JPS63118150A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To considerably decrease the smell of a photosensitive resin plate material while maintaining a satisfactory photosensitive characteristic and printability by incorporating a base body resin as a binder, photopolymerizable unsatd. compd. having ethylenic double bonds at the terminal and >=150 deg.C b.p. and compd. having 50-2,000mol.wt. and having an -SH group at the terminal into a titled compsn. CONSTITUTION:This compsn. has (a) 100pts.wt. base body resin as the binder, (b) 20-200pts.wt. photopolymerizable unsatd. compd. having the ethylenic double bonds at the terminal and >=150 deg.C b.p. and (c) 0.01-10pts.wt. compd. having 50-2,000mol.wt. and having the -SH group at the terminal. The mol.wt. of the component (c) is more preferably 70-1,000. The compd. to be used as the component (c) is alkyl thiol, arom. thiol, alkanol thiol, etc. The smell of the plate material itself and the waste liquid after the development thereof is thereby considerably decreased without impairing the photosensitive characteristic and printability of the plate material.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention eliminates the odor of the photosensitive resin plate material, improves the working environment during development, and provides high image reproducibility and printability. This article relates to a photosensitive resin composition comprising:

[Conventional technology]

Photosensitive resin plate materials for letterpress, lithographic and intaglio printing, which have a structure in which a photopolymerizable photosensitive resin layer is provided on a metal or plastic base material, have recently been put into practical use. These plate materials are made by attaching a negative or positive original film with a transparent part to a photosensitive resin layer, and then irradiating it with actinic rays to cause photopolymerization of the photosensitive resin layer corresponding to the transparent part of the original film. Then, a relief is formed on the substrate by eluting the unpolymerized portion with a suitable solvent. Photosensitive resin compositions that utilize photopolymerization reactions are used in various applications including printing plates.

The photosensitive resin plate material has a photosensitive resin layer of polycrystalline vinyl, polyamide, polyvinyl alcohol, polymethyl acrylate, polyacrylonitrile, unsaturated polyester with double bonds in the molecule, There are unsaturated polyurethane-based and silicone-based photosensitive resin printing materials. Furthermore, there are photosensitive flexographic printing materials using polystyrene-polybutadiene block copolymers, polystyrene-polyisoprene copolymers, ethylene-vinyl acetate copolymers, natural rubber, nitrile rubber, and the like.

In addition to monoacrylates and monomethacrylates, photopolymerizable unsaturated compounds used in such photosensitive resin compositions include polyhydric alcohols such as ethylene glycol and unsaturated carboxylic acids such as acrylic acid and methacrylic acid. Acid reactants, polyhydric acrylates synthesized by the reaction of unsaturated epoxy compounds and unsaturated carboxylic acids, polyhydric methacrylates, acrylamide derivatives, polyhydric acrylamides synthesized by the condensation reaction of acrylamide X4 and polyhydric alcohols. , polyvalent methacrylamide-based photopolymerizable monomers, etc. are blended singly or in combination with the base resin.

Many photopolymerizable tops have a unique odor even if their boiling point is 150°C or higher. In particular, when the unsaturated group is an acryloyl group or a methacryloyl group, there is a unique irritating odor, and if these are used in large quantities, the photosensitive resin composition or plate material produced may have an irritating odor, or the developing During the process, the odor of the developer that has eluted the unpolymerized portion may cause discomfort to workers.

[Problem that the invention seeks to solve]

The present invention was devised in view of the various drawbacks of the prior art, and its purpose is to significantly reduce the odor of the plate material itself and the waste liquid produced from it, without impairing the photosensitive characteristics, developability, and printability of the plate material. An object of the present invention is to provide a photosensitive resin composition that can

[Means for solving problems]

The present invention is a photosensitive resin composition comprising at least the following components (a) to (c).

