In addition, there are problems such as hexavalent chromium pollution in waste liquid treatment, and for this reason, dichromate-containing photosensitive resin compositions are difficult to put into practical use. It's getting difficult. Furthermore, the stability and storage stability of photosensitive resin compositions containing diazonium salts are better than those containing dichromate, but they are not satisfactory.
In particular, its sensitivity is inferior to that of dichromate-containing photosensitive resins, and the strength of the cured film obtained by exposure is also insufficient. In order to solve the above-mentioned problems of conventional water-soluble photosensitive resin compositions, Japanese Patent Publication Nos. 56-5761 and 56-5762 disclose photosensitive polyvinyl alcohol derivatives containing styrylpyridinium groups. Disclosed. Further, JP-A-56-11906 discloses a photosensitive polyvinyl alcohol derivative containing a styrylquinolinium group. Although these photosensitive polyvinyl alcohol derivatives containing a styrylpyridinium group or a styrylquinolinium group have excellent sensitivity and water solubility, they have the following problems. (1) This derivative is produced by adding a styrylpyridinium compound or a styrylquinolinium compound having an aldehyde group or an acetal group to polyvinyl alcohol by an acetalization reaction, but the degree of polymerization of the polyvinyl alcohol component is is greater than or equal to 1000,
As the content of added styrylquinolinium or styrylpyridinium groups increases, the viscosity of the reaction mixture increases accordingly;
In extreme cases, the reaction mixture gels, making it difficult to continue the reaction operation. (2) The strength of the cured film formed by exposing the obtained photosensitive resin to light and the adhesion to the substrate are insufficient, so when the cured film is developed with water, the strength of the cured film is insufficient. Depending on the type, the cured film may easily peel off from the substrate or be partially damaged, resulting in unsatisfactory resolution. In order to put the above styrylpyridinium group- or styrylquinolinium group-containing polyvinyl alcohol derivative into practical use as a water-soluble photosensitive resin material, it is necessary to solve the above problems. The purpose of the present invention is to have high water solubility and photosensitivity;
It is an object of the present invention to provide a photosensitive resin composition in which a cured film obtained by exposure to light has excellent strength and adhesion to a substrate. Another object of the present invention is to provide a photosensitive resin composition that is less difficult to manufacture. The above objects are achieved by the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention has, as a mixed component A, (1) a polyvinyl alcohol main chain having a degree of saponification of 70 to 100% and a degree of polymerization of less than 1000; (2) the polyvinyl alcohol main chain; As part of the following general formula (): [However, in the above formula, Y is a group having the following general formulas () and (): and (However, in the above formula, R ₁ represents a hydrogen atom, an alkyl group, or an aralkyl group, and the alkyl group or aralkyl group is each selected from the group consisting of a hydroxyl group, a carbamoyl group, an ether bond, and an unsaturated bond. It may contain at least one member, and R ₂ is a hydrogen atom, or
represents a lower alkyl group, X ^- represents an anion), m represents 0 or 1, and n represents an integer from 1 to 6. , contains a polymer constitutional unit having a photosensitive styrylpyridinium group or a styrylquinolinium group, and (3) the content of the photosensitive group is relative to the total amount of polymer constitutional units of the polyvinyl alcohol main chain. 1
and 30 mol%. Photosensitive styrylpyridinium group is styrylquinolinium group-containing polyvinyl alcohol derivative A
and, as mixed component B, (1) has a polyvinyl alcohol main chain having a degree of saponification of 70 to 100% and a degree of polymerization of 1000 or more, (2) as a part of the polyvinyl alcohol main chain, the above general formula At least 1 represented by ()
