JPS5921013B2 - Photosensitive composition for non-silver salt film - Google Patents

Description

Detailed Description of the Invention [5] The present invention relates to a photosensitive composition for non-silver salt films containing a polyvinyl alcohol derivative having photolytic crosslinking type photosensitivity as an active ingredient. It is an object of the present invention to provide a photosensitive resin composition for use in non-silver salt films, which exhibits excellent photosensitivity to light in the long wavelength region and is extremely stable.

Polyvinylazide benzacetal (US Pat. No. 3,096,311) is known as a well-known photodegradable crosslinking type photosensitive resin, but since its photosensitive range is limited to wavelengths shorter than 340 mμ, it is difficult to use in actual use. Not only is it usually necessary to add about 10% sensitizer to the resin, but also at least 5% to improve the contrast of the image.
0m01% or more of hydroxyl groups must be acetalized,
The photosensitive resin composition obtained as a result has the drawback of being expensive, and moreover, its sensitivity to light with a wavelength longer than 400 mμ is insufficient for practical use.

Therefore, there has been a demand for photosensitive resins with higher sensitivity.
In order to meet these demands, the present inventors introduced various photosensitive groups into a copolymer of polyvinylazide benzacetal, but the long wavelength sensitization of the copolymer was not an apparent spectral sensitization. Common unsaturated aldehydes such as crotonaldehyde have poor thermal stability and may gel during storage, or cause dark reactions just by coating and drying. Its use was accompanied by great difficulties, as it sometimes became impossible to develop.

The present invention provides a photosensitive resin for non-silver salt films that does not have these drawbacks, and its gist is that the following structural units (1), ([[), 45 mol% (I [) 5 to 20 mol% 0] 18 to 70 mol% [V) 2 to 20 mol% In the composition.

That is, in the present invention, p is added to the side chain of polyvinyl alcohol.
-Azide A photosensitive composition for non-silver salt films containing a composition having the above structure into which cinnamoylaldehyde, an acetyl group, and a putalol group are introduced as a photocurable component.

The polyvinyl alcohol used in the present invention has a polymerization degree of 30.
0 to 3000 is preferable, and at least 5
Those having m01% or more of hydroxyl groups include, for example, polyvinyl alcohol, partially saponified polyvinyl alcohol, polyvinyl partial acetal resin, and copolymers of polyvinyl alcohol and general vinyl monomers.

Particularly preferred are polyvinyl alcohol and partially saponified polyvinyl alcohol. The p-azidocinnamoylaldehyde is described in J. Chem. SOc. 97,
254 (1910) or U.S. Pat. No. 359,884
It can be manufactured by No. 4.

The method of acetalizing polyvinyl alcohol with p-azidocinnamoylaldehyde of the present invention is to swell polyvinyl alcohol in acetic acid or a solvent such as dioxane or dimethyl sulfoxide, add p-azidocinnamoylaldehyde, and What is necessary is just to make it react at -60 degreeC.

As a catalyst, a small amount of acid such as sulfuric acid, hydrochloric acid, phosphoric acid, p-toluenesulfonic acid, etc. is added. Furthermore, J. POl
ymer,. Sci, Dan, 225 (1952), Polymer Chemistry. , 5, 439 (1949): E, 265 (19
50); Dan, 80 (1951). , Industrial Chemistry Magazine 57,
867 (1954): U, 870 (1954), etc. may be used. The degree of acetalization of the polyvinyl alcohol of the present invention is suitably in the range of 5 to 90%.

Further, the remaining hydroxyl group is acylated by introducing an acetic acid or a putarol group as an acyl group.

In this case, the acyl group is usually esterified in the form of acid anhydride or acid chloride. In this case, the above-mentioned p-azidocinnamoylaldehyde may be reacted first and then copolymerized, or the reacted product may be acylated. The photosensitive composition of the present invention is soluble in an organic solvent,
As cellosolves methyl cellosolve, ethyl cellosolve, butyl cellosolve or cellosolve acetate, such as methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate or ketones such as acetone, methyl ethyl ketone, cyclohexanone, or halogen hydrocarbons such as dichloroethane,
Chloroform, trichlorethylene, tetrachlorethylene, chlorobenzene, or cyclic ethers such as dioxane, tetrahydrofuran, or r-butyrolactone, N-methyl-2-pyrrolidone, dimethylformamide, and the like are used alone or in combination.

The photosensitive composition for non-silver salt films of the present invention is dissolved in these solvents to form a solution, and if desired, conventional auxiliary agents such as photopolymerization initiators, sensitizers, colorants, thermal polymerization inhibitors, etc. are added. You can add.

