JPS62215262A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To remarkably reduce the odor of a material for a plate and the odor of a spent developing soln. without deteriorating the satisfactory developability, photosensitive characteristics or suitability to printing by using a base resin as a binder, a photopolymerizable unsatd. compound, an inorg. ammonium salt compound and at least one kind of polyether. CONSTITUTION:This photosensitive resin composition contains 100pts.wt. base resin as a binder, 20-200pts.wt. photopolymerizable unsatd. compound having ethylenic double bonds at the terminals and >=150 deg.C b.p., 0.01-20pts.wt. inorg. ammonium salt compound, and 0.1-30pts.wt. at least one kind of polyether selected among polyoxyethylene, polyoxypropylene and an oxyethylene- oxypropylene copolymer each having 150-5,000mol.wt. The inorg. ammonium salt compound and the polyether can deodorize the photosensitive resin composition.

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 produced by adhering a negative or positive original film with a transparent part to a photosensitive resin layer, and then irradiating it with actinic light to cause photopolymerization of the photosensitive resin layer corresponding to the transparent part of the original film. Then, a relief is formed on the base material by eluting the unpolymerized portion with a suitable solvent. Photosensitive resin compositions that utilize photopolymerization reactions are used in various applications including printing plates.

Photosensitive resin plates include those based on polyvinyl cinnamate, polyamide, polyvinyl alcohol, polymethyl acrylate, and polyacrylonitrile, as well as those based on unsaturated polyester and unsaturated polyester with double bonds in the molecule. There are saturated polyurethane-based and silicone-based photosensitive resin printing materials. There are also photosensitive flexographic printing plates made of polystyrene-polybutadiene block copolymers, polystyrene-polyisoprene copolymers, low molecular weight ethylene-vinyl acetate copolymers, natural rubber, nitrile rubber, and the like.

Photopolymerizable unsaturated compounds used in such photosensitive resin compositions include monoacrylates, monomethacrylates, polyhydric alcohols such as ethylene glycol, and unsaturated carboxylic acids such as acrylic acid and methacrylic acid. Reactants: polyacrylates, polymethacrylates, acrylamide derivatives synthesized by the reaction of unsaturated epoxy compounds and unsaturated carboxylic acids; polyacrylamide, polyhydric compounds obtained by condensation reaction of acrylamide derivatives with polyhydric alcohols. Photopolymerizable monomers such as methacrylamide are used alone or in combination with the base resin.

Many photopolymerizable monomers 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 a large amount of these is used, the solution or plate material of the photosensitive resin composition obtained may have an irritating odor. During the development process, the odor of the developer that has eluted the unpolymerized portions may cause discomfort to production 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 provide a photosensitive material that can significantly reduce the odor of the plate material itself and developer without impairing the photosensitive characteristics or developability of the plate material. To provide a synthetic resin composition.

(Means for solving the problems) 'The present invention has the following features:
A photosensitive resin composition comprising at least the following components (a) to (d).

(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 photopolymerizable unsaturated compounds (c) 0.01 to 20 parts by weight of inorganic ammonium salt compounds (d>polyoxyethylene, polyoxypropylene and oxypropylene having a molecular weight in the range of 150 to 5000) 0.1 to 30 parts by weight of at least one polyether selected from the group consisting of ethylene/oxypropylene copolymers The base resin as a binder used as component (a) of the present invention is usually a commonly used base resin. All base resins for photosensitive resin plates can be used: fully saponified and partially saponified polyvinyl acetate, polyvinylpyrrolidone, polyethylene oxide, polyvinyl ether, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, water-based alkyd resins. , polyamide, polyvinyl cinnamylidene acetate,
Polyvinyl cinnamate/cinnamylidene acetate.

Diazo resins such as p-diazodiphenylamine/paraformaldehyde condensation products, polyazidovinyl benzoate,
Azide polymers such as vinyl polyazidophthalate, polystyrene-polyisoprene block copolymers, polystyrene-polybutadiene block copolymers, synthetic rubbers such as polyisoprene, poly3-ethylbutadiene, nitrile rubber, and polybutadiene, Examples include unsaturated polyesters, unsaturated polyurethanes, and unsaturated aryl urethane oligomers having multiple bonds.