(3) The content of the photosensitive group is less than 1 mol % based on the total amount of polymer constituent units of the polyvinyl alcohol main chain. It is characterized by containing a photosensitive styrylpyridinium group or styrylquinolinium group-containing polyvinyl alcohol derivative B. The polyvinyl alcohol main chains of mixture component A and mixture component B both have a degree of saponification of 70 to 100%. If the degree of saponification is less than 70%, the water solubility of the resulting mixed component will be unsatisfactory. In mixed component A, the degree of polymerization of the polyvinyl alcohol main chain is less than 1000, and the content of photosensitive groups (styrylpyridinium group or styrylquinolinium group) is equal to the total number of polymerized constituent units of the polyvinyl alcohol main chain. On the other hand, it is within the range of 1 to 30 mol%. If the above-mentioned limiting conditions are not met, the object of the present invention cannot be achieved. In particular, when the photosensitive group content is greater than 30 mol%,
The resulting mixed components will have insufficient water solubility. Furthermore, if the degree of polymerization is 1000 or more and the content of photosensitive groups is less than 1%, the resulting mixed component will be the same as the mixed component B. In mixed component A, the degree of polymerization of the polyvinyl alcohol main chain is preferably 700 or more, particularly 200 to 700, and in this case, the photosensitive group content is 5 mol% or more, that is, 5 to 30 mol%. It is preferable. In mixture component B, the degree of polymerization of the polyvinyl alcohol main chain is 1000 or more, and the content of photosensitive groups is less than 1.0 mol%. If the above limiting conditions are not met, the resulting mixture components will be
It becomes the same as mixed component A, and the object of the present invention cannot be achieved. In mixed component B, in order to obtain a cured film with high strength, the degree of polymerization of the polyvinyl alcohol main chain is preferably 1400 or more, particularly 1400 to 2600. In the photosensitive group-containing polymer structural unit of general formula (), the alkyl group represented by R ₁ in general formula () and () has 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl group, etc. The aralkyl group represented by R ₁ is preferably one having 7 to 19 carbon atoms, such as a benzyl, phenethyl, trityl group, etc. Further, the alkyl group and aralkyl group represented by R ₁ above include at least one selected from the group consisting of a hydroxyl group, a carbamoyl group, an ether bond, and an unsaturated bond, such as hydroxyethyl, carbamoylmethyl, or , methoxymethyl group, etc. In addition, in the general formula (), the lower alkyl group represented by R ₂ is one containing 1 to 4 carbon atoms, such as methyl, ethyl, propyl,
or a butyl group is preferable. Furthermore, the anion represented ^by
-Toluenesulfonate ion is preferred. Mixed components A and B in the composition of the present invention can be prepared by known methods, for example, Japanese Patent Publication No. 56-5761.
No. 56-5762 or JP-A-55-
No. 136265 and No. 56-11906. That is, polyvinyl alcohol having a saponification degree of 70 to 100% and the following general formula () [However, in the above formula, Y, m and n are the same as defined above.] The styrylpyridinium salt compound or styrylquinolinium salt compound of
A stilbazolium group-containing polyvinyl alcohol derivative is obtained by reacting in the presence of a normal amount of an acid catalyst at a temperature of room temperature to 100° C. for 1 to 24 hours. Examples of the styrylpyridinium compound of the above general formula () include α-(p-formylstyryl)pyridinium, γ-(p-formylstyryl)pyridinium, α-(m-formylstyryl)pyridinium, N-methyl-α-( p-formylstyryl)pyridinium, N-methyl-β-
(p-formylstyryl)pyridinium, N-methyl-α-(m-formylstyryl)pyridinium, N-methyl-α-(o-formylstyryl)
Pyridinium, N-ethyl-α-(p-formylstyryl)pyridinium, N-(2-hydroxyethyl)-α-(p-formylstyryl)pyridinium, N-(2-hydroxyethyl)-γ-
