JPS59185332A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain an image easily soluble and high in gradation reproducibility, and high in contrast by using a specified photosensitive polyvinylalcohol deriv. mixed with a wax emulsion. CONSTITUTION:A PVA deriv. used as a photosensitive element has 200-4,000 main chain polymn. degree and 70-98mol% saponification degree, and contains styryl-pyridinium or styrylquinolinium groups as polymn. monomer units in an amt. of 0.3-40mol% of the total monomer units. Said PVA has formula I in which Y is formula II or III; R1 is alkyl or aralkyl optionally substd. by at least one of OH, CONH2, or a group having an ether bond or unsatd. bond; R2 is H or lower alkyl; X<-> is an anion; (m) is 0 or 1; and (n) is 1-6. Such a photosensitive element is mixed in a wax emulsion in a weight ratio of (1/0.5)-1/5. Further, 0.01-1wt% colloidal soln. of silicic acid anhydride polymer represented by the formula: XSi(OR)3 (X being amino, vinyl, or the like, and R being methoxy or the like) to enhance adhesion of an image part and its physical strength.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a photosensitive resin composition, and more particularly to a photosensitive resin composition containing polyvinyl alcohol containing a photosensitive styrylpyridinium group or a styrylquinolinium group, which is easily soluble in water. The present invention relates to a photosensitive resin composition having good gradation reproducibility.

Background of the technology Photosensitive resins harden or become insoluble when exposed to light, and are generally used in printing plate materials such as letterpress, lithography, plano intaglio, and gravure plates, or metal corrosion processing in the production of printed circuit boards, integrated circuits, name plates, etc. Widely used in photoresists. Furthermore, photosensitive resins are also widely used for forming image-forming films on substrates such as films, glass plates, screens, or fabrics.

Photosensitive resins having photosensitive residues such as azide groups, cinnamoyl groups, and acryloyl groups have been known so far. These resins do not necessarily have satisfactory sensitivity, and many of them are insoluble in water. Therefore, when using an organic solvent or alkaline aqueous solution as a solvent,
There are inconveniences in handling during coating and developing processes.

On the other hand, as water-soluble photosensitive resins, compositions of water-soluble resins such as polyvinyl alcohol, gelatin, glue, and dichromate or diazonium salts are known. Among these water-soluble photosensitive resin compositions, compositions containing dichromate have poor stability and storage stability of the aqueous solution and the film formed by coating, and when treating trench waste water, the composition containing dichromate has poor stability and storage stability. It has drawbacks such as pollution problems caused by chromium, and for this reason, it has become difficult to put dichromate-containing photosensitive resin compositions into practical use. In the case of photosensitive resin compositions containing diazonium salts, their stability and storage properties are better than those containing dichromates, but they are still far from satisfactory, especially their sensitivity is lower than those containing dichromates. The sensitivity is inferior to that of the photosensitive resin it contains, and the strength of the cured film obtained by exposure is also insufficient.

In order to solve the above-mentioned problems of water-soluble photosensitive resins, a photoinsolubilizable resin which is a polyvinyl alcohol derivative containing a styrylpyridinium group and a method for producing the same have been published in Japanese Patent Publication No. 56-5761 and Japanese Patent Publication No. 56-5762. Disclosed in the issue. Similarly, a photo-insolubilizable polyvinyl alcohol derivative containing a styrylquinolinium group and a method for producing the same are disclosed in JP-A-56-11906. Although these photosensitive styrylpyridinium group- or styrylquinolinium group-containing folivinyl alcohol derivatives have excellent sensitivity and water solubility, they have the following problems.

That is, it is produced by adding a styrylpyridinium compound or a styrylquinolinium compound having a haaldehyde group or an acetal group to polyvinyl alcohol through an acetalization reaction. However, since the styrylpyridinium polyvinyl alcohol aqueous solution or styrylquinolinium polyvinyl alcohol aqueous solution produced in this way is inherently water-soluble, the image area (7) tends to swell after photocrosslinking, making it difficult to obtain sufficient image strength. do not have.

