JPS58173741A - Formation of photorelief - Google Patents

Abstract

PURPOSE:To obtain a photorelief while improving the work environment, the danger of a fire and the cost by forming a film consisting of specified polyvinyl alcohol (PVA) resin and a photoreaction accelerator, irradiating the film with ultraviolet rays through a negative image, and wshing the film. CONSTITUTION:A film made of a mixture of polyvinyl alcohol resin contg. acetoacetic ester groups or allyl groups with a photoreaction accelerator is formed on a substrate. The film is irradiated with ulraviolet rays through a negative image, and the unexposed part is removed by washing. The substrate having the resulting image may be subjected to hardening treatment with metallic salt or ammonium salt to form a photorelief image with much more superior resolving power. Said PVA resin contg. acetoacetic ester groups is preferably obtd. by the addition reaction of diketene to PVA resin or the transesterification of PVA resin with acetoacetic ester.

Description

DETAILED DESCRIPTION OF THE INVENTION It is well known that cinnamate ester of polyvinyl alcohol has photosensitivity, but the resin is insoluble in water. , the use of organic solvents such as toluene, chlorobenzene, and trichlene is essential. However, the use of such organic solvents poses practical problems in terms of deterioration of the working environment, risk of fire, and increased costs.

However, as a result of various studies, the present inventors found that polyvinyl alcohol resin containing an acetoacetate group or an allyl group is water-soluble unless it is irradiated with ultraviolet rays, but on the other hand, when the resin film is irradiated with ultraviolet rays, only the irradiated portion The resin has the property of being water-insoluble, and when this property is used to form the resin IjllN on a substrate and irradiate it with ultraviolet rays through a negative direction, it becomes extremely sensitive and the photosensitive area is exposed. The image forming base material obtained above is highly suitable for the purpose of forming a photorelief because it is water-insoluble, while the unexposed part remains water-soluble and can be easily removed by washing with water. It was discovered that dura mater treatment with gold maple salt or ammonium salt can produce a remarkable effect in that a photorelief image with even better resolution can be formed, leading to the completion of the present invention.

In the present invention, a clear photoresist image can be formed simply by using water without using an organic solvent. All problems can be solved, and it is extremely advantageous for practical application.

In addition, conventionally, photopolymerizable monomers are often used together to form photoreliefs, but the acetoacetyl group- or allyl group-containing polyvinyl alcohol resin of the present invention itself crosslinks with light and is strong. A major feature is that it can form relief. Therefore, in the present invention, there is no need to use a Shako polymerizable monomer in combination.

The polyvinyl alcohol resin having an acetoacetate group in the present invention can be produced by any method, and there are no particular restrictions on the production method, but it is preferable to add diketene to the polyvinyl alcohol resin or add acetoacetate to the polyvinyl alcohol resin. Obtained by transesterification. Similarly, a preferred method for producing an allyl group-containing polyvinyl alcohol resin is a method in which an allyl compound such as allyl chloride or allyl chloride is reacted with a polyvinyl alcohol resin. The base polyvinyl alcohol resin may include a partially saponified polyvinyl ester such as polyvinyl acetate, or a monomer mainly composed of vinyl acetate and copolymerizable with it, such as an unsaturated carboxylic acid or a portion thereof, or Complete ester, salt, anhydride, amide,
Nitrile, unsaturated sulfonic acid or its salt, carbon &2~'
"Copolymerization modification" in which a copolymer with 50 α-olefins, vinyl ethers, etc. is saponified. "Post-modification" in which polyvinyl alcohol or polyvinyl alcohol is acetalized, phretanized, etherified, grafted, or phosphoric acid esterified. Polyvinyl alcohol can also be used.

The content of the acetoacetate ster group or allyl group in the resin may be 0.05 mole or more, up to the maximum within the range of water solubility, but it is usually 0.1 to 35 mole, especially 0.05 mole or more. It is often selected from the range of .2 to 60 beats. If the content of the acetoacetate group or allyl group is too low, water discoloration by ultraviolet irradiation will not be sufficient and a satisfactory photorelief image will not be obtained. Introduction of more acetoacetate groups or allyl groups than necessary is unsuitable for the purpose of the present invention, since it becomes water-insoluble. Also, the average degree of polymerization is 20
0-3000 preferably 10-2000
It is desirable to select from a range of i35 mol or less, preferably 30 mol or less.