(p-formylstyryl)pyridinium, N-anyl-α-(p-formylstyryl)pyridinium, N-methyl-γ-(p-formylstyryl)
Pyridinium, N-methyl-γ(m-formylstyryl)pyridinium, N-benzyl-α-(p
-formylstyryl)pyridinium, N-benzyl-γ-(p-formylstyryl)pyridinium, N-carbamoylmethyl-γ-(p-formylstyryl)pyridinium, and the like. Examples of styrylquinolinium compounds of the general formula () include 2-(p-formylstyryl)-quinolinium, 4-(p-formylstyryl)-quinolinium, and 1-methyl-2-(p-formylstyryl). -Quinolinium, 1-methyl-
4-(p-formylstyryl)-quinolinium,
1-ethyl-4-(p-formylstyryl)-quinolinium, 1-(2-hydroxylethyl)-
4-(p-formylstyryl)-quinolinium,
1-benzyl-4-(p-formylstyryl)-
Quinolinium, 1-methyl-2-[p-(formylstyryl)styryl]-quinolinium, 1-methyl-4-[p-(formylmethoxy)styryl]
-Quinolinium, 1-methyl-4-[m-(formylmethoxy)styryl]-quinolinium, 1-
Methyl-4-[o-(formylmethoxy)styryl]-quinolinium, 1-methyl-2-[p-
Examples include (3-formylpropoxy)styryl]-quinolinium and 1-methyl-2-[p-(2-formylethoxy)styryl]-quinolinium. The above quaternary salts include hydrochloride, hydrobromide, hydroiodide, perchlorate, hydroborate, methosulfate, phosphate, sulfate, methanesulfonate, p- It may also exist in the form of toluenesulfonate or the like. These compounds are
It is obtained by condensing the corresponding picoline or N-alkylpicolinium salt with an aromatic dialdehyde, that is, formylbenzaldehyde, and is used as a formylstyrylpyridine salt or a quaternized salt. Generally, mixture components A and B are manufactured separately. The composition of the present invention can be prepared by mixing reaction mixtures of each component, or by precipitating each component from each reaction mixture using a poor solvent, separating and refining the precipitated products, and then mixing the resulting mixture. prepared. However, the method of mixing the reaction mixture of each component has the following problems. That is, if the respective reaction mixtures are mixed without performing a reaction termination measure, the degree of acetalization of each component will be made uniform in the mixture of reaction mixtures. Therefore, before the above mixing operation, it is important to neutralize each reaction mixture, deactivate the acid catalyst, and stop the acetalization reaction. In the composition of the invention, mixture components A and B
The mixing ratio can be appropriately determined depending on the structure of each component, degree of polymerization, content of stilbazolium groups, purpose of use of the composition, etc. Generally, the mixing ratio of mixture components A and B is between 1:100 and 1:
It is preferable that it is in the range of 1. Even if the content of photosensitive styrylpyridinium or styrylquinolinium groups contained in the composition of the present invention varies over a fairly wide range, the viscosity of the aqueous solution of the composition changes relatively little. For example, the viscosity at 20° C. of a 10% (by weight) aqueous solution of polyvinyl alcohol with a degree of polymerization of 1700 and a degree of saponification of 88% is 1500 to 2000 cp. When 0.7 mol% of styrylpyridinium groups are added to the above polyvinyl alcohol, 10% of the resulting derivative
The viscosity of the aqueous solution at 20° C. increases significantly to 7,000 to 10,000 cp, making it difficult to use this aqueous solution as a coating solution. Furthermore, if the content of the styrylpyridinium group-containing structural unit is 2.5 mol % or more, the resulting 10% aqueous solution of the derivative will no longer exhibit fluidity during gelation and will be unusable as a coating solution. On the other hand, in the composition of the present invention, for example, (1) the polyvinyl alcohol main chain has a polymerization degree of
1700, a saponification degree of 88%, and a content of 0.2 mol% of styrylpyridinium group-containing structural units, (2) a polyvinyl alcohol main chain having a polymerization degree of 650 and a saponification degree of 88%. However, in a mixture with 10 parts of mixture component A in which the content of styrylpyridinium group-containing structural units is 5.0 mol%, the average content of styrylpyridinium group-containing structural units is about 0.7 mol% as above. The viscosity of its 10% aqueous solution is extremely low, 2000 to 2500 cp. Further, when 52 parts of the above mixed component B and 48 parts of the above mixed component are mixed, the average content of styrylpyridinium group-containing structural units in the resulting composition is about 2.5 mol%, but 10 parts of this composition