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 monomethafrylates. Polyhydric acrylates and polyhydric methacrylates obtained by the reaction of polyhydric alcohols such as ethylene glycol and unsaturated carboxylic acids such as acrylic acid or methacrylic acid. Polyvalent acrylates and polyvalent methacrylates synthesized by the reaction of polyglycidyl ethers such as ethylene glycol diglycidyl ether with unsaturated carboxylic acids such as acrylic acid and methacrylic acid. Polyhydric acrylates synthesized by the reaction of unsaturated epoxy compounds such as glycidyl methacrylate and unsaturated carboxylic acids such as acrylic acid or methacrylic acid, and polyhydric methacrylates 1 to 1
. Acrylamide, methacrylamide, N-methylolacrylamide, diacetone acrylamide, methylenebisacrylamide, N-methylolacrylamide or polyhydric acrylamide synthesized by a condensation reaction of N-methylolmethacrylamide and a polyhydric alcohol;
and polyvalent methacrylamide-based photopolymerizable monomers.

Furthermore, vinyl compounds such as divinylbenzene can also be used.

Component (b) must have a boiling point of +50'c or higher.If the boiling point is less than '150'c, the photopolymerizable monomer may scatter during molding of the plate material or may occur during storage of the raw plate. However, problems such as photopolymerizable monomer scattering and unstable performance occur.

If the amount of component (b) used is less than 20 parts by weight based on 100 parts by weight of the base resin of component (a), the density of the crosslinked structure refined by photopolymerization will be insufficient, resulting in insufficient image reproducibility. I can't get 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, making the resulting relief extremely brittle.As a result, the relief may crack during printing. For the above reasons, the amount of photopolymerizable monomer used as component (b) is 2 parts by weight per 100 parts by weight of component (a).
A range of 0 to 200 parts by weight is required, preferably 50 parts by weight.
~150@ parts.

The inorganic ammonium salt compound used as the (c) component of the present invention and the polyether used as the (d> component) are the base resin of the (a) component and the photopolymerizable unsaturated compound of the (b) component. The odor can be eliminated by blending it into a photosensitive resin composition containing component (c). Even when the inorganic ammonium salt compound of component (c) is blended alone, the effect of erasing the odor of the photosensitive resin composition has been observed. However, (d
By using the polyether component () in combination with the component (c), the deodorizing effect can be further enhanced, and a photosensitive resin composition with very little odor can be obtained.

Inorganic ammonium salt compounds used as component (c) of the present invention include thioFiAM ammonium, ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium nitrite, ammonium chloride, and thiocyanate. Examples include ammonium acid, ammonium perchlorate, and ammonium carbonate, but preferably ammonium sulfate, ammonium nitrate, 11-ammonium thiosulfate, and ammonium chloride are used.

The amount of component (c) to be used is 0.01 to 20 parts by weight per 100 parts by weight of the base resin of component (a). (c)
If the amount of the component used is less than 0.01 part by weight, the deodorizing ability by adding component (c) will be small and no effect will be achieved. In addition, if the amount used exceeds 20 parts by weight, the compatibility with the photopolymerizable monomer may deteriorate, causing seepage on the surface of the photosensitive resin plate.
In most cases, the photopolymerization reaction is inhibited and the density of the crosslinked structure becomes insufficient, resulting in a significant decrease in image reproducibility. For these reasons, the amount of the inorganic ammonium salt compound (c) used is 0.00 parts by weight per 100 parts by weight of the base resin (a).
It is necessary that the amount is in the range of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight. It is also possible to mix two or more types of components (c>).

The polyether used as the (d> component of the present invention) is
Either polyoxyethylene, polyoxypyrene or oxyethylene/oxypropylene copolymers can be used. Of course, it is also possible to use a mixture of two or more types.

The molecular weight of component (d) polyether is 150 to 5000.
If the molecular weight is less than 150, it is expected to be included in the base resin of component (a) and only act as a plasticizer, and no odor improving effect will be observed. Conversely, if the molecular weight exceeds 5000 (a”)
The compatibility with the component base resin and the component (b) photopolymerizable monomer deteriorates, causing seepage on the surface of the photosensitive resin plate.

