JPS59136731A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive resin composition having superior flowability, coatability, photosensitivity and high adhesive strength to a substrate and capable of being easily removed with water at the unexposed part by adding modified polyvinyl alcohol having anionic groups in the molecule and a diazonium compound. CONSTITUTION:A photosensitive resin composition is blended with modified polyvinyl alcohol having anionic groups in the molecule and a diazonium compound. The anionic groups mean chemical structural units which are negatively charged when dissociated in an aqueous soln., and they include carboxyl groups, sulfone groups and phosphoric acid groups. The modified polyvinyl alcohol is preferably prepd. by copolymerizing an ethylenic unsatd. monomer having an anionic group with vinyl acetate and by saponifying the copolymer in the presence of an alkali catalyst. The suitable amount of the anionic groups contained in the modified polyvinyl alcohol is 0.01-30mol%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive resin composition containing a modified polyvinyl alcohol (PVA) $-diazonium compound having an anionic group in the molecule.

Photosensitive resins are mostly used as image forming materials, and image forming methods using photosensitive resins include resist images, relief images, transferred images, colored images, light scattering images, bubble images, Various methods have been used, including electrostatic imaging. By forming these images, they are used for printing plate materials, precision processing applications using photoresists, and J4a printing.

Photosensitive resins made of PVA s- and diazonicum compounds are inexpensive and have good properties of the resulting photosensitive film, and water can be used as the solvent for washing and removing unexposed areas, that is, for development. Because it is easy and safe to handle, it has been used in resist agents such as emulsions for screen printing plate making and offset PS thousand plates, but recently the development of minute devices in the electronics field has been remarkable, and photosensitive resins Nowadays, there is a demand for resist agents and plate-making agents that can form finer images. As a result, the number of fields where intramuscular injection is utilized is increasing, such as the ability to remove water from unexposed areas. In view of these circumstances, we conducted various studies and found that a photosensitive resin composition containing modified PVA and diazonium compound gold having an anion group in the molecule has good fluidity, coatability, and excellent photosensitivity. It also has excellent water removability from unexposed areas, and Juku et al. found that it also has good adhesion to substrates.

Common sense suggests that since diazonium compounds are cationic, they must be used with anionic film-forming polymers.
Although it seems impossible to blend Mr. What happened is surprising.

Furthermore, according to the present invention, the following effects can be obtained.

That is, the modified PVA containing an anionic group in the molecule of the present invention
A photosensitive solution consisting of a water bath solution containing a diazonium compound has low foaming properties and good fluidity, so it can be applied thinly and uniformly to substrates such as stainless steel plates, polyester films, and glass. Furthermore, when the film layer obtained by coating and drying is rendered unsuitable for developing water by irradiation with light, the amount of exposure can be reduced compared to the case of a conventional photosensitive solution using unmodified PVA'i. What is even more important is that compared to using conventional PVA, the insolubilized photosensitive film has better adhesion to metals such as stainless steel plates, plastics such as polyester sheets, and inorganic substrates such as glass plates. Because the insolubilized portion is less prone to peeling or falling off when exposed to light, and the unexposed portion has excellent water solubility, a clear image can be obtained.

This will be explained in detail below.

The anionic group contained in the modified PVA having an anionic group in the molecule used in the present invention refers to a chemical structural unit that dissociates in an aqueous solution and becomes negatively charged, such as a carboxyl group, a sulfone group, or a phosphoric acid group. means.

Modified P■A having all anionic groups in the molecule may be completely introduced with anionic groups by post-modification by subjecting ordinary PVA to a chemical reaction. Scissors completely copolymerized with vinyl acetate, and modified f'VA obtained by curing this copolymer as a catalyst, give particularly favorable results. Alternatively, all of the monoelectric materials may be combined together to form an anionic group during the saponification reaction.