% aqueous solution exhibits an unexpectedly low viscosity of 3000-3500 cp, and this aqueous solution is fully usable as a coating solution. The composition of the present invention also exhibits good adhesion to metals, glass, and other substrates, and its photosensitivity,
It also shows extremely excellent performance in terms of resolution and strength of the cured film. Hereinafter, the present invention will be explained in more detail with reference to Examples and Reference Examples. Reference example 1 100g of N-methyl-α-picolinium p-toluenesulfonate and 200g of terephthalaldehyde
was dissolved in 400 c.c. of ethanol while heating, 3 c.c. of piperidine was added, and the mixture was refluxed at 100°C for 3 hours. After cooling, 200 c.c. of ethanol was distilled off from the reaction mixture under reduced pressure, ethyl acetate was added to the remaining reaction mixture, and the yellow precipitate formed was separated by decantation and washed twice with ethyl acetate. When this precipitate was dissolved in hot ethanol and ethyl acetate was gradually added thereto, bright yellow crystals were precipitated. The crystals were collected, washed with ethyl acetate, and dried. In this way, N
110 g of -methyl-α-(p-formylstyryl)pyridinium p-toluenesulfonate was obtained. Reference Example 2 N-methyl-γ-picolinium, p-toluenesulfonate was reacted in the same manner as described in Reference Example 1, and N-methyl-γ-(p-formylstyryl)pyridinium p- 115 g of toluenesulfonate was obtained. Reference Example 3 After adding 37.6 g of γ-picoline to 100 c.c. of methanol, 50.4 g of dimethyl sulfate was added dropwise while cooling with water. After that, 134 g of terephthalaldehyde was uniformly dissolved in the reaction mixture, and then piperidine was added to this.
5.6 cc was added and refluxed at 100°C for 5 hours. After heating the reaction mixture to remove a small amount of crystals, a mixed solvent consisting of 400 c.c. of ethanol and 400 c.c. of acetone was added to the remaining reaction mixture and left overnight.
Slight yellow crystals precipitated. The crystals were collected, washed with acetone, and then dried. In this way, 67 g of N-methyl-γ-(p-formylstyryl)pyridinium methosulfate was obtained. Reference example 4 97.6g of m-hydroxybenzaldehyde and 33
of caustic soda was dissolved in 200 c.c. of 2-ethoxyethyl alcohol, then 148 g of bromoacetaldehyde dimethyl acetal was added and the resulting reaction mixture was refluxed at 160° C. for 20 hours. The reaction mixture was cooled, benzene was added, and the resulting benzene solution was washed once with water and then with dilute alkali until no hydroxyaldehyde was detected. After drying this benzene solution over anhydrous potassium carbonate, 70.8 g of m-formylphenoxyacetaldehyde dimethyl acetal having a boiling point of 138° C. was obtained by distillation under reduced pressure. 68 g of m-formylphenoxyacetaldehyde dimethyl acetal thus obtained and 78 g of N-methyl-α-picolinium iodide were
cc of methanol, 12 c.c. of piperidine was added to this solution, and the mixture was refluxed for 4 hours. Thereafter, the reaction solution was cooled, the precipitated crystals were collected, and the crystals were washed with a small amount of methanol and then thoroughly with acetone.
43.4 g of (2,2-dimethoxyethoxy)styryl}pyridinium iodide was obtained. In exactly the same manner as above, o-formylphenoxyacetaldehyde dimethyl acetal (bp ₅ 147°C) was prepared using o-benzaldehyde and p-
p-formylphenoxyacetaldehyde dimethyl acetal (bp ₃ 145
°C) was obtained. The thus obtained o-formylphenoxyacetaldehyde dimethyl acetal and N-
From methyl-α-picolinium iodide,
1-Methyl-2-{o-(2,
2-dimethoxyethoxy)styryl}pyridinium iodide was obtained. Also, m. from p-formylphenoxyacetaldehyde dimethyl acetal and N-methyl-α-picolinium iodide.
