JPS5911894B2 - photosensitive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive composition, and more specifically, a hydroxystyrene polymer or copolymer partially crosslinked with a diisocyanate compound;
The present invention relates to a photosensitive composition containing an aromatic azide compound.

Photosensitive compositions containing a polymer compound having a phenolic hydroxyl group, such as a phenol-formaldehyde resin, and an aromatic azide compound are already known, and these compositions can be used as photoresists, photoreliefs, etc. It is used in practical applications.

For example, a photosensitive composition containing an alkali-soluble novolak resin and an aromatic azide compound was disclosed in Japanese Patent Publication No. 50-26962.
This method is known from Japanese Patent Publication No. 49-4481, Japanese Patent Publication No. 16801-1987, and the like.

In addition, a photosensitive polymer in which an aromatic azide unit is bonded to an alkali-soluble novolac resin was disclosed in Japanese Patent Application Laid-Open No. 47-3478.
It is described in Publication No. 7/.

The above-mentioned photosensitive compositions have good film-forming properties when exposed to light, and can be easily developed with a weak alkaline aqueous solution. Moreover, the photosensitive film does not swell with this developer, so it has good resolution. It is widely used as a printing plate material because it has high corrosion resistance and is relatively easy to treat waste water such as developer.

However, in existing photosensitive compositions such as those mentioned above, a novolac resin with a relatively small molecular weight is used as a binder or basic base resin, so the resulting photosensitive film (relief image) is brittle and easily scratched. Not only is the general mechanical strength insufficient, but also the mechanical strength when immersed in developer, etching agent, etc. is insufficient, and as a result, the image may become thin or deformed during various processes. There are drawbacks such as Alkali-soluble resins having phenolic hydroxyl groups include, in addition to novolac resins, hydroxystyrene polymers or copolymers, and photosensitive compositions containing this hydroxystyrene polymer and aromatic azide compounds are described, for example, in Japanese Patent Publication No. Showa 50-9500
It is described in Publication No. 2.

However, the photosensitive film (relief image) obtained from such a photosensitive composition also has insufficient general mechanical strength, such as being brittle and easily scratched, and has low mechanical strength in developing solutions and etching solutions. It has drawbacks such as poor storage stability. The purpose of the present invention is to provide a photosensitive film (relief image) that is strong and scratch-resistant, has high mechanical strength even in various processing solutions, has a high shelf life, and can be easily developed with an alkaline aqueous solution. The object of the present invention is to provide a photosensitive composition that is possible and has high sensitivity.

The above objects can be achieved by the photosensitive composition of the present invention.

That is, the photosensitive composition of the present invention comprises an aromatic azide compound and at least 65 hydroxystyrene polymerized units represented by the following general formula (1) (wherein R represents hydrogen or a halogen atom). mol% of hydroxystyrene polymer, characterized in that 3 to 15% equivalent of the hydroxyl groups in the hydroxystyrene polymer are bonded to a diisocyanate compound and modified with urethane. be.

The diisocyanate compound has the general formula (), in which A is an alkylene group of the following general formula (): (However, n in the above formula represents an integer of 2 to 6) toluylene group, the following general formula () 4,4'-phenylmethane group: (B in the above formula represents a hydrogen atom, halogen atom, thyl group, or methoxy group) xylylene group (〈○?), ν▲▲Z Following formula (V) Biphenylene group: (However, B in the above formula is the same as defined above) or a naphthylene group ("○T (5))" is preferred.

The urethane-modified hydroxystyrene polymer of the present invention contains at least 65% (mol) of hydroxystyrene units of general formula (1), preferably from 1000 to 2000 hydroxystyrene units.
It has a backbone chain made of a hydroxystyrene polymer having an average molecular weight of 0, and 3 to 15% (equivalent), preferably 5 to 10%, of the hydroxyl groups of the backbone chain.
% (equivalent) of the diisocyanate compound of the general formula (1) in an inert organic solvent to form a side chain.