#i photoreaction accelerator is used in combination with such acetoacetate group- or allyl group-containing polyvinyl alcohol resin.

Examples of photoreaction accelerators include benzoin alkyl ethers such as benzoin methyl ether, pentuin ethyl ether, and pentuin isopropyl ether, organic iodine compounds such as dibutyl sulfide, benzyl sulfide, and decylphenyl sulfide, diazonium salts, tetrazonicum salts, or salts thereof. Complex salts with zinc or condensates thereof, azobisisobutyronitrile, dyes such as methylene blue, or combinations thereof with p-)luenesulfonate ions, organic peroxides, hydrogen peroxide, pyrylium salts or thiavirillicum salts, Ammonicum dichromate, ayatophenone, benzophenone, benzyl, phenanthrene, thioxanthone, dichloropropylphenyl ketone,
Anthraquinone, 2-chloroanthraquinone, 2-bromoanthraquinone, anthraquinone β-sulfonic acid sodium, 1,5-cyni) o7anthraquinone, 1,2-pensanthraquinone, 7-enanthrenequinone, 5-benzoylacenaphthene, 5-nitro Examples include acenaphthene, 1.4=naphthoquinone, 1,8-7 taloylnaphthalene, 2-nitrofluorene, p-nitroaniline 1, biclamide, benzaldehyde, etc.
Two or more types are used in combination.

Not limited to those listed above, reactions by light, cross-linking,
Anything that promotes this can be used.

Among these, benzoin alkyl ether and anthraquinone β-sulfone soda give particularly good results in terms of cost and sensitivity.

To carry out the method of the present invention, a mixture of the acetoacetate group-containing or allyl group-containing polyvinyl alcohol resin and a photoreaction accelerator as described above is applied to a substrate in the form of an aqueous solution and dried. 01! in advance with an acetoacetate group- or allyl group-containing polyvinyl alcohol resin and a photoreaction accelerator! A film is produced from the mixture by any method and is adhered to a substrate. At this time, there is no problem even if some organic solvent is included. In addition, there is no problem in using a known water-resistant agent such as a metal salt, aldehyde, or amine film.

The resin concentration in the aqueous solution is usually selected from the range of 1 to 20% by weight in view of workability when coating on a base material and the use of the resulting photorelief image. The appropriate thickness of the film is 1-1011.

As the base material, zinc plates, aluminum plates, magnesium plates, steel plates, copper plates, etc. are usually used.

Using the coated plate obtained in this way, by irradiating ultraviolet rays through the flesh of the plate, the exposed areas become water-insoluble and the unexposed areas remain water-soluble, so if you wash it with water, only the unexposed areas will be removed. is removed and a photorelief image is formed on the substrate. Light sources include low-pressure mercury lamps, high-pressure mercury lamps,
Ultra-high pressure mercury lamps, carbon arc lamps, xenon lamps, etc. are used.

This plate may be used as it is for letterpress printing, intaglio printing, and offset printing.

Note that the base material is not limited to the above-mentioned metal plate; for example, the above-mentioned polyvinyl alcohol derivative film can be used on cotton, rayon,
It is formed on the surface of wool, woven fabrics made of polyester-based, polyamide-based, polyacrylonitrile-based, polyvinyl alcohol-based synthetic fibers, etc., non-woven fabrics, etc., and then ultraviolet rays are irradiated through a negative screen and the unexposed areas are washed away with water. However, it is also possible to add a pattern to the fabric by subsequently dyeing it.

In addition, paper, synthetic resin sheets, etc. may be used as the base material.

Although the substrate on which the photorelief image has been formed can be put to practical use as it is, an image plate with even better properties can be produced by treating the substrate with an IK metal salt or ammonium salt.

That is, this treatment further strengthens the hardening of the photosensitive area, eliminates any concerns about abrasion during printing, and provides a very clear image.

When using polyvinyl alcohol-based S stimulants, such hardening treatment is usually carried out using, for example, chromic anhydride, but when using polyvinyl alcohol-based resins containing acetoacetate groups or allyl groups, the amount used is This can be significantly reduced compared to unmodified polyvinyl alcohol69, which is one of the characteristics of the acetoacetate group- or allyl group-containing polyvinyl alcohol resin used in the present invention.