1-methyl-4-{p-(2,2
-dimethoxyethoxy)styryl}pyridinium iodide was obtained. Synthesis Example A-1 <Preparation of aqueous solution of mixed component A> 50 g of N-methyl-γ-(p-formylstyryl) pyridinium methosulfate and 100 g of polyvinyl alcohol with a degree of polymerization of 600 and a degree of saponification of 88% were mixed into 900 g
ml of water and add 5g of 85% phosphoric acid to this solution.
was added, and the reaction mixture was heated and stirred at 60° C. for 5 hours, and then further stirred at room temperature for 1 day and night. After that, the reaction mixture was neutralized with 10% ammonia aqueous solution and heated at 25℃.
An aqueous solution of Mix Component A was prepared with a viscosity of 4500 cp. The content of styrylpyridinium groups in this mixed component A, based on the total amount of polyvinyl alcohol polymer constituent units, was measured by ultraviolet absorption spectroscopy and was found to be approximately 9.0 mol %. Synthesis Example B-1 <Preparation of aqueous solution of mixed component B> 1.0 g of N-methyl-γ-(p-formylstyryl) pyridinium methosulfate and 100 g of polyvinyl alcohol with a degree of polymerization of 2000 and a degree of saponification of 88%,
The mixture was heated and dissolved in 900 ml of water, 5 g of 85% phosphoric acid was added to this solution, and the resulting reaction mixture was heated and stirred at 60° C. for 5 hours, and then further stirred at room temperature all day and night. The resulting reaction mixture was neutralized with a 10% ammonia aqueous solution to prepare an aqueous solution of mixed component B having a viscosity of 1300 cp at 20°C. The content of styrylpyridinium group-containing structural units in this mixed component B was measured by ultraviolet absorption spectroscopy and was found to be approximately 0.16 mol%. Example 1 12.8 g and 87.2 g of the aqueous solutions of mixed components A and B obtained in Synthesis Example A-1 and Synthesis Example B-1, respectively.
were mixed to prepare an aqueous photosensitive resin composition solution having an average content of 1.1 mol % of the stilbazolium group-containing structural unit. The viscosity of this composition aqueous solution was 2100 cp at 25°C. This photosensitive resin composition aqueous solution was diluted with water to make the solid content concentration 3%,
Coating was performed on a ball-polished aluminum plate using a rotary coating machine at 60 revolutions per minute. Kodatsu step tablet No. 2 and 100 and 150 wires/
A negative film having a diameter of 25.4 mm was placed, and after vacuum contact, it was irradiated with an ultra-high pressure mercury lamp of 2 kW from a height of 1 m for 5 seconds. When this exposed cured film was developed with running tap water for 60 seconds, there were 6 steps remaining. Also, 100 and 150 wire/25.4mm
The resolution was good. In the same manner, this photosensitive resin composition aqueous solution was applied to a sufficiently polished mirror-finished aluminum plate, glass plate, stainless steel plate, and polyester film to a film thickness of 2 μm, respectively. Next, the entire surface of the coated film was exposed to light for 20 seconds from a height of 1 m using a 2 kW ultra-high pressure mercury lamp. Thereafter, the coated film was developed with running tap water for 60 seconds, and the cured photoresist film was firmly held on each support. Comparative Example 1 7.0 g of N-methyl-γ-(p-formylstyryl) pyridinium sulfate and a degree of polymerization of 200 and a degree of saponification of 88%.
100 g of polyvinyl alcohol and 100 g of polyvinyl alcohol were dissolved in 900 ml of water by heating, and 5 g of 85% phosphoric acid was added thereto. The resulting reaction mixture was heated and stirred at 60° C. for 5 hours, and further stirred at room temperature for 1 day and night. Then add 10% of the reaction mixture
% ammonia aqueous solution, viscosity at 25℃
A photosensitive resin aqueous solution having 12000 cp was prepared.
(Compared to Example 1, this aqueous solution showed a significantly higher viscosity.) The content of styrylpyridinium group-containing structural units in this photosensitive resin was approximately 1.1 as measured by ultraviolet absorption spectrum.
It was in mol%. As a result of performing various measurements similar to those in Example 1 using the above photosensitive resin, the remaining number of steps was 6.