The photosensitive composition for non-silver salt films of the present invention has higher sensitivity than conventional compositions, exhibits excellent photosensitivity to light in the long wavelength region, has good thermal stability, and has excellent storage stability. It is possible to create a non-silver salt film that does not undergo gelation or dark reaction and becomes undevelopable.

It is also useful as a photosensitive composition for printing plates. Next, the present invention will be described in further detail with reference to Examples.

Example 1 Completely saponified polyvinyl alcohol (trade name: GOHSENOL NM-14 manufactured by Nippon Gosei Kagaku Kogyo) 447 (1 mol) was immersed in 500 CC of glacial acetic acid at 25°C all day and night.The temperature was raised to 50°C and p- Azide cinnamoyl aldehyde 5
1.887 (0.3 mol) was added, and then 57 cc of sulfuric acid and 20 cc of water were added sequentially.

Stir for 3 hours and add anhydrous sodium sulfate 2107 for dehydration.
1807 sodium acetate anhydride and 26.4 f (0.2 mol) of phthalic anhydride are added, the temperature is raised to 92° C., and the reaction is allowed to proceed for 1 hour. Furthermore, acetic anhydride 807 was added, the temperature was raised to 98°C, and the mixture was allowed to react for 1 hour. Add 500 cc of methanol to the obtained viscous dope, pour it into water, wash thoroughly with water, and dry. Yellow-red fever monolithic polymer 95.5f
get. The obtained acetal ester resin has the following structure. (In the formula, the subscript of each structural unit indicates the mol% of each component.

) Example 2 Polymer 37 obtained in Example 1 was mixed with methyl cellosolve 1
00CC and added 0.3t of 4-(4-amyloxyphenyl + 2,6-bis←4methoxyphenyl thiapyrylium perchlorate) as a sensitizer. Apply photosensitive liquid to polyester film 1
Apply and dry so that it becomes 5η/d.

The negative film was vacuum-adhered, exposed for 30 seconds with a chemical lamp, and then developed with 3% sodium metasilicate. After immersing in a crystal violet aqueous solution containing 30% ethyl cellosolve at 30℃ for 1 minute, treating with 10% phosphoric acid and drying*
When dried, a film with a clear blue-violet image is obtained. Example 3 Instead of crystal violet in Example 2, common
Basic dyes such as aniline black, malachite green, or direct dyes such as Congolet also give good colored films.

For comparison, an azide polymer (B) consisting of p-azidobenzaldehyde and an azide polymer (B) consisting of 4-azidocinnamoylaldehyde 1-2-sulfonate were used for comparison with the azide polymer obtained based on Example 1. (
1) and D were synthesized and a non-silver salt film was prepared using them.

((C) to (P) were water-soluble, but if the viscosity was high and it was difficult to apply, dimethylformamide was added to adjust the viscosity.

) [Coating conditions] Coating liquid... (A), (10 wt% methyl cellosolve solution (0 to (O is dimethylformamide:water)
10wt% solution of 1:1) (Add 5wt0AJP of 5-nitroacenaphthene to the polymer as a sensitizer) Support: Polyester coated with an acrylic resin binder (to improve adhesion) film.

Coating method: After coating with a wire bar (0.2 mm), dry with hot air at 90°C for 2 minutes. [Exposure conditions] Irradiation for 5, 10, and 30 seconds with a 2KW ultra-high pressure mercury lamp (distance 1 m) (The negative film used is IEICE chart with 200-line dots) [Development conditions] Commercially available Nexen [F] processor 1 (manufactured by Fujirex Co., Ltd.) (development time 20 seconds, washing with water, after dyeing, rinsing,
Developing device equipped with a drying process) Developing solution: 0.5% sodium metasilicate + anionic activator aqueous solution Test results under the above conditions are shown in Table 1.

Therefore, (C) to (5) cannot be used as photosensitive materials for non-silver salt films under the above conditions. Furthermore, if the developer is only water, it takes a long time to develop (60 seconds), and even if an image is formed, it will not be a brightly colored image in the next dyeing process.

Furthermore, for comparison of (A) and (B), the sensitizer was changed to 4-(4-amyloxyphenyl)-2,6-bis-(-4-methoxyphenyltiti) instead of 5-nitroacenaphthene. When a film is made using Apyrillium perchlorate, (A) can be photographed, but (B) cannot.

Therefore, the photosensitive compositions of the present invention are preferred materials for making non-silver salt films. Furthermore, the cinnamic acid-based copolymers shown below have low photosensitivity;
It is unsuitable for the use of the present invention.

Claims (1)

[Scope of Claims] 1 The following structural units (I), (II), (III), and (IV), (I) 2.5 to 45 mol%, (II) 5 to 20 mol%, (III) 18 to 70 mol% (IV) A photosensitive composition for a non-silver salt film, characterized in that it contains a copolymer containing 2 to 20 mol% as a photocurable component. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
(IV)