JPS58224350A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain superior resolution, by using an aq. dispersion of a synthetic resin contg. acetoacetylated PVA type resin or an allylated PVA type resin. CONSTITUTION:A photoreaction accelerator is added to an aq. synthetic resin dispersion contg. an acetoacetylated or allylated PVA type resin. A degree of acetoacetylation or allylation in said resin is >=0.05mol% and it may be raised the upper limit of a solubility limit, but it is usually 0.1-35mol%. It is preferable to have 200-3,000 average polymn. degree, and <=35mol% residual acetyl groups. To prepare an aq. synthetic resin dispersion, for example, acetoacetylated or allylated PVA is used as an emulsifyer or a protective colloid, and a monomer is emulsion or suspension polymerized.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel photosensitive #1 resin composition, particularly a photosensitive resin composition suitable for screen plates.

BACKGROUND ART Conventionally, as a photosensitive resin composition for screen plates, a composition in which polyvinyl acetate emulsion is blended with a photosensitizer such as polyvinyl alcohol and a diazonicum salt is known.

However, emulsion-type photosensitive resin compositions such as those mentioned above require relatively long exposure times, and as society progresses, original images with more complex and special compositions are handled. There is room for further improvement in terms of efficiency of plate-making work, such as the need for excellent resolution.

However, as a result of extensive research in order to solve this problem, the inventors of the tree added a photoreaction accelerator to a synthetic resin aqueous dispersion containing an acetoacetylated polyvinyl alcohol resin or an allylated polyvinyl alcohol resin. This composition exhibits even better resolution, and also has a photocurable part. i It was discovered that it is useful as a photosensitive resin composition because it has high mechanical strength, good printing resistance, and excellent adhesion to various base materials, and the present invention I was able to complete it.

The aceto, acetylated polyvinyl alcohol (hereinafter abbreviated as acetoacetylated PVA)-based resin in Kippatsu tJ11 can be produced by any method, and there is no limitation on the manufacturing method, but preferably, it is an addition reaction of digtene to the polyvinyl alcohol-based resin. or by transesterification of acetoacetate. Similarly, a preferred method for producing allylated polyvinyl alcohol (hereinafter abbreviated as allylated PVA) based sI fat is a method in which a polyvinyl alcohol based resin is reacted with an allyl compound such as allyl chloride or allyl bromide. The base polyvinyl alcohol resin may include partially or completely saponified polyvinyl esters such as polyvinyl acetate, as well as vinyl acetate-based resins and other copolymerizable hexamers such as unsaturated carboxylic acids or "Copolymer modified" polyvinyl made by saponifying its parts or copolymers with complete esters, salts, anhydrides, amides, nitriles, unsaturated sulfonic acids or their derivatives, α-olefins having 2 to 30 carbon atoms, vinyl ethers, etc. Polyvinyl alcohol that has been modified after acetalization, phretanization, etherification, grafting, phosphoric acid esterification, etc. of alcohol or polyvinyl alcohol can also be used.

The degree of acetoacetylation or degree of allylation in the above resin is 0.
．． Although it is possible to increase the water solubility at 0.05 mol % or more, it is usually selected from the range of 0.1 to 55 mol %, particularly 0.2 to 50 mol %. If the degree of acetoacetylation or allylation is too low, curing by light irradiation will not be sufficient and a satisfactory image (2) will not be obtained.

Acetoacetylation or allylation of more than necessary H is unsuitable for the purpose of the present invention since it results in water insolubility.

Moreover, the average degree of polymerization is 200 to 5000, preferably 300 to
2000 Remaining acetic acid group #i Preferably 55 mol% or less 30
It is desirable to select from a range of mol% or less.

In order to prepare the aqueous separation solution of the acetoacetylated PVA or allylated PVA-containing composite Fft resin of the present invention, the monomers are subjected to a-polymerization or suspension using acetoacetylated PVA or allylated PVA as an emulsifier or a protective colloid. turbidity polymerization, ■ Post-emulsifying or post-suspending a solution or melt of Fftm fat in the presence of acetoacetylated PVA or allylated PVA, ■ Synthetic Si fat emuldigon or suspension obtained by any method. The above six cases include adding acetoacetylated PVA or allylated PVA to Chiron. Below, we will explain each case button in detail.