In terms of row and resolution, the case of 100 lines/25.4 mm was good, but the case of 150 lines/25.4 mm was poor. In addition, when testing the retention of exposed coatings on well-polished mirror-surfaced aluminum plates, glass plates, stainless steel plates, and polyester films, we found that the coatings were washed away or even wrinkled during development under running tap water. It was defective. In this development, even if the exposure time was 60 seconds, three times that of Example 1,
It was not improved. Examples 2 to 14 and Comparative Examples 2 to 14 Examples 2 to 14 were prepared in the same manner as in Example 1 using the mixed components A and B listed in Table 1, and Comparative Example 1 was prepared using the resin listed in Table 2. Comparative example 2~
He did 14 things. The results are shown in Tables 1 and 2. In Tables 1 and 2, the examples with each number correspond to the comparative examples with the same number.

【table】

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[Table] Synthesis Example A-2 <Preparation of aqueous solution of mixed component A> 91 g of N-methyl-4-(p-formylstyryl)quinolinium methosulfate and 100 g of polyvinyl alcohol with a degree of polymerization of 300 and a degree of saponification of 88%, 900ml
5 g of 85% phosphoric acid was added to this solution, and the reaction mixture was heated and stirred at 60° C. for 5 hours, and then further stirred at room temperature for 1 day and night. Then add the reaction mixture to 10
% ammonia aqueous solution and 4800cp at 25℃
An aqueous solution of mixture component A was prepared having a viscosity of . The content of styrylquinolinium groups in this mixed component A, based on the total amount of polyvinyl alcohol polymer constituent units, was measured by ultraviolet absorption spectroscopy and was found to be about 15.0 mol %. Synthesis Example B-2 <Preparation of aqueous solution of mixed component B> 0.3 g of N-methyl-4-(p-formylstyryl)quinolinium methosulfate and 100 g of polyvinyl alcohol with a degree of polymerization of 2400 and a degree of saponification of 78% are heated in 900 ml of water. After dissolving, 5 g of 85% phosphoric acid was added to this solution, and the resulting reaction mixture was heated and stirred at 60° C. for 5 hours, and then further stirred at room temperature for 1 day and night. The resulting reaction mixture was neutralized with a 10% ammonia aqueous solution and incubated at 20°C.
An aqueous solution of mixture component B was prepared with a viscosity of 1600 cp. The content of styrylquinolinium groups in this mixture component B based on the total amount of polyvinyl alcohol polymer constituent units was measured by ultraviolet absorption spectroscopy and was found to be about 0.05 mol %. Example 15 3 g and 97 g of the aqueous solutions of mixed components A and B obtained in Synthesis Example A-2 and Synthesis Example B-2 were mixed, respectively, and the average amount based on the total amount of styrylquinolinium-based polyvinyl alcohol polymer constituent units was determined. A photosensitive resin composition aqueous solution having a content of 0.5 mol% was prepared. The viscosity of this composition aqueous solution at 25℃ is
It was 1700 cp. This photosensitive resin composition aqueous solution was diluted with water to a solid content concentration of 3%, and coated onto a ball-polished aluminum plate using a rotary coater at 60 revolutions per minute. On this coated aluminum plate are Kodatsu step tablet No. 2 and 100 and 150 wires / 25.4 mm.