In order to solve such problems, Japanese Patent Application Laid-Open No. 55-6244
It has been proposed to add something that imparts water resistance, such as a vinyl acetate emulsion as described in '6. However, with this method, the water resistance is still insufficient, the gradation reproducibility is poor, high contrast cannot be obtained, and the edges of the image are sharp and large.

OBJECTS OF THE INVENTION An object of the present invention is to provide a composition containing polyvinyl alcohol or a polyvinyl alcohol derivative having a styrylpyridinium group or a styrylquinolinium group, which is easily soluble and provides high-contrast images with good gradation reproducibility. .

Structure of the Invention The present invention is a wax emulsion of polyvinyl alcohol or a polyvinyl alcohol derivative obtained by adding a compound having a styrylpyridinium group or a styrylquinolinium group by an acetalization reaction.

(8) It is a good KLJC product when mixed in the image forming property, especially gradation reproducibility. The present invention further improves the adhesion of the image to the substrate by adding and mixing a silane coupling agent represented by the general formula (1) and/or a colloidal solution of high molecular weight silicic anhydride. That is, the present invention provides a composition containing a photosensitive polyvinyl alcohol derivative as a photosensitive element, wherein the photosensitive polyvinyl alcohol derivative has a main chain polymerization degree of 200 to 4000 and a main chain polymerization degree of 70 to 4000.
It has a saponification degree of 98 molar coefficient and 0 based on the total amount.
．． The following general formula (■) with a mole ratio of 3 to 40: (in the formula, Y is the general formula Ql) and a group having a plow: R1 represents one member selected from the group consisting of a hydrogen atom, an alkyl group, or an aralkyl group. each of the alkyl and aralkyl groups may contain at least one member from the group consisting of a hydroxyl group, a carbamoyl group, an ether bond and an unsaturated bond, and R2 is a hydrogen atom, or It represents a lower alkyl group, X- represents an anion, m represents 0 or 1, and n represents an integer of 1 to 6. ) is a photosensitive polyvinyl alcohol derivative containing a styrylpyridinium group or a styrylquinolinium group, and the photosensitive element is mixed in a wax emulsion. .

In the composition containing the photosensitive trivinyl alcohol derivative of general formula (1), the alkyl group represented by R1 in general formulas (U) and (g) has 1 to 4 carbon atoms, such as methyl, ethyl, Propyl and butyl groups are preferred, and the aralkyl group represented by R4 preferably has 7 to 19 carbon atoms, such as benzyl, phenethyl, and trityl groups. Furthermore, the alkyl group and aralkyl group represented by R1 include at least one selected from the group consisting of a hydroxyl group, a carbamoyl group, an ether bond, and an unsaturated bond;
For example, it may be a hydroxyethyl, carbamoylmethyl or methoxymethyl group.

The lower alkyl group represented by R2 in the general formula (Tsukuda) preferably contains 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or butyl group. Furthermore, the anion represented by
-1 luenesulfonate ion is preferred.

Waxes used in the present invention include beeswax, animal waxes such as shellac, vegetable waxes such as carnauba wax, nografine wax, and other synthetic waxes such as higher fatty acids, higher alcohols, and polyhydric alcohols of higher fatty acids. Esters, higher ketones, higher amines,
Higher amides, condensates of higher fatty acids and amines, synthetic paraffins, chlorinated paraffins, and other low-molecular polyethylenes,
Examples include low-molecular polypropylene, which is used as an emulsion. These waxes need to be solid at room temperature and preferably have a melting point or softening point of 65° C. or higher. Also, sticky wax is not preferred.