(2) Method by Emulsion Polymerization or Suspension Polymerization This method is usually preferably carried out when producing a polymer emulsion of a vinyl compound. Of course, suspension polymerization is also possible, but emulsion polymerization is practically carried out. For the 1L polymerization, a normal 1L polymerization method is used, in which a vinyl compound is added temporarily or continuously in the presence of water, acetoacetylated PVA or allylated PVA, and a polymerization medium, and the mixture is heated and stirred. It can be implemented. The amount of acetoacetylated PVA used is preferably 0.1 to 30% by weight, and suitably about 2 to 20% by weight, based on the solid content of the polymer. If it is less than 2% by weight, no sufficient effect will be obtained, and if it is more than 20% by weight, the effect will not increase in proportion to the amount used. The acetoacetylated P'/A or allylated PV
Although it can be added at any point in time, such as at the start, during or after the end of the A emulsion polymerization, it is usually added at the start or in the middle of the Vi polymerization.

Vinyl compounds used in this method include vinyl acetate, vinyl propionate, acrylic ester, methacrylic ester, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, styrene, ethylene, propylene resin, glycidyl acrylate, glycidyl methacrylate, Glycidyl group-containing compounds such as glycidyl divinyl ether and glycidyl vinyl ether, N
- Methylol group-containing compounds such as methylol acrylamide and N-methylol methacrylamide; - alkoxy group-containing derivatives thereof; carboxylic acid amides such as acrylamide and methacrylamide F; carboxylic acids such as acrylic acid and methacrylic acid; Examples include divinyl adipate, divinyl succinate, triallyl ciaslate, diallyl fumarate, triallyl citrate, diallyl maleate, vinyl perzatate, etc., and these are homopolymerized or copolymerized. Particularly suitable is the instant copolymerization of vinyl acetate.

Disintegrated nonionic surfactants and ionic surfactants can also be used in combination with acetoacetylated PVA or allylated 1'VA. Still other 11. inhibitors, such as PVA, cell O-M conductors (carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, etc.), polyacrylic acid derivatives, (anhydrous) maleic acid-vinyl ether copolymers, (
anhydride) maleic acid-vinyl acetate copolymer, vinyl acetate-
(Meth)allylsulfonic acid (salt) copolymer pycnide and the like can also be used in combination as appropriate. Other various additives, regulators, etc. used in ordinary emulsion polymerization can also be used as appropriate.

(2) Method by post-condensation or post-suspension This method is preferably carried out when preparing a synthetic resin emulsion or suspension that is difficult to produce by diluting polymerization or suspension polymerization.

In this method, the post-1L conversion method is particularly advantageous, and the acetoacetylated PVA or allylated PVA is dissolved in water, and a solution or molten resin is added dropwise and stirred, or the molten resin is added dropwise and stirred. An aqueous solution of acetoacetylated PVA or allylated P, V, or A may be added dropwise into the solution and stirred. There is no particular need for heating during emulsification, but if necessary, it may be heated to about 45 to 80°C.

The substances to be emulsified are not particularly limited, and include epoxy resin, urethane resin, urea-formaldehyde initial condensate, phenol-formaldehyde initial condensate, alkyd resin, polyester resin, ketene dimer, silicone resin, wax, polypropylene. , polyethylene, etc.

The amount of acetoacetylated PVA and allylated PVA to be used varies somewhat depending on the resin content of the required emulsion or suspension, but it is usually 0.00000000000000000000000000000000000000000000000.
It is selected from the range of 1 to 60% by weight, preferably 1 to 25% by weight. If necessary, a nonionic activator such as a polyoxyethylene-alkyl ether type, a polyoxyethylene-anolephenol type, a polyhydric alcohol-olester type, or a higher aleamine salt, etc., may be added together with the resin, if necessary. A cationic activator can also be used in combination as appropriate.

It is also possible to mix these active agents into the object to be dispersed.

(2) Post-addition method In this method, acetoacetylated PVA or 7lylated PVA is added to a synthetic resin emulsion or suspension obtained by any method.