After placing a negative film with a 100% polyurethane in a vacuum, it was irradiated with an ultra-high pressure mercury lamp of 2 kW from a height of 1 m for 5 seconds. When this exposed cured film was developed with running tap water for 60 seconds, there were 5 steps remaining. Also, the resolution of 100 and 150 lines/25.4 mm was good. In the same manner, this photosensitive resin composition aqueous solution was coated onto a sufficiently polished mirror-finished aluminum plate, glass plate, stainless steel plate, and polyester film to a film thickness of 2 μm, respectively. Next, the entire surface of the coated film was exposed to light for 20 seconds from a height of 1 m using a 2 kW ultra-high pressure mercury lamp. Thereafter, the coated film was developed with running tap water for 60 seconds, and the cured photoresist film was firmly held on each support. Comparative Example 15 2.8 g of N-methyl-4-(p-formylstyryl) quinolinium methosulfate and 100 g of polyvinyl alcohol with a degree of polymerization of 2400 and a degree of saponification of 78% were heated and dissolved in 900 ml of water, and 5 g of 85% phosphoric acid was dissolved in this. The resulting reaction mixture was heated and stirred at 60°C for 5 hours,
The mixture was further stirred at room temperature for one day and night. Then add the reaction mixture
Neutralize with 10% ammonia aqueous solution and reduce viscosity at 25℃
A photosensitive resin aqueous solution having a viscosity of 8800 cp was prepared (compared to Example 2, this aqueous solution showed a significantly higher viscosity). The content of styrylquinolinium group-containing structural units in this photosensitive resin was Approximately 0.5 mol% as measured by ultraviolet absorption spectrum
It was hot. As a result of performing various measurements similar to those in Example 2 using the above photosensitive resin, the remaining number of steps was 5.
In terms of row and resolution, the case of 100 lines/25.4 mm was good, but the case of 150 lines/25.4 mm was poor. In addition, during retention tests of exposed coatings on well-polished mirror-surfaced aluminum plates, glass plates, stainless steel plates, and polyester films, the coatings were washed away or wrinkled during development under running tap water. It was defective. This development was not improved even when the exposure time was increased to 60 seconds, three times that of Example 2. Examples 16 to 18 and Comparative Examples 16 to 18 Examples using mixture components A and B listed in Table 3
Comparative Examples 16 to 18 were carried out in the same manner as in Comparative Example 15 using the resins listed in Table 4. The respective results are shown in Tables 3 and 4. In Tables 3 and 4, the examples with each number correspond to the comparative examples with the same number.

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Claims (1)

[Claims] 1. Mixing component A includes (1) a polyvinyl alcohol main chain having a degree of saponification of 70 to 100% and a degree of polymerization of less than 1000; (2) one of the polyvinyl alcohol main chains; As part, the following general formula (): [However, in the above formula, Y is a group having the following general formulas () and (): and (However, in the above formula, R ₁ represents a hydrogen atom, an alkyl group, or an aralkyl group, and the alkyl group or aralkyl group is each selected from the group consisting of a hydroxyl group, a carbamoyl group, an ether bond, and an unsaturated bond. It may contain at least one member, and R ₂ is a hydrogen atom, or
represents a lower alkyl group, X ^- represents an anion), m represents 0 or 1, and n represents an integer from 1 to 6. , contains a polymer constitutional unit having a photosensitive styrylpyridinium group or a styrylquinolinium group, and (3) the content of the photosensitive group is based on the total amount of polymer constitutional units of the polyvinyl alcohol main chain. Against 1
A photosensitive styrylpyridinium group-containing or styrylquinolinium group-containing polyvinyl alcohol derivative A which is 30 to 30 mol%, and (1) a saponification degree of 70 to 100% and a polymerization degree of 1000 or more as a mixed component B. (2) contains at least one kind of polymer constitutional unit represented by the general formula () as a part of the polyvinyl alcohol main chain, and (3) the photosensitive A photosensitive resin containing a styrylpyridinium group or a styrylquinolinium group-containing polyvinyl alcohol derivative B, in which the content of functional groups is less than 1 mol % based on the total amount of polymer constituent units of the polyvinyl alcohol main chain. Composition. 2. The composition according to claim 1, wherein the mixing weight ratio of the mixing component A and the mixing component B is in the range of 1:100 to 1:1. 3. The composition according to claim 1, wherein the degree of polymerization of the polyvinyl alcohol main chain of the mixed component A is 700 or less, and the content of the photosensitive group is 5 to 30 mol%. 4. The composition according to claim 1, wherein the polyvinyl alcohol main chain of the mixed component B has a degree of polymerization of 1400 or more. 5 In the general formulas () and (),
2. The composition according to claim 1, wherein the anion represented by X ^- is a halogen ion, a phosphate ion, a sulfate ion, a methosulfate ion, or a p-toluenesulfonate ion.