The structure of the side chain formed by this reaction is not yet fully clear, but some hydroxyl groups are graft-polymerized with a diisocyanate compound, and the other two hydroxyl groups are formed intramolecularly or intermolecularly by diisocyanate compounds. It appears to be cross-linked. The urethane-modified hydroxystyrene polymer having side chains modified in this way maintains good solubility in aqueous alkaline solutions, and when cured by photo-sensitization, is flexible and tough, is resistant to scratches, and is resistant to processing liquids. Among these, it is possible to provide a film (relief image) having sufficient mechanical strength and corrosion resistance. When the diisocyanate compound is bonded in an amount less than 3% (equivalent) to the hydroxyl group, the mechanical strength of the photosensitive cured film formed from the resulting photosensitive composition is insufficient, and scratches are particularly likely to occur. If the amount is more than 15%, the resulting photosensitive composition will have poor solubility in organic solvents, and development with an alkaline aqueous solution will become difficult. In the urethane-modified hydroxystyrene polymer of the present invention, it is important that the hydroxyl group in the backbone chain is modified with a diisocyanate compound.

Even if a hydroxystyrene polymer is modified using a monoisocyanate compound, an acylation reagent, an etherification reagent, etc. instead of a diisocyanate compound, the resulting modified polymer will not meet the objectives of the present invention. This is not fully achievable, and this has been confirmed by many experiments. The photosensitive composition comprising urethane-modified polyhydroxystyrene and an aromatic azide compound of the present invention has improved photocurability compared to a photosensitive composition comprising unmodified polyhydroxystyrene and an aromatic azide compound, Furthermore, the development latitude is significantly improved. First of the attached drawings
The figure is a graph showing the photocurability and development latitude of the photosensitive composition comprising urethane-modified polyhydroxystyrene and an aromatic compound of the present invention.

In FIG. 1, curve A is a curve showing the characteristics of the photosensitive composition of the present invention obtained in Example 1, which will be described later.

The vertical axis is a 2K
The number of remaining steps is shown when contact baking was carried out for 2 minutes at a distance of 1 m using a W ultra-high pressure mercury lamp, and then was developed with a 1% sodium hydroxide aqueous solution and then washed with water. The horizontal axis represents the development time, which is expressed based on the minimum time required to develop the unexposed area (unexposed area omission time). In other words, the development time is extended (
(Development press), double the unexposed missing time to 100%
, 3 times is displayed as 200%. Curve A in FIG. 1 shows that the photosensitive composition of the present invention made of urethane-modified polyhydroxystyrene and an azide compound has a wide development latitude, with almost no change in the number of steps remaining even if the development time is extended. It shows.

For comparison, unmodified polyhydroxystyrene (curve B) was used instead of the urethane-modified polyhydroxystyrene of Example 1.
) and metacresol novolak (curve C) were used to compare their performance.

As a result, as is clear from curves B and C, in both cases of unmodified polyhydroxystyrene and azide and the combination of metacresol novolak and azide, the number of remaining steps decreases as the development time increases; That is, it is recognized that it is unstable in the developer. Examples of diisocyanate compounds suitable for obtaining the urethane-modified polyhydroxystyrene of the present invention include trimethylene diisocyanate, tetramethylene diisocyanate,
Hexamethylene diisocyanate, 2,4-toluylene diisocyanate. ! l') 7 dianate, 2,6-tolylene diisocyanate, metaxylylene diisocyanate, metaxylidene diisocyanate, 4,1-diphenylmethane diisocyanate, 3,3! -dichloro-4,4'-diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4
'-biphenylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3
'-dichloro-4,47-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, and the like.

The urethane-modified hydroxystyrene polymer used in the present invention is a hydroxystyrene homopolymer containing at least 65% (mol) of hydroxystyrene units, such as polyhydroxystyrene, polyhydroxychlorostyrene, or polyhydroxybromostyrene, or It is obtained from polyhydroxystyrene copolymer.