Representative examples of metal salts include chlorides, bromides, nitrates, sulfates, acetates of polyvalent metals such as aluminum, copper, zinc, tin, titanium, nickel, antimony, magnesium, and chromium. Specific examples include cupric chloride, aluminum chloride, ferric chloride, tin chloride, zinc chloride, nickel chloride, magnesium chloride, aluminum sulfate, copper acetate, chromium acetate, and the like.

However, it is not limited to these. Particularly preferred salts are nickel chloride, magnesium chloride, ferric chloride, and the like.

Next, as ammonium salts, ammonium salts of mineral acids such as ammonicum chloride, ammonicum sulfate, ammonicum nitrate, and ammonium dichromate, and ammonium salts of organic acids such as ammonium acetate and ammonium fropionate are used. These metal salts and ammonium salts can be used alone or in combination.

For hardening, the base material obtained as described above is treated with a metal salt or ammonium salt solution by squirting, coating, dipping, etc., followed by drying, and heat treatment if necessary.
It is carried out by doing tsubo.

Hereinafter, the method of the present invention will be explained in more detail by giving examples. Parts and Fi% are based on weight unless otherwise specified.

Example 1 A 15% aqueous solution of acetoacetate group-containing polyvinyl alcohol containing 25 moles of acetoacetate groups, 1 mole of remaining acetate groups, and an average degree of polymerization of 500 was prepared, and this was further added to Kbenzenediasonicum. 5 parts of chloride were mixed.

Apply the aqueous solution uniformly onto a zinc plate using a rotating applicator,
After drying to form a film with a thickness of 10 tones, the line drawing negative was placed in close contact with the film and exposed to ultraviolet light for 3 minutes using a 400W low-temperature mercury lamp kept at a distance of 15 mm, then washed with water and printed as a photorelief on a zinc plate. An image was formed and a good printing plate was obtained. The resolution when printing using a chain plate is 180 lines per inch. The above 15% aqueous solution was prepared, and the aqueous solution was applied onto a glass plate and dried to a thickness of 40%.
A .mu. film was formed, and then ultraviolet rays were irradiated for 3 minutes using an AOOW low-pressure mercury lamp while keeping the distance between the light source and the film at 15 am, and then thoroughly washed with water. When the photosensitivity at this time is expressed as a relative value of residual film yield and a 25-step gray scale manufactured by Eastman Kodak, the former is 170% and the latter is 20.

Example 2 Ayato acetate base ji13 morti, residual acetate group 5
An aqueous solution of polyvinyl alcohol containing acetoacetate groups with an average degree of polymerization of 1100 was prepared, and 5 parts of sodium 4.4'-diazidostilbene-2,2'-disulfonic acid was further mixed therein. .

Apply the aqueous solution uniformly onto a zinc plate using a rotating applicator,
Dry and 10p thick! l! After making the 1I, a line drawing negative was brought into close contact with the film and irradiated with ultraviolet rays for 3 minutes using a 400 W low pressure mercury lamp kept at a distance of 15 mm, and then washed with water to form a photorelief image on the zinc plate. Second, the resulting image plate was immersed in a 10% aluminum sulfate aqueous solution for about 60 seconds, and then burned to obtain a good printing plate. The resolution when printing using the chain plate was 160 lines per inch. In addition, the relative residual film yield measured under the same conditions as in Example 1 was 95 mm, and that of Brennis School was 19 mm.
Deah nine.

Examples 6-6 Example 2 under the conditions shown in Table 1. An experiment was conducted in accordance with @The results are shown in Table 1.

Table 1 Example 7 In place of the acetoacetate group-containing polyvinyl alcohol resin, allyl group-containing melivinyl alcohol thread resin (denaturation amount 13 mol, presence of vinegar group 5 mol, average degree of polymerization 110)
The same method as in Example 2 was carried out using 0) 〇 Number of strokes 160, relative residual film yield 95 S1 gray scale 1
8 and 9.

Claims (1)

[Claims] 1.1 A film made of a mixture of a polyvinyl alcohol resin containing a heptoacetic acid ester group or an allyl group and a photoreaction accelerator is formed on a substrate, UV light is irradiated through the rough surface, and then the unexposed area is exposed. A photorelief formation method characterized by removing by washing with water. A film made of a mixture of a polyvinyl alcohol resin containing a 2-7toacetic acid ester group or an allyl group and a photoreaction accelerator is formed on a substrate, and ultraviolet rays are irradiated through the negative surface,
A method for forming a photorelief, which is characterized in that the unexposed areas are then washed away with water and then hardened with a metal salt or ammonium salt.