Targeted synthetic resins include styrene/butadiene polymers, cis-1,4 polyisoprene polymers, chloroprene polymers, acrylonitrile/butadiene polymers, vinylpyridine polymers, methyl methacrylate/butadiene polymers, polyurethane, and acrylic esters. Examples include vinyl acetate polymers, ethylene/vinyl acetate polymers, vinyl chloride polymers, polystyrene, polyethylene, silicone, polybutene, thiocol, and the like.

Acetanatylated P in emulsion or suspension
When adding and mixing VA or allylated PVA, 9. P
When adding VA as an aqueous solution, it is sufficient to simply add the aqueous solution to the emulsion or suspension at room temperature while stirring, but when adding the PVA powder, do not stir the emulsion or suspension. ) Adding the powder and heating it to 60 to 80°C is preferable because uniform mixing can be completed in a short time. The amount of acetoacetylated PVA or allylated PVA used is approximately 0.1 based on the emulsion or suspension solids content.
It ranges from 1 to 20% by weight, preferably from 1 to 20% by weight.

In this way, the emulsion or suspension obtained in steps (1), (2), and (3) may be used as is, or it is usually further combined with acetoacetylated PVA or allylated PVA, so that the ratio of aPVA to the solid content of the emulsion or subendibon is 5 to 500% by weight. Adjust so that it is %. If the mixing ratio is less than 5% by weight, sufficient photosensitivity and mechanical strength for coating cannot be imparted, while if the mixing ratio is more than 500% by weight, workability during plate making becomes a problem.

It is also possible to add a water-soluble polymer substance for the purpose of increasing viscosity. The amount added is usually in the range of 5 to 500% in terms of solid content based on the emulsion or suspension. Such water-soluble polymer substances include PVA,
Examples include starch, CMC, hydroxymethylcellulose, hydroxyethylcellulose, methylcellulose, casein, etc., and these may be mixed in any form such as an aqueous solution or a powdered form.

A photoreaction accelerator is used in combination with the aqueous synthetic resin dispersion in the form of an emulsion or suspension thus obtained.

As photoreaction accelerators, benzoin alkyl ethers such as benzoin methyl ether, benzine ethyl ether, and benzoin isopropyl 1-thyl, organic iodine compounds such as digtylsulfide, benzyl sulfide, and decylphenyl sulfide F, diazonium salts, tetrazonium salts, or Complex salts of these and zinc chloride or condensates thereof, dyes such as azobisisoprodylonitrile and methylene blue, or combinations thereof with p-) toluenesulfonate ions, organic peroxides, hydrogen peroxide, pyrylium salts, or Thiapyrylium salt, ammonium dichromate, ayatophenone, penzophene/benzyl, phenanthrene, thiodicytone, cycloglopylphenyl ketone, acitraquinodi, 2-chloroanthraquinone, 2-bromoanthraquinone, anthraquinone β-sulfonic acid sodium, 1 .5-dinitroanthraquinone, 1,2-pengenthraquinone, phenanthrenequinone, 5-benzoylacenaphthene, 5-nitroacenaphthene, 1,4-naphthoquinone, 1.8-phthalofurenaphthalene, 2-nitrofluorene, p -Nitroaniline picramide, benzurdehyde, etc., and these may be used alone or in combination of two or more.

Not limited to those listed above, but also reactions, cross-linking,
Any substance that promotes polymerization can be used.

In order to form #t by light irradiation using the composition of the present invention, the composition is first applied to a base material and dried, or a film is prepared in advance from the composition by any method. Adhere to the base material.

Base materials include cotton, rayon, wool, polyester,
Polyamide thread/polyacrylonitrile/Volibi =...
Woven fabrics, non-woven fabrics, gauze, curved lead plates, aluminum plates, magnesium plates, steel plates, copper plates, etc. made of synthetic fibers based on A...-''□... are used.

Using the thus obtained coated plate, by irradiating it with ultraviolet rays through the negative screen, the exposed areas become water-insoluble, and the unexposed areas can be redispersed with water.
If you wash it with water, only the unexposed areas will be removed. As a light source, a pressure water lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a kusenoshi lamp, etc. are used.