Examples of such ethylenically unsaturated monomers include acrylic acid, methacrylic acid, tarotonic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid or their alkyl esters, carboxyl bases such as 1J anhydride or acrylamide. M monomer, or 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylic, middle 1-methylglobansulfone, vinylsulfone, acrylic. Sulfone group-containing monomers such as sulfone (tR, 6 or their a) V potassium salts, or 3-methacrylamido-3-methylbutanline 66 or its alkali salts A, any phosphoric acid group-containing monomers. Of these, carboxyl group-modified PVA=
The ethylenically unsaturated monomer giving i is maleic acid,
Ethylenically unsaturated dicarboxylic acids such as fumaric acid and itaconic acid are particularly good. Also, as a monomer that provides sulfonic group-modified PVA, sodium 2-acrylamido-2-methylglobanesulfonate is preferred because it gives particularly good results.

These carboxyl or sulfonic groups are preferably bases, for example alkaline bases such as sodium bases, potassium bases, ammonium bases, etc. Among these, sodium bases give good results.

The content of anionic groups, degree of saponification, or degree of polymerization in the anionic group-modified PvA used in the present invention is selected as appropriate, but in order to obtain a composition with excellent performance, these three anion groups should be carefully selected. It is important to combine the

For the purposes of the present invention, the content of anionic groups is 0.01
-30 molti is a suitable range. If it is less than 0.01 mole, there is no significant difference in sensitivity, adhesion, water developability, etc. from unmodified PVA, but if it is more than 30 mole, the compatibility with diazonium salts becomes poor, and the storage stability and uniform coating are reduced. However, considering the practical cost, the degree of modification is 01 to 2.
0 mol, 60 to 100 mol, degree of polymerization is 1
A range of 00 to 6000 is preferable. Furthermore, the content of anionic groups is 0.1 to 5 mol, the degree of saponification is 70 to 98, and the degree of polymerization is 200 to 5,000.
Photosensitivity of photosensitive film, water developability, @layer property of exposed film, water resistance,
Creating the best photosensitive resin composition with a good balance in terms of chemical resistance.The diazonilla J compounds used in the present invention include tetrazonium salts, diazide compounds, diazo resins, and the like.

For example, diphenylamine-4-diazonium chloride.
Diazo resins such as formalin condensed resin, dimethylaniline-4-diazonium chloride/formalin 8 resin, 2.5-dimethoxyphenylmorpholine-4-diazonium zinc chloride double salt/formalin condensed selenium, 3.3
'-dimethoxydiphenyl-4,4'- and diazonium chloride ammonium chloride, 3,3'-diethyldiphenyl-4,4'-bisdiazonium chloride zinc chloride double salt, diphenyl-4,4'-bisdiazonium talon Lido zinc chloride fJ1 salt s ”-ether-N-penzylanil
) 7-4-dianonicum chloride zinc chloride compound, L'
J-dinonalaniline-4-diazonium chloride, 3
．． 3'-dimethoxydiphenyl-4,4'-bisdiazonium chloride, 3,3'-dimethoxydiphenyl-4
, 4'-bisdiazonium sulfate and other tetrazonium salts, siazonium salts, 6-azido-2-(4'-
Examples include diazide compounds such as azidostyryl) penzimitazole and 4,4'-diazidostilbene-2,2'-disulfonamide. Among these diazo compounds, preferred are diphenylamine-4-diasonium chloride formalin condensed resin, 3,s'-diethyldiphenyl-4,4'-bisdiazonium chloride zinc chloride double salt, and 3,3'-dimethoxydiphenyl. -4,4'
-Bisdiazonium chloride zinc chloride double salt, 4,4'-
Diazidostilbene-2,2'-disulfonamide and the like are preferred.

In addition to these photodegradable diazonium materials, known sensitizers such as acetic acid cranylated adducts can be used as appropriate. In addition, additives such as cjjm agents, dispersants, antifoaming agents, etc. may be added as necessary, phosphor particles in the case of making fluorescent surfaces for television cathode ray tubes, pigments in the case of photocurable paints, etc. Ru.

Modified PVA having an anion group in the molecule used in the present invention
The amount to be blended with the diazonium compound varies depending on the type of diazonium compound or the use of the photosensitive resin composition, but it is 2 to 20 (M ratio).
It is best to mix it at 8 degrees.

The photosensitive composition of the present invention includes letterpress or screen M,
This effect can be particularly exhibited in the production of printing plate materials such as.