(a>100 parts by weight of base resin as a binder (b) has an ethylenic double bond at the end and has a boiling point of 150
20 to 200 parts by weight of a photopolymerizable unsaturated compound (c) 0.01 to 10 parts by weight of a compound having a molecular weight of 50 to 2.000 and having a 18H group at the end (as component (a) of the present invention) As the base resin used as a binder, all of the base resins for photosensitive resin plates commonly used can be used.Completely saponified and partially saponified polyvinyl acetate, polyvinylpyrrolidone, Ethylene oxide, polyvinyl ether, hydroxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, water-based alkyd resin, polyamide, polyvinyl cinnamylidene acetate, polyvinyl cinnamate/cinnamylidene acetate.Diazo such as p-diazodiphenylamine/paraborumaldehyde condensation product Resin, Boriasitoben 1 vinyl,
Azide polymers such as vinyl polyazidophthalate, polystyrene-polyisoprene block copolymers, polystyrene-polybutadiene block copolymers, polyisoprene, synthetic rubbers such as nitrile rubber, polybutadiene, and unsaturated polyesters with double bonds in the molecule. , unsaturated polyurethane, unsaturated aryl urethane oligomer, etc.

As the photopolymerizable monomer used as component (b) of the present invention, any monomer that has a certain level of compatibility with component (a) can be used. Specifically, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, etc. Monoacrylates and monomethacrylates. Polyhydric acrylates and methacrylates produced by the reaction of a polyhydric alcohol such as ethylene glycol with an unsaturated carboxylic acid such as acrylic acid or methacrylic acid. Polyvalent acrylates and methacrylates are synthesized by the reaction of polyvalent glycidyl ethers such as ethylene glycol diglycidyl ether and unsaturated carboxylic acids such as acrylic acid and methacrylic acid. Photopolymerization of polyacrylamide and polymethacrylamide synthesized by the condensation reaction of acrylamide, methacrylamide, N-methylolacrylamide, diacetone acrylamide, methylenebisacrylamide, N-methylolacrylamide or N-methylolacrylamide with a polyhydric alcohol. Examples include sexual monomers. Vinyl compounds such as divinylbenzene can also be used.

Component (b) needs to have a boiling point of 150°C or higher. If the boiling point is less than 150° C., problems such as the photopolymerizable monomer scattering during molding of the plate material and the photopolymerizable monomer scattering during storage of the green plate, resulting in unstable performance, occur.

If the amount of component (b) used is less than 20 parts by weight per 100 parts by weight of the base resin of component (a), the density of the crosslinked structure produced by photopolymerization will be insufficient, resulting in insufficient image reproducibility of 1q. I can't do it. On the other hand, if the amount of component (b) used exceeds 200 parts by weight, the density of the crosslinked structure produced by photopolymerization becomes excessive, and the resulting relief becomes extremely brittle. This causes problems such as cracks in the relief during printing. For the above reasons, it is necessary to use the photomerizable monomer of component (b) in a range of 20 to 200 parts by weight per 1 part of component (a) 100 parts by weight, preferably 50 to 150 parts by weight. is.

The compound having a -3H group at the end used as component (c) of the present invention is contained in a photosensitive resin composition in which a photopolymerizable unsaturated compound as component (b) is blended with a base resin as component (a). Odors can be eliminated by blending them.

Compounds used as component (c) of the present invention include:
Edylthiol, provildiol, isopropylthiol, n-butylthiol, allylthiol, n-peptylthiol, n-hexylthiol, n-peptylthiol, n-octylthiol, n-nonylthiol,
Alkylthiols such as n-decylthiol, n-undecylthiol, n-dodecylthiol, n-tridecylthiol, n-octadecylthiol. Aromatic thiols such as thiophenol and benzylthiol. 2-mercaptoethanol, 2-mercaptopropertool, 2-
Alkanol diols such as mercaptopentanol, 2-mercaptohexanol, thioglycol, and thioglycerin. Thiocarboxylic acids such as dioxic acid, thioglycolic acid, and thioacrylic acid. Polysulfide with one SH group at the end, molecule ff150-2.

000, but is not limited to these. n-decylthiol, n-undecylthiol, n-dodecylthiol, n-, tridecylthiol,
Edilenedioglycol and thioglycerin are particularly preferably used.