For purposes such as printing, a non-woven fabric or gauze is used as a base material, and the holding board obtained by the above treatment is used after being twisted.
You can add patterns to the fabric by dyeing it.

For the purpose of letterpress printing, intaglio printing, printed wiring, etc., the above-mentioned image formation 1. 9. Etching and exposing the base material (metal) (also corroding the metal part).

In case of misfire 1, a more excellent suppressor plate can be obtained by further hardening the suppressor plate as described above.

Examples of drugs used for such purposes are listed below.

Aldehydes (glyoxal, glutaraldehyde) Isocyanate compounds (e.g. tolylene diisocyanate, hydrogenated tolylene diisocyanate, trimethylolpropane-tolylene diisocyanate adduct, triphenylmethane triisocyanate, methylene bis(4)
- Phenylmethane triisocyanate, inphorone diisocyanate, and their ketoxime products or phenol glock products) Epoxy compounds (ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin di- or triglycidyl ether, 1,6 −
Hexasidiol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diglycidylanine) Amine compounds (urea, melamine, and their methylolated products, hexamethylenediamine, triethanolamine) Compounds with radical generating ability (Hydrogen peroxide, potassium persulfate, asimonicum persulfate, benzoyl peroxide, succinic peroxide, t-butyl peroxide maleic acid, 1-butyl hydroperoxide bensoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether organic iodine compounds such as pentwin alkyl ethers, dibutyl sulfide, besidyl sulfide, decylphenyl sulfide, diazonium salts, tetrazonicum salts, or complex salts or condensates of these with zinc chloride;
azobisisobutyronitrile I, 2,2'-azodis(2-azidinopropane) hydrochloride, dyes such as methylene blue or combinations thereof with p-toluenesulfonate ions, pyrylium salts or thiapyrylium salts, dichromium ammonium acid, acetophenone, benzophenone, benzyl, phenanthrene, thioxacitone, dichloroglopylphenyl ketone, acitraquinone,
2-Chloroacitraquinone, 2-but6kianthraquinone, acitraquinone β-sulfonic acid sodium, 1,5-dinitroanthraquinone, 1,2-benzanthraquinone, phenanthrenequinone, 5-benzoylacenaphthene, '
5-nitroacenaphthene, 1.4-naphthokinoshi, 1,
8-phthaloylnaphthalene, 2-nitrofluorene, p
-nitroaniline, picramide) Oxidizing agents (potassium dichromate, ammonium dichromate, calcium perchlorate) Polymerizable monomers (2- and droxyethyl acrylate,
-Hydroxyethyl methacrylate, 2-hydroxyglopylacrylate, 2-hydroxypropyl methacrylate, N-vinylpyrrolidone, 2-hydroxyethyl acryloyl phosphate, acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethoxy Methylacrylamide, N-ethoxymethylacrylamide, ethylene glycol monoacrylate, dipropylene glycol monoacrylate), N,N-dimethyl rare trinoethyl acrylate, styrene, vinyltoluene, monochlorostyrene, diallyl phthalate, vinyl acetate, glycidyl methacrylate) Metal salts (aluminum, iron, copper, zinc, tin, titanium,
Chlorides, bromides, nitrates, sulfates of polyvalent metals such as nickel, antimodium, magnesium, vanadium, chromium, etc.
Salts such as acetate (specifically cupric chloride, aluminum chloride, ferric chloride, tin chloride, zinc chloride, nickel chloride, magnesium chloride, aluminum sulfate, copper acetate, chromium acetate) °r ammonium salts ammonium salts of ferric acids such as ammonium chloride, ammonium sulfate, aluminum nitrate, ammonium dichromate, ammonium salts of organic acids such as ammonium acetate and ammonium propionate) The prepared plate is subjected to appropriate treatment by spraying, coating, dipping, etc. with the above-mentioned chemical solution, followed by drying and, if necessary, heat treatment.

Next, the present invention will be explained in more detail by giving examples.

Example 1 Average degree of polymerization +400. PVA with average saponification degree of 92 mol%
An emulsion was prepared in the following manner using Ar1=dodectylated PVA (i7) with a degree of acetoacetylation of 5 mol %.