Photosensitivity in the present invention? In the composition containing a ribinyl alcohol derivative as a photosensitive element, the wax emulsion has a solid content weight ratio of 0 to the photosensitive element 1.
．． If it is less than 5, the water resistance will be insufficient and the gradation reproducibility will also be poor. If the solid content weight ratio is more than 5, the proportion of the photosensitive layer elements in the solid content is too low to be used as a photosensitive composition. Therefore, the solid content weight ratio is 1:0.5
An image with good gradation reproducibility can be formed if the ratio is in the range of 1:5 to 1:5, and preferably 1:1 to 1:3.

In the present invention, the general formula (IV
) XSI(OR)3(IV) (In the formula, A hydrolyzable group, including a methoxy group,
It is an ethoxy group. ) can also be added. This is generally called a silane cassilling agent, and by adding it to the photosensitive composition, it improves the adhesion to the substrate without impairing gradation reproducibility. In addition, the appropriate amount of addition is 0.001 part by weight to 1 part by weight,
Preferably it is 0.01 part by weight to 0.1 part by weight. 0.
If the amount is less than 0.001 part by weight, no effect will be observed, and if it is more than 1 part by weight, the adhesion to the substrate will be too improved, resulting in poor developability and poor gradation reproducibility.

Examples of this compound include γ-methacryloxyglopyltrimethoxysilane, γ-glycidoxyglopyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,
Examples include methyltrimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, and vinyltrimethoxysilane.

Furthermore, in a preferred embodiment of the present invention, high molecular weight silicic anhydride may be added to the composition comprising the photosensitive element and the emulsion containing the ester. It is preferable that the silicic anhydride has a suitable particle size, and a particle size of 20 mμ to 70 mμ is suitable. If the particle size is smaller than this, the ionic nature of the silicic anhydride will cause a total decrease in the storage stability of the photosensitive composition, and if the particle size is larger than this, the surface of the image will be rough and clear images cannot be obtained. Further, the silicic anhydride is added in the form of a colloidal solution, and the amount added is 0.0
0.01 parts by weight to 1 part by weight is appropriate, preferably 0.0 parts by weight.
1 part by weight to 0.1 part by weight. This addition improves the adhesion of the image area and the physical strength of the image.

When the photosensitive resin composition of the present invention is used as a coating liquid, additives such as dyes, pigments, viscosity modifiers, and adhesion improvers to substrates can be added as appropriate depending on the purpose and type.

As the support for the photosensitive resin composition of the present invention, aluminum plates, zinc plates, glass, plastic films, paper, etc. can be used.

The present invention will be explained in detail below with reference to Examples.

Example I A 10% solution of B-24 (electrified PVA) with 1.0 mol% SBQ added and T-350 (wax emulsion manufactured by Hekinuto Japan) as a lavender binder
-22-RE3 (Red fluorescent pigment made by Kasei Ozotonics)
The mixture was well dispersed in a sol mill, coated on an aluminum plate with a Whaler at a density of 4 m9/J, dried, and passed through a step tablet from a distance of 1 m using a 2 kW ultra-high pressure mercury lamp.
exposed for minutes. Thereafter, when the image was developed with spray (15) -, an image with a high gamma value (good gradation reproducibility) was obtained due to the addition of the wax emulsion. The results are shown in Table 1 and FIG. 1. Table 1 The gamma value is determined by varying the amount of light irradiated onto the photosensitive layer and measuring the residual film thickness rate of the photosensitive layer after development.

The way to find it is 100% from this graph of residual film thickness and light amount.
A straight line connects the remaining point to the 0% remaining point, and the - inclination θ from the X axis is defined as the gamma value, and the larger this value, the better the gradation reproducibility.

The pigment to binder ratio was 11.