The molecular weight of component (c) must be in the range of 50 to 2,000. If the number of molecules is less than 50, the volatility is extremely high, and most of it will be scattered during preparation of the photosensitive resin composition or molding of the plate material. Conversely, the molecular mouth is 2.0
If it exceeds 00, the compatibility with the photosensitive composition decreases, so it is often unusable. For the above reasons, the molecular weight of component (c) needs to be in the range of 50 to 2,000, more preferably 70 to 1,000.

Component (C) should be used in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the base resin of component (a). (c)
) When the amount of the component used is less than 0.01 part by weight, (c)
The deodorizing ability due to the addition of ingredients is small and the effect is not expressed. Moreover, if the amount used exceeds 10 parts, the photopolymerization reaction is often inhibited, and the odor of component (c) itself becomes significant. For these reasons, the amount of the compound having an S H group at the end of component (c) is the same as the base resin of component (a.).
0.00 parts by weight, it is necessary to be in the range of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight. It is also possible and necessary to use a mixture of two or more types as component (c).

As the photosensitizer for rapidly carrying out the photopolymerization reaction of the composition of the present invention, all conventionally known compounds can be used. Examples include benzoin alkyl ethers, benzophenones, anthraquinones, benzyls, acetophenones, and diacetyls.

These photosensitizers should be added in an amount of 0.01 to 10 to the total composition.
Can be used within the range of @ffi%.

All conventionally known polymerization inhibitors can be used to increase the thermal stability of the photosensitive resin composition of the present invention. Preferred thermal polymerization inhibitors include phenols, hydroquinones, catechols, and the like. These heat stabilizers can be used in an amount of 0.001 to 5 m% based on the composition. Further, dyes, pigments, surfactants, antifoaming agents, ultraviolet absorbers, fragrances, etc. can be added.

The method for producing the photosensitive resin composition of the present invention includes (
After heating and dissolving the base resin as the component (a) alone or in a mixed solvent, the photopolymerizable monomer as the component (b) and -S as the component (c) are added.
Generally, a compound having an H bond, a photosensitizer, a heat stabilizer, and the like are added and thoroughly mixed by stirring. In this way, a photosensitive resin solution is obtained.

In order to form a photosensitive layer from the above-mentioned mixed solution, for example, most of the solvent can be distilled off, and then the mixture can be heated to a molten state and extruded onto a support to be molded. It is also possible to make a photosensitive sheet by a flexible film forming method and adhere this sheet onto a support to form a photosensitive layer. It is also possible to directly form a dry film on the support to form a photosensitive layer of 1 q.

As the support, metal plates such as steel, stainless steel, aluminum, and copper, plastic sheets such as polyester films, and synthetic rubber sheets such as styrene-butadiene copolymer are used.

The photosensitive layer is preferably formed to have a thickness of 0.1 to 1 Qmm.

In order to form a relief image for printing using the photosensitive resin composition of the present invention, a negative or positive original film is closely adhered to the photosensitive layer prepared as described above, and the wavelength is usually centered at 300 to 400 nm. high-pressure mercury lamp,
It is cured by photopolymerization by irradiating ultraviolet light from an ultra-high pressure mercury lamp, metal halide lamp, xenon lamp, carbon arc lamp, chemical lamp, etc. Next, a relief is formed on the support by dissolving the unpolymerized portion into a solvent using a spray developing device, a brush developing device, or the like.

The photosensitive resin composition of the present invention eliminates the odor observed in the plate material itself and the developer used to develop it, and can improve the working environment for plate making and development operators. This is (c
) is obtained by adding an appropriate amount of a compound having a --SH group. The mechanism for this is not clear, but since the -SH group at the end of component (c) is highly reactive, it is likely that aldehydes, which are the source of the irritating odor contained in the photopolymerizable resin of component (b), It is thought that it reacts with impurities and becomes odorless. however,
The compound of component (c) generally has a strong odor itself and also has the property of inhibiting light gathering.

Therefore, the amount of component (c) to be added needs to be determined carefully. That is, the amount of component (c) added must be kept to the minimum necessary to improve odor, and addition beyond that will reduce odor and image reproducibility.