Equipped with stirrer, reflux condenser, lI@5 funnel, and thermometer.
In a separable flask, add 5 parts of water + 3 L, 11.5 parts of the above acetoacetylated PVA, and 10 parts of vinyl acetate monomer.
The temperature inside the flask was 2il-6 while stirring.
The temperature was raised to 0°C. Meanwhile, while purging the inside of the flask with nitrogen gas, 10% H20, 2 Wrl of water, and 10 parts of tartaric acid (5 d) were added to initiate polymerization. Perform initial polymerization for 50 minutes,
The remaining 90 parts of vinyl acetate monomer was added dropwise over 5 hours to prepare all the monomers, and the mixture was aged at 70° C. for 1 hour and then cooled.

A photosensitive textile printing composition having the following composition was produced using the above emulsion.

The #8 likelihood composition was applied in a packet onto 150 mesh Tetron gauze to a film thickness of 20 μm.

This was exposed through a line drawing negative, most of the unexposed portion was eluted with tap water, and the water was completely removed using a spray gun and dried.

When this printing screen was actually printed on 1L, which has excellent water resistance and solvent resistance, it was possible to print more than 20,000 sheets.

Example 2 The suppression plate of Example 1 was treated with a 5% ammonium persulfate aqueous solution Kfi*
t, *0980=. "Pa, fm, ll l, *4
(7) “It withstood more than 10 pages of printing.

Practical Example 5 The holding plate of Practical Example 1 was immersed in a 10% ethylene glycol diglycidyl ether solution for 6 minutes and then treated at 60°C for 2 hours 1
．． Tamonoke withstood more than 50,000 prints.

Example 4 Epoxy resin (manufactured by Kobunshi Kagaku Co., Ltd., Evodite EL-
2) 45 parts, nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd.,
Octopol 50) 1 part, acetoacetylated PvA (degree of acetoacetylation 25 mol%, residual acetate group 0.5 mol%)
, polymerization degree +200) was emulsified using a homogenizer to obtain an emulsion.

20 parts of the emulsion and a degree of ayatoacetylation of 8 mol%,
Allylation degree 4 mol%, residual acetic acid group 5 mol%, polymerization degree 50
100 parts of acetoacetylated and allylated PVA (1
(0% aqueous solution) and 5 parts of benzoin isopropyl ether were mixed to obtain a photosensitive composition.

The composition was spin-coated onto a previously cleaned stainless steel plate, pre-dried at 50°C for 20 minutes, and then irradiated with a 5 KW high-pressure mercury lamp for 5 minutes with a line drawing negative kept in close contact with the plate at a distance of 60 cm [7. .

The unexposed areas were then washed away to form an image. Next, immerse in 5% aluminum sulfate aqueous solution for 6 parts 1. Thereafter, heat treatment was performed at 120''C for 20 minutes.

When a spray set was etched using a drinking water solution containing 5% 40° Baume's hydrochloric acid, the etching depth was 0.
A relief with good linearity without 5% resist peeling was obtained.

It showed good printability.

Example 5 Degree of acetoacetylation 10 mol%, residual acetate group 1 mol%,
A vinyl acetate/2-ethylhexyl acrylate copolymer emulsion was prepared using acetoacetylated PvA having a degree of polymerization of 1200 as a protective colloid, and the following photosensitive composition was prepared.

The tuna composition was applied to a uniform thickness of 1 c of polyester film 50 μm, and the resulting photosensitive resin film was pressure-bonded using a squeegee to a stainless steel metal screen (50 mesh) coated with the same photosensitive composition in advance. A screen photosensitive plate was obtained. A line drawing positive was applied closely to this (7) It was irradiated with a high-pressure mercury lamp from a distance of 1σ for 2 minutes, and then washed and developed, and a good screen plate was obtained.

This material was particularly suitable for concave printing, had good adhesion to wire mesh, and had excellent rigidity resistance such as ink resistance.

Claims (1)

[Claims] A photosensitive resin composition prepared by adding a photoreaction accelerator to a synthetic resin aqueous dispersion containing acetoacetylated polyvinyl alcohol + St fat or allylated polyvinyl alcohol resin.