Examples regarding the photosensitivity of photoinsolubilization by ultraviolet rays and the properties of the seven films of the photosensitive composition of the present invention will be described below, but the invention is not limited thereto. Nafu, capital and % are not specified in particular, and take into account weight parts and M'ik parts.

Example 1 A product obtained by co-alkaline saponification of maleic acid and vinyl acetate, having a maleic acid unit capacity of 3 mol %, a degree of saponification of 89 mol, and a B-type viscosity at 20°C of an aqueous solution of 4
Add 1 part of diphenylamine-4-diazonium chloride/formalin condensation resin to 100 parts of 1O% aqueous solution of 0Cp anionic substrate PVA, mix to make V@, and apply the photosensitive solution evenly onto a zinc plate using a spin coater. After the cloth is dry,
The line drawings were placed in close contact in a vacuum frame, exposed for 3 minutes using a 2000 lux chemical lamp as a light source, and then washed and developed. The image plate was immersed in an aqueous dichromic acid solution for 30 minutes, hardened twice, and then burned at 120° C. for 10 minutes to form an acid-resistant image resist. After rubbing this with 10-thiosulfuric acid according to the usual method,
A letterpress printing image was obtained by dow rot. gills n
Table 1 shows the performance of the photosensitive composition.

Also, for comparison, the same as the above example was used except that unmodified PVA (saponification degree sr 7, bath solution viscosity at 20°C of 4% water-filled solution was 39 cp) was used instead of the above-mentioned anion substrate PVA. Prepare a photosensitive solution and make a letterpress printing image 1#! The performance was evaluated and shown in Table 1 as Comparative Example 1.

From the performance comparison of the Examples and Comparative Examples in the table, is it unclear whether PVA has anionic properties or not? ! ：The photosensitive glue that contains the material has two advantages: it produces clearer images than the photosensitive material.

Number of printable line drawings of positive image seen after unexposed Example 7 of Example 1
A photosensitive solution was prepared under the same conditions as in Example 1 except that various anion group-modified PVA1 shown in 2 was used, and the ability to form a letterpress printing image was evaluated. Table 2 Table 3 Next, the water removability of the unexposed area of the photosensitive resin composition obtained in this example, and the adhesion and resistance of the exposed area are shown. Table 4 shows the smoothness, water resistance, and foaming properties.

Below/:・-1 Table-4 Comparative Example 2...Ke/degree of conversion 88 mol%, 4% viscosity tx 9
Photosensitive resin composition obtained using cps unmodified 1'VA 3,3'-diethyldiphenyl-44'-
Add a photosensitive solution containing 5% bisdiazonium chloride zinc chloride double salt to PVA, adjust the solids concentration to 10%, pass it through a 250-mesh strainer, and then apply it to the substrate. In order to make it easier to see the state of the bubbles during application, I applied one coat with a roll coater,
Dry at °C.

Water removability of unexposed coating film... Substrate coating film is immersed in water at 40°C.
The solubility was observed when the ice was immersed for a time and the ice surface was gently stirred.

Adhesion of exposed coating film...Fifth plate test (vertical, horizontal IW)
N cross cut lines with 11 lines at intervals.
After inserting with a T-cutter, office tape was applied and peeled off at a constant speed, and the percentage of the remaining 1rIa square was determined. ) was measured. For exposure, the light source is 3O.
One A-arc lamp was irradiated for 2 minutes at a distance of 30α.

Water resistance: The remaining state of the exposed coating film was visually observed after being immersed in water at 80°C for 1 hour.

Alkali resistance...1 in 2% NaOH aqueous solution at 80℃
The remaining state of the exposed coating film after time immersion was observed with the naked eye.

Acid resistance: The remaining state of the exposed coating film was visually observed after being immersed in a 5-H01 aqueous solution at 80° C. for 1 hour.