This homopolymer or copolymer has a molecular weight of 1,000 to 20,000
It is preferable that the average molecular weight is . Hydroxystyrene units can be combined with other polymerized units such as styrene, α-methylstyrene, chloromethylstyrene, various vinyl ethers, vinyl ketones, acrolein,
Acrylonitrile, acrylic acid, acrylic esters, methacrylic esters, acrylamide, N-N'
It may be copolymerized with at least one of -dimethylacrylamide, N-morphoylacrylamide, various diene compounds, divinylbenzene, isoprene, butadiene, cyclobentadiene, and maleic anhydride. The reaction of the hydroxystyrene polymer or copolymer with the diisocyanate compound is generally carried out in an inert organic solvent in the presence of a Lewis base, such as a tertiary amine, at a temperature above the boiling point of the solvent used. It is carried out under reflux.

Suitable inert organic solvents include dioxane, cyclohexanone, dimethylformamide and methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, tetrahydrofuran, and the like. Further, as the photosensitizing agent contained in the photosensitive composition of the present invention, an aromatic azide compound soluble in an organic solvent is used, and such an azide compound is described, for example, in U.S. Pat. ) (Eastman Kodak Co.)
It is described in Japanese Patent Publication No. 51-485, Japanese Patent Publication No. 16801/1980, etc.

Examples of aromatic azide compounds suitable as the photosensitizer of the present invention include 4,4'-diazidostilbene, 4
・4'-Diazidochalcone, 4,4'-diazidobenzophenone, 2,6-bis(4'-azidobenzylidene)
Cyclohexanone, 6-azido-2-(4'-azidostyryl)benzimidazole, 3,3'-dimethoxy-
4,4'-diazidobiphenylene, 1-azidopyrene,
1,6-diazidopyrene, 2-(4'-methoxyanilino)-5-azidobenzoic acid methyl ester, 2-anilino-5-azidobenzoic acid, 2-(41-azidophenyl)-[naphtho-1'. 4,5-oxazole] and 2-(4'-azidophenyl)-6-methylbenzothiazole.

However, the aromatic azide compounds used in the present invention are not limited to those exemplified above. The photosensitive composition according to the present invention preferably contains an aromatic azide compound in an amount of 5 to 50 parts by weight based on 100 parts by weight of the urethane-modified hydroxystyrene polymer, and contains these in an organic solvent, e.g. , ethyl cellosolve, methyl cellosolve, butyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diethyl carbitol, cyclohexanone, methyl ethyl ketone, dioxane, dimethyl formamide, and butyl acetate alone or in a mixture at a concentration of 1 to 30% by weight. Can be used.

In order to further increase the practical sensitivity of the photosensitive composition of the present invention,
Sensitizers, for example aromatic nitro compounds such as 5-nitroacenaphthene, 2-nitrofluorene, 2,7-dinitrofluorene, 1-nitropyrene, and 1,8-dinitropyrene, Michler-ketone, Thiomihira - ketones, etc., and quinones, such as 1,2-benzanthraquinone, may be added.

In this case, the amount of sensitizer added is 10% of the aromatic azide compound.
0.1 to 2.0 parts by weight is suitable for 0 parts by weight.
Furthermore, a storage stabilizer may be added to the photosensitive composition of the present invention, if necessary.

Suitable storage stabilizers include, for example, hydroquinone, 2
・6-di-tert-butylphenol, tert-butylcatechol, phenyl-α-naphthylamine, phenyl-β-naphthylamine, di-β-naphthyl p-phenylenediamine, N●N'-diphenyl-p-phenylenediamine , methylthio-m-cresol, and the like are suitable. The amount of storage stabilizer added to the photosensitive composition is preferably 0.5 to 1.0 parts by weight per 100 parts by weight of the urethane-modified hydroxystyrene polymer.

Since the alkali-soluble polymer contained in the photosensitive composition according to the present invention has a relatively large molecular weight, it has excellent anti-film-forming properties and adhesion to the substrate compared to photosensitive compositions using novolak resin. mechanical strength such as scratch resistance,
It is also excellent in terms of corrosion resistance against chemicals, etc., but in order to further improve the coating properties, film properties, developability, etc. of the photosensitive composition of the present invention, other resins may be mixed therein. It's okay.

Examples of such resins for mixing include acrylic acid resins, methacrylic acid resins, epoxy resins, novolak resins, styrene-maleic anhydride copolymers, partial esterification products thereof, polyvinyl acetate, and parts thereof. Saponified products, maleated polybutadiene, polyvinyl butyral, poly-N-N-dimethylacrylamide, poly-N-morphoylacrylamide, and cellulose derivatives such as ethylcellulose are preferably used. The amount of these additive resins used is preferably 5 to 40 parts by weight per 100 parts by weight of urethane-modified polyhydroxystyrene.