The photosensitive resin composition of the present invention is most effective when used as a letterpress printing material, but it can also be used as a lithographic printing material, an intaglio printing material, a stencil stamp 111 material, and a photoresist.

[Example] The present invention will be explained in more detail with reference to Examples below.

Example 1 100 tonne parts of partially saponified polyvinyl acetate with saponification degree of 80 mol% and average polymerization degree of 900 was mixed with ethanol/water = 40/6
0 (weight ratio) in 250 parts by weight of a mixed solvent at 70°C for 2 hours. Next, as a photopolymerizable monomer, 70 weight parts of a compound obtained by an addition reaction of 1 mole of ethylene glycol diglycidyl ether and 2 moles of acrylic alcohol were added and thoroughly stirred.

Further, 1 part by weight of thioglycerin, 15 parts by weight of diethylene glycol as a plasticizer, 2 parts by weight of dimethylbenzyl ketal as a photosensitizer, and 0.1 part by weight of hydroquinone monomethyl ether as a heat stabilizer were added and mixed with thorough stirring. The photosensitive resin solution thus obtained had no irritating odor at all.

Next, this photosensitive composition was coated onto a 300 μm thick steel substrate on which an epoxy adhesive had been applied and cured in advance so that the thickness after drying was 950 μm (including the substrate). This was then placed in a 60°C oven for 4 hours to remove the solvent.

It was confirmed that there was almost no odor in the processed plate material and developing waste solution. It was also confirmed that there was no problem in image reproducibility. The results of the printing test were also good.

Comparative Example 1 A photosensitive resin composition solution was prepared in the same manner as in Example 1 except that 1 part by weight of thioglycerin was not added. This solution had a strong pungent odor.

This photosensitive resin composition was formed into a plate material under the same conditions as in Example 1. The obtained plate material and developer waste had a considerable odor.

From the above results, it was found that the addition of thioglycerin significantly reduced the odor of the photosensitive composition and plate material.

Example 2 1 part of N-methoxymethylated 6-nylon 100Iff with a methoxymethylation rate of 30 mol% was mixed with ethanol/water = 80
/20 (weight ratio) mixed solvent 120 at 80°C
Dissolved by heating. Add 3 glycidyl methacrylate to this
A double bond was introduced into the end of the nylon by weighing parts by weight and reacting with SO'C for 1 hour. Next, 70 parts by weight of glycerol dimethacrylate as a photopolymerizable pot, 25 parts by weight of N-butylbenzenesulfonamide as a plasticizer,
0.2 parts by weight of n-dodecylthiol and 2 parts by weight of benzoin ethyl ether as a photosensitizer were added and thoroughly mixed. The photosensitive resin composition solution thus obtained was almost odorless.

This solution was cast onto a polyester film having a thickness of 200 μm, which had been previously coated with a polyester adhesive and cured, so that the thickness (including the thick substrate after drying) would be 700 μm. Thereafter, the mixture was placed in an oven at 60° C. for 3 hours to remove the solvent. It was confirmed that this plate material was almost odorless and had good photosensitive properties. Also, good results were obtained in printing tests 1 to 1.

Comparative Example 2 A photosensitive resin composition solution was prepared under the same conditions as in Example 2 except that n-dodecylthiol was not added. This solution had a strong pungent odor.

Next, a plate material was prepared in the same manner as in Example 2 using this solution. The obtained plate material had a considerable pungent odor remaining.

[Effects of the Invention] Since the photosensitive resin composition according to the present invention has the grooves as described above, it is possible to significantly reduce the odor of the photosensitive resin plate material while maintaining good photosensitive characteristics and printability. This has a remarkable practical effect.

Claims (1)

[Scope of Claims] A photosensitive resin composition comprising at least the following components (a) to (c). (a) 100 parts by weight of base resin as a binder (b) Has an ethylenic double bond at the end and has a boiling point of 150
20 to 200 parts by weight of a photopolymerizable unsaturated compound with a molecular weight of 50 to 2,000 and a terminal -SH group (0.01 to 10 parts by weight)