Example 2 1.2 mol% in Denka Popal B-24T (manufactured by Denka)
A 10% solution and Eponol (17%) containing SBQ
) (16) (trade name of polyethylene wax emulsion manufactured by Ichipo Co., Ltd.) was added three times to the amount of the photosensitive element, and MTB-10 (black pigment manufactured by Morishita Bengara Co., Ltd.) was added as a coloring agent to prepare a photosensitive composition. 1.
After coating and drying, the film was exposed to light from a distance of 1 frL through a step tablet using a 2 kW ultra-high pressure mercury lamp for 5 minutes. After that, it was developed with Nusolet. As shown in Table 1, by adding polyethylene wax emulsion, comparative example Toshitenigazol H-03 (trade name of vinyl acetate emulsion, manufactured by Nippon Carbide Co., Ltd.) was coated with the same treatment and conditions as the above formulation, instead of adding PE wax emulsion. After drying and exposure development, an image with good gradation reproducibility was obtained.

Table 2 Example 3 A 10% solution of Kuraray Bhopal 224 (PVA manufactured by Kuraray) with 0.9 mol% SBQ added and Pegamal G (
Microwax emulsion (trade name, manufactured by Mobil Oil Company) was used at a solid content weight ratio of 1=3, and T-glycidoxyprobyltrimethoxysilane was added at 0 parts per 100 parts of the total weight of the photosensitive element and the wax emulsion. .0
5 parts by weight were added, and a coating of 1.5 μ/i was applied on a glass plate, and after drying, it was exposed to light from a distance of 1 m for 2 minutes using a 2 kW ultra-high pressure mercury lamp through a step tablet. Thereafter, when developed by spraying, an image with good gradation reproducibility (gamma value 5.5) and good adhesion to the substrate was obtained.

Example 4 A 10% solution of Kuraray Bhopal 224 (PVA manufactured by Kuraray) with O19 mol% SBQ added and Pegamal G (
Microwax emulsion (trade name, manufactured by Mobil Oil Company) with a solid content weight ratio of 1:3 and an average particle size of 25yy.
0.05 parts by weight of a colloidal solution of high molecular weight silicic anhydride of +μ is added to 100 parts of the total weight of the photosensitive element and the wax emulsion, and the mixture is coated onto a glass plate at a rate of 1.5μ/i.
After drying, it was exposed to a 2 kW ultra-high pressure mercury lamp from a distance of 1 m for 2 minutes through a step tablet. After that, it was developed with Nusolet, and the gradation reproducibility was good (gamma value 5.0).
) and an image with good adhesion to the substrate was obtained.

Example 5 10% solution of Kuraray Bhopal 224 (PVA manufactured by Kuraray) with 0.9 mol% SBQ added and Vegamaru G
(Micro Wax Emulsion trade name manufactured by Mobil Oil Company) with a solid content weight ratio of 1:3 and γ-glycidoxyprobyltrimethoxysilane and an average particle size of 25fnμ.
of a colloidal solution of high molecular weight silicic anhydride at a total weight of 100% of the photosensitive element and the wax emulsion, respectively.
Add 0.05 parts by weight to 1.5 parts by weight and place 1.5 parts on a glass plate.
m9/cm 2 was applied, and after drying, it was exposed to light from a distance of 1 m for 2 minutes using a 2 kW ultra-high pressure mercury lamp through a step tablet.

After that, the film was developed by spraying, and the following results as shown in Table 3 were obtained.

(19) (20) Table 3 shows that the addition of a colloidal solution of r-glycidoxyzorobyltrimethoxysilane and high molecular weight silicic anhydride improves the adhesion to the substrate without significantly reducing gradation reproducibility. Additionally, a competitive effect was observed.