In addition, in order to further improve the physical properties of the coating film formed by the photosensitive composition of the present invention, plasticizers such as dibutyl phthalate, dioctyl phthalate, dioctyl adipate, tricresyl phosphate, trioctyl phosphate, etc. , etc. may be added.

When the photosensitive composition of the present invention is used as a second original, an intermediate film for plate making, etc., it reacts with an aromatic azide compound to form a dye in order to obtain a photochromic image or a colored image with high density. You may also add Katsupura-ichi which can be used. In this case, the dye-forming coupler may be one which is generally well known in the field of azo dye chemistry, such as 2-hydroxynaphthalene, 1-hydroxynaphthalene, 2,3-dihydroxynaphthalene, 4
-Methoxy-1-hydroxynaphthalene, 2-hydroxy-3-naphthanilide, 2,4-dichloro-1-naphthol, 4-acetylphenol, N-N-diethylaniline, m-N-N-dimethylaminophenol, N-
Ethyl-N-benzylaniline, N-methyldiphenylamine, acetoacetanilide, and 1-phenyl-3
Examples include methyl-5-pyrazolone.
The amount of the dye-forming coupler added to the photosensitive composition of the present invention is preferably 10 to 100 parts by weight per 100 parts by weight of the aromatic azide compound.

The film formed from the photosensitive composition of the present invention has excellent light blocking properties against ultraviolet rays. For example, the photosensitive composition of the present invention obtained in Example 2 described later has light absorption properties as shown in FIG. 2 of the accompanying drawings. In FIG. 2, the light absorption properties of the photosensitive composition of Example 2 when films were formed at coating amounts of 87/d, 57/wl, and 37/d are shown by curves A, B, and C. . As is clear from FIG. 2, the photosensitive composition film of Example 2 has high light-shielding properties (absorption properties) in the ultraviolet region (420 nm or less). If it is necessary to enhance the light-shielding property of the photosensitive composition of the present invention in the visible region and increase the coloring density, an organic solvent-soluble dye may be added to the photosensitive composition of the present invention. . Examples of dyes for this purpose include C.I. I. Solvent Yellow - 2, 6, 14, 1
5, 16, 56C. I. Solvent orange 1, 2,
5.C. I. Solvent Red 1, 3, 8, 23, 2
4, 25C. I. Solvent Violet 25, 49
C. I. Solvent blue 2, 25, 55, 73, C
．． I. Solvent Brown 2, 5 C. I. Examples include Solvent Black 3, 5, and 7.

To prepare a photosensitive material using the photosensitive composition of the present invention, first, it is dissolved in an organic solvent, and this solution is applied to aluminum plates, zinc plates, copper plates, paper, various plastic films (polyester films, It is coated on a suitable support such as cellulose triacetate film (cellulose triacetate film, etc.) and dried.

During this coating, it is desirable that the total solid weight of the photosensitive composition in the coating solution be 5 to 5%, more preferably 10 to 30%, based on the weight of the organic solvent. . To apply the photosensitive composition solution of the present invention onto a support, any conventional method can be used, such as spin coating, roll coating, dip coating, and spray coating.

A photosensitive material produced using the photosensitive material of the present invention is used by a conventional method.

For example, a transparent original image having a desired image such as a halftone image or a line image is overlaid on the photosensitive surface of a photosensitive material and brought into close contact with the photosensitive material, and exposed.
By developing with a suitable alkaline aqueous solution, a negative relief image can be obtained from the original image. The alkaline aqueous solution used for development includes sodium metasilicate, tertiary
Aqueous solutions such as sodium phosphate and sodium hydroxide are used. In this case, a small amount of a surfactant, a water-miscible organic solvent, etc. may be added to promote development and prevent uneven development. The relief image obtained from the photosensitive composition of the present invention is resistant to scratches and has excellent mechanical strength, abrasion resistance, chemical strength, chemical resistance, adhesion to a support, and storage stability. Therefore, it can be used for a wide range of purposes.