For the above reasons, the molecular weight of polyether is 150 to 50.
It is necessary that the value is between 00 and more preferably 20.
0~4000. Most preferably it is 300-3000.

The amount of component (d) used is 0.1 to 30 parts by weight per 100 parts by weight of the base resin of component (a). When the amount of component (d) used is less than 0.1 part by weight, the odor improvement level is the same as when component (c) is blended alone;
) No tax odor effect was observed due to the addition of ingredients. In addition, if the amount used exceeds 30 parts by weight, the compatibility with the photopolymerizable monomer may deteriorate, causing seepage on the surface of the photosensitive resin plate, or inhibiting the photopolymerization reaction, resulting in insufficient density of the crosslinked structure, resulting in an image Reproducibility is often significantly reduced. For the above reasons (d)
The amount of the component used must be in the range of 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight.

As the photosensitizer for rapidly carrying out the photopolymerization reaction of the crude Li 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.
It can be used in a range of % by weight.

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% by weight based on the total amount of 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 component (a) alone or in a mixed solvent, the photopolymerizable monomer as component (b), the inorganic ammonium salt compound as component (c), the polyether and photosensitizer as component (d), and heat It is common to add stabilizers and the like and stir to mix thoroughly. 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 produce a photosensitive sheet by a dry film forming method and adhere this sheet onto a support to form a photosensitive layer. Furthermore, a photosensitive layer can also be obtained by directly forming a dry film on a support.

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 10 mm.

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 a wavelength of 300 to 400 mμ is usually centered on the photosensitive layer. high-pressure mercury lamp,
UV light from an ultra-high pressure mercury lamp, metal halide lamp, xenon lamp, carbon arc lamp, chemical lamp, etc. is irradiated to cause photopolymerization. A relief is then formed on the support by dissolving the unpolymerized portion into a solvent using a spray developing device or a brush developing device.

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
This is achieved by adding the inorganic ammonium salt compound (component) and the polyether (component (d)), and although the mechanism is not clear, it can be used without impairing the image reproducibility of the plate material or the durability during printing. Odor can be significantly improved.

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 printing material, and a photoresist.

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

Example 1 100 parts of partially saponified polyvinyl acetate with a degree of saponification of 88 mol% and an average degree of polymerization 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 photopolymerizable monomers, 1 mol of propylene glycol diglycidyl ether and 2 mol of acrylic acid were added.
70 parts by weight of the following compound obtained by a molar addition reaction was added and stirred for 10 minutes.

H)1 0H011 In addition, 1 part by weight of ammonium sulfate, 5 parts by weight of polyoxyethylene with a number average molecular weight of 11000 as a polyether, 10 parts by weight of glycerin, 2 parts by weight of dimethylbenzyl ketal as a photosensitizer, and 0 parts by weight of hydroquinone monomethyl ether as a heat stabilizer. .1 part by weight was added and thoroughly stirred and mixed.

The photosensitive resin solution prepared in this way had no irritating odor at all.

The photosensitive resin composition thus prepared was cast onto a 250 μm thick steel substrate coated with an epoxy adhesive and cured so that the dry thickness including the substrate was 950 μm. Then, the mixture was placed in a hot air oven at 60° C. for 4 hours to completely remove the solvent.

After applying a thin layer of ethanol/water (40/60 (weight ratio)) to the surface of the photosensitive layer thus obtained,
A cover film was attached by pressing a polyester film matted by chemical etching and having a thickness of 100 μm. When this plate material was stored in a dark place for 10 days and the cover film was peeled off, the irritating odor completely disappeared and an odorless plate material could be obtained. Furthermore, the water temperature is 30℃ and the water pressure is 4 kg.
/ ca conditions and the photosensitive resin composition concentration in the developer solution was adjusted to 3%, 5%, and 10% by weight, and almost no odor was detected. It becomes odorless developer waste.