Example 11 Anionic group-modified PVA containing 3 moles of itaconic acid as a copolymerized unit, having a degree of saponification of 87 moles, and a B-type viscosity of 29 Cp in a 4% aqueous solution of 20C was prepared with 5 grams of anionic group-modified PVA, 3,3'
An aqueous solution of -dimethoxydiphenyl-4,4'-bisdiazonium chloride zinc chloride double salt prepared at a ratio of 15% to the PVA was coated onto a glass plate in the form of a 12μ thick film and dried. After that, apply Eastman and Kodak's neutral density filters.
UV irradiation was performed for 30 seconds using a 2 KW metal halide lamp kept at a distance of 5 crn, followed by washing for 1 minute with a constant amount of water. The photosensitivity at this time is shown in Table 5 as a relative value of the exposure amount corresponding to the remaining photosensitive hardening film.

For comparison, conventional unmodified PVA (average degree of polymerization 2,
000, degree of saponification 88 mol%s 4% water fyfU.

The photosensitivity was measured in the same manner as in the examples using the viscosity (29.5 cp at 20°C) and is shown as Comparative Example-3.

Table 5: 2) It can be seen that the photosensitivity is about 1.5 times higher than that of conventional photosensitive compositions made of PVA.

Further, the adhesion of the photosensitive film to the substrate was evaluated by the following method. The photosensitive solutions of the anion group-modified PVA of Example 11 and the conventional PVA of Comparative Example 2 were each coated on a glass plate in the form of a 15 μm thick film and dried at 50° C. for 5 minutes. A black plate with 625 circular holes per 100 cpl was irradiated with ultraviolet rays for 30 seconds using a 2KW metal halide lamp kept at a distance of 25 crn, and then washed with a constant amount of water for 3 minutes. At this time, the remaining circular photoresist film dots were observed and the number of missing dots was determined, and the result was 6.

The photoresist film made of the anion group-modified PVA of the present invention is different from that of the conventional PVA.
It can be seen that the adhesion to the base material is better than that obtained by VA. Further, the circles of the photoresist film dots in the example are formed into a fine shape, whereas the dots in the comparative example have noticeable chipped edges and are unclear, and the composition of the present invention is v! J was found to be able to produce clear photosensitive images.

Table 6 Example 12 Saponification degree 86 obtained by curing an Itaconic acid-vinegar vinyl copolymer containing 3 moles of itaconic acid as a copolymerized unit.
Molch, B type viscosity at 20℃ of 4% aqueous solution is 26C
100 parts of a 10% aqueous solution of anion-modified PVA of p, 20 parts of polyvinyl acetate emulsion (solid content concentration 50%),
20 parts of 4,4'-diazidostilbene-2,2'-disulfonamide (10% aqueous solution) were mixed to obtain a photosensitive composition dispersion number. This dispersion was applied to a polyester screen plate (150 mesh) using a bar coater and dried with ventilation to obtain a photosensitive screen. Next, the positive original was placed in close contact with the original image and exposed to a 3F (vV) ultra-high pressure mercury lamp at a distance of 1m for 3 minutes, washed with water in a shower at room temperature, developed, dried, and had fine edges with no sharpness until fine lines of 100μ. A reproduced screen printing plate was obtained. When this printing plate was used for printing, more than 10,000 very clear prints were obtained, and the reproducibility of the n1 image was also good.

Example 12 except that for comparison, unmodified PVA (saponification degree 86 molar, B-type precision 27 Cp at 20°C of 4-chi aqueous solution) was used instead of anionically modified PVA.
A photosensitive composite hZ material and a screen printing plate were prepared in the same manner as above. Compared to the case of anion-modified PVA, adhesion and developability were poor, and the dryness of the dried plate was poor.

Patent applicant: RiRashi Co., Ltd. Agent: Patent Attorney Ken Honda

Claims (1)

[Claims] (υ Modified polyvinyl alcohol H having an anion group in the molecule and diazonium compound Kanakura Photosensitivity 4+!
1 fat composition. (2) When the anionic group is a carboxyl group or its base, I? F. The photosensitive resin composition according to claim 1. (8) The photosensitive resin composition according to item 1, wherein the anion & is a sulfone group or a base of 7. (4) The photosensitive tree B'fl" according to claims 1 to 3, wherein the content of anionic groups is 0.1 to 30 mol.
Composition. (6) The photosensitive resin composition according to any one of claims 1 to 3, wherein the content of 2 groups is 0.1 to 5 mol.