Example 6 1.0 mol% S in 0M14 (PVA made by Nippon Gosei)
A 15% solution of BQ added and T-130 (trade name of wax emulsion manufactured by Hoechst) were mixed at a solid content weight ratio of 1:4, and vinyltrimethoxysilane was added as a coloring agent to create Shanin Peacock Blue ( Mix blue pigment (manufactured by Toyo Ink Co., Ltd.) and spread the liquid on an aluminum plate. Oq/a
Coating on n 2, after drying, pass through the step tablet to 2
After being exposed to a kW ultra-high pressure mercury lamp for 2 minutes and then developed by spraying, the results shown in Table 4 were obtained.Table 4 Note: Total weight of the photosensitive element and wax emulsion 1. 1.1 mol% S in Example 7 GH23 (PVA manufactured by Nippon Gosei) based on 0 parts of O
A 10% solution of the additive added to BQ and T-730 (trade name: Rough-in Wax Wax Emulsion (manufactured by Hoechst)) were mixed at a solid content weight ratio of 1:2.5, and the total of the photosensitive element and wax emulsion was mixed. The amount of high molecular weight anhydrous silicic acid colloid solution with an average particle size of 30 to 40 mμ was varied relative to 100 parts by weight, and this solution was coated on an aluminum plate and treated by the method of Example 1 to observe the effect. and Table-5
It will look like this.

Margin Table 5 Below: Effects of the Invention According to the present invention, a photosensitive resin composition with excellent image forming properties, particularly gradation reproducibility, can be obtained.

[Brief explanation of the drawing]

FIG. 1 shows the relationship between the number of steps and the residual film yield in Example 1.

Claims (1)

Claims: 1. A composition comprising a photosensitive polyvinyl alcohol derivative as a photosensitive element, wherein the photosensitive polyvinyl alcohol derivative has a main chain polymerization degree of 200 to 4000 and a main chain polymerization degree of 70 to 9.
It has a degree of saponification of 8 mol, and a saponification degree of 0.
3 to 40 molar ratio of the following (where Y represents a group having the following general formulas (II) and (Ill): amount 1), R1 represents a hydrogen atom, an alkyl group, or an aralkyl group, The alkyl group and aralkyl group each may contain at least one member selected from the group consisting of a hydroxyl group, a carbamoyl group, an ether bond, and an unsaturated bond, R2 represents a hydrogen atom or a lower alkyl group, and - represents an anion, m represents 0 or 1, and n represents an integer of 1 to 6. A composition characterized in that the photosensitive element is mixed into a wax emulsion. 2. 2. The composition of claim 1, wherein the solids weight ratio of said photosensitive element to said wax emulsion is from 1:0.5 to 1:5. 3. In a composition containing a photosensitive polyvinyl alcohol derivative as a photosensitive element, the photosensitive polyvinyl alcohol derivative has a main chain polymerization degree of 200 to 4000 and a main chain polymerization degree of 70 to 9.
It has a degree of saponification of 8 mol, and a saponification degree of 0.
3 to 40 mol of the following general formula (wherein Y represents a group having the following general formula (II) and I: ■ 1 and 1 , and R1 represents a hydrogen atom, an alkyl group, or an aralkyl group) , each of the alkyl group and aralkyl group may contain at least one member selected from the group consisting of a hydroxyl group, a carbamoyl group, an ether bond, and an unsaturated bond, R2 represents a hydrogen atom or a lower alkyl group, X- represents an anion, m represents 0 or 1, and n represents an integer of 1 to 6. Wow, in the wax emulsion in which this photosensitive element is mixed, the general formula (IV) xs I (OR) 3 (IV) (wherein and R is a methoxy group, an ethoxy group, etc.) and/or a colloidal solution of high molecular weight silicic anhydride. 4. The weight ratio of the photosensitive element and the wax emulsion is 1:0.5 to 1:5, and the compound is expressed by the formula (IV) based on 100 parts of the total weight of the photosensitive element and the wax emulsion. The content of the compound contained in the compound is 0.
4. The composition according to claim 3, wherein the amount is from 0.001 parts by weight to 1 part by weight. 5. The weight ratio of the photosensitive element and the wax emulsion is 1:0.5 to 1:5, and the content of the colloidal solution is based on 100 parts of the total weight of the photosensitive element and the wax emulsion. The composition according to claim 3, wherein the amount is 0.001 part by weight to 1 part by weight.