In addition, a test negative film (1
33 lines 3%, 5%, 10% halftone dots, diameter 200μ, 300
The independent points of μ and thin line portions with widths of 50 μ and 70 μ) were brought into close contact under vacuum, and exposed for 2 minutes using a high-pressure mercury lamp exposure device. Then, by using a spray cleaning device containing neutral water at 30° C. and developing at a pressure of 4 kg/aK for 3 minutes, the unexposed areas were completely dissolved and removed, and a relief image was formed on the substrate.

When this relief was examined, it was confirmed that even minute parts such as 3% halftone dots, 200μ independent dots, and 50μ fine lines were sufficiently reproduced2. This has the same performance as the plate material before adding components (c) and (d). When a printing test was conducted using the plate material obtained in this way, a sharp printed product was obtained with no thick lines. Furthermore, even though 500,000 copies were printed, no problems such as relief cracks occurred.

Comparative Example 1 A photosensitive resin plate material was prepared in the same manner as in Example 1 except that ammonium oxide and the polyether component were not added. At this time, a strong irritating odor thought to be caused by the acrylic ester odor was found in the composition preparation stock solution during the manufacturing process, the plate surface when the cover film of the plate material was peeled off, and the developing waste solution after developing with the spray developing device. Felt.

Example 2 α obtained by adding acrylonitrile to both ends of polyoxyethylene with a number average molecular weight of 400 and reducing it with hydrogen,
50 parts by weight of an equimolar salt of ω-diaminopolyoxyethylene and adipic acid and 50 parts by weight of ε-caprolactam were melt-polymerized under normal conditions to obtain a polyamide with a relative viscosity of 2.30.

100 parts by weight of this polyamide was mixed with ethanol/water = 70/
It was heated and dissolved at 80° C. in 120 parts by weight of a mixed solvent of 30% (weight ratio). Next, as photopolymerizable monomers, 70 parts by weight of an addition reaction product of ethylene glycol diglycidyl ether and methacrylic acid and 0.2 parts by weight of ammonium nitrate,
1 part by weight of polyoxyethylene having a number average molecular weight of 600 was added as polyether. Further, 2 parts by weight of benzoin ethyl ether as a photoinitiator, 15 parts by weight of diethylene glycol as a plasticizer, and 5 parts by weight of triphenylphosphine as a heat stabilizer were added and thoroughly stirred and mixed. The odor of the photosensitive resin solution thus obtained disappeared, confirming that it was odorless. In addition, this solution was cast onto a 200 μm thick polyester film coated with a polyester adhesive in advance so that the thickness after drying would be 950 μm including the substrate, and placed in a hot air oven at 60°C for 5 minutes. After some time, the solvent was completely removed. The obtained plate material was thinly coated with ethanol/water - 80/20 (weight ratio), and a cover film was attached by pressing a polyester plain film with a thickness of 100 μm. When this plate material was stored in a dark place for 7 days and the cover film was peeled off, the irritating odor of the plate material disappeared and there was no discomfort. A test negative film (1
33 lines 3%, 5%, 10% halftone dots, diameter 200μ, 300
μ independent points, widths of 50 μ and 70 μ with thin line portions) were brought into close contact under vacuum and exposed to light using an ultra-high pressure mercury lamp.

The film was then developed for 8 minutes using a brush-type washing device containing neutral water at 30°C, and the unexposed areas were completely removed to form a relief image on the substrate. This exposure and development process was repeated to prepare developing solutions with concentrations of 5% and 15%, and when the odor was observed, it was confirmed that the developer had almost no odor.

In addition, when the obtained relief was examined, it was found that 3% halftone dot, 2
Even minute parts such as 00μ independent points and 50μ thin lines were sufficiently reproduced, and good printed matter could be obtained even in printing tests using this plate material.

Comparative Example 2 A photosensitive resin plate material was produced in the same manner as in Example 2 except that ammonium nitrate and polyether components were not added. When we observed the odor of the photosensitive resin composition preparation stock solution during the manufacturing process, the plate surface when the cover film of the plate material was peeled off, and the odor of the developing waste solution after developing with a brush type developing device, we found that all samples had a strong odor. I felt a pungent odor.

Example 3 100 parts by weight of partially saponified polyvinyl acetate with a degree of saponification of 80 mol% and an average degree of polymerization of 600 was added to ethanol/water = 5015
It was heated at 80° C. and dissolved in 150 parts by weight of a mixed solvent of 0 (weight ratio). Next, 2 parts by weight of glycidyl methacrylate was added and reacted at 70°C for 1 hour. Analysis results by potentiometric titration revealed that the terminal carboxyl group of the partially saponified polyvinyl acetate disappeared, and the epoxy group of glycidyl methacrylate reacted to introduce an unsaturated bond at the polymer terminal. Thereafter, 60 parts by weight of 2-hydroxyethyl methacrylate and 5 parts by weight of diethylene glycol dimethacrylate were added as photopolymerizable monomers, 0.5 parts by weight of ammonium thiosulfate, 10 parts by weight of polyoxypropylene with a molecular weight of 400 as a polyether, and 5 parts by weight of diethylene glycol dimethacrylate. 3 parts by weight of benzoin methyl ether as a sensitizer and 0.1 part by weight of t-butylcatechol as a heat stabilizer were added and mixed with thorough stirring.

The photosensitive resin solution obtained in this way is prepared in advance.
On a 250μ thick steel substrate coated with epoxy adhesive and cured, the thickness after drying (including the substrate) is 60
Casting was carried out so that the thickness was 0μ.

This was placed in a hot air oven at 60° C. for 4 hours to remove the solvent. Using the same negative film as in Example 1, the plate material thus obtained was exposed to a chemical lamp for about 4 minutes, and then developed using a neutral water spray developing device at a water temperature of 30°C. In the above-mentioned plate manufacturing process and plate making process, we investigated the odor of the photosensitive resin composition solution, the plate material before exposure and plate making, and the developer waste solution after developing the plate material, and found that there was no irritating odor. , it was confirmed that it was odorless.

Example 4 100 parts by weight of partially saponified polyvinyl acetate with a degree of saponification of 75 mol% and an average degree of polymerization of 900 was mixed with ethanol/water-60/
40 (weight ratio) in 300 parts by weight of a mixed solvent at 80°C. Next, 3 parts by weight of glycidyl methacrylate was added and reacted at 80° C. for 1 hour to introduce unsaturated bonds at the ends of the polymer.

Furthermore, as a photopolymerizable unsaturated compound, 3-chloro-2-
100 parts by weight of hydroxyethyl acrylate-1 and 30 parts by weight of dimethylaminoethyl methacrylate polymer were added. Next, 3 parts by weight of ammonium chloride, 3 parts by weight of polyoxyethylene with a number average molecular weight of 2000 as polyether, 4 parts by weight of photosensitizer benzophenone, and 0.0'1 part by weight of hydroquinone, a thermal polymerization inhibitor. The mixture was added and thoroughly stirred and mixed.

The photosensitive resin solution thus obtained was cast onto a 250 μm thick polyester film substrate coated with a polyester adhesive so that the dry thickness (including the substrate) was 950 μm, and the solution was heated at 60°C. Placed in oven for 3 hours to remove solvent.

The obtained plate material was exposed and developed under the same conditions as in Example 1.

In the above manufacturing process, the odor of each was investigated using the photosensitive resin composition solution, immediately after the cover film was peeled off during exposure, and a developer from which the unexposed areas were eluted. It was confirmed that it was R2.

F Effect of the Invention J Since the photosensitive resin composition according to the present invention is configured as described above, it can significantly reduce the odor of the plate material itself and developer waste while maintaining good developability, photosensitive characteristics, and printability. This has the remarkable practical effect of being able to.

Claims (1)

[Scope of Claims] A photosensitive resin composition comprising at least the following components (a) to (d). (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
℃ or higher photopolymerizable unsaturated compound 20 to 200 parts by weight (c) Inorganic ammonium salt compound 0.01 to 20 parts by weight (d) Polyoxyethylene, polyoxypropylene and oxypropylene having a molecular weight in the range of 150 to 5000 0.1 to 30 parts by weight of at least one polyether selected from the group consisting of ethylene/oxypropylene copolymers