For example, it is suitable for use in letterpress printing, intaglio printing, name plates, printed wiring boards, etc. In addition, since the relief image has good oil sensitivity, it is also excellent as a photosensitive material for planography. It can also be used as a second original drawing for copying, an intermediate negative for plate making, a master for overhead projector, etc. Next, the present invention will be explained with reference to examples, but the present invention is not limited to the following synthesis examples and examples.

In addition, parts and % in the synthesis examples and examples mean parts by weight and % by weight unless otherwise specified. Synthesis Example 1 Polyp-hydroxystyrene (average molecular weight 3600,
800 parts (manufactured by Maruzen Oil Co., Ltd.) were dissolved in 1000 parts by volume of dioxane, a catalytic amount of triethylamine was added, and while stirring, 40 parts of hexamethylene diisocyanate was added.
The temperature was raised to 100 to 110°C, and the reaction was carried out at this temperature for 4 hours.

The resulting reaction mixture was then diluted with 25,000 parts by volume of water to precipitate the product, which was filtered and dried to obtain 840 parts of a light brown powder. When the content of hydroxyl groups in the obtained urethane-modified polyhydroxystyrene was determined by an acetylation method, it was found that 7.1% of the hydroxyl groups in the polyhydroxystyrene before treatment had been consumed by modification. Synthesis Example 2 Poly-p-hydroxystyrene (average molecular weight 3600,
Dissolve 700 parts of Maruzen Sekiyu) in 1000 parts of dioxane, add a catalytic amount of triethylamine, and stir while stirring.
Add 37.9 parts of 2,4-toluene diisocyanate,
This reaction mixture was heated to 99 to 105°C, and then reacted at this temperature for 4 hours.

The resulting reaction mixture was diluted with 25,000 parts by volume of water to precipitate the product, which was filtered and dried to obtain 735 parts of a light brown powder. When the hydroxyl groups in the modified polyhydroxystyrene thus obtained were fixed by an acetylation method, it was found that 7.6% of the hydroxyl groups in the polyhydroxystyrene before treatment had been consumed by modification.
Synthesis Example 3 800 parts of poly-p-hydroxybromostyrene (average molecular weight 3500, Maruzen Oil Co., Ltd.) (about 1.5 bromine groups exist per unit molecule) was added to 1000 parts of cyclohexanone.
A catalytic amount of N-N-dimethylbenzylamine was added to the mixture, and 7.2 parts of tetramethylene diisocyanate was added while stirring. After raising the temperature to 150 to 160°C, the mixture was reacted at this temperature for 4 hours.

The reaction mixture was then diluted with 30,000 parts by volume of water to form a precipitate, filtered and dried to form a pale yellow powder.
I got 00 copies. When the thus obtained urethane-modified polyhydroxybromostyrene was fixed by the method of Synthesis Example 1, 3% of the hydroxyl groups in the polyhydroxybromostyrene before treatment had been consumed by modification. Synthesis Example 4 Poly-p-hydroxystyrene (average molecular weight 19400
, made by Maruzen Oil)! After dissolving in 1000 parts by volume of T, methyl ethyl ketone and adding a catalytic amount of triethylene diamine, 33.5 parts of 4,1-diphenylmethane diisocyanate was added while stirring, and the solution was 75-80 parts by volume. After heating the CK to raise the temperature, the mixture was reacted at this temperature for 5 hours.

Next? Methyl ethyl ketone was removed from the reaction mixture under C mechanical pressure and the residue was dried to obtain 830 parts of a pale orange powder. In the urethane-modified polyhydroxystyrene thus obtained, 8% of the hydroxyl groups in the polyhydroxystyrene before treatment were consumed by modification. Synthesis Example 5 In the process of Synthesis Example 1, 45 parts of 1,5-naphthalene diisocyanate was used instead of 40 parts of hexamethylene diisocyanate, but in the same manner as in Synthesis Example 1, 830 parts of light brown powder was obtained. .

In the modified polyhydroxystyrene thus obtained, 7% of the hydroxyl groups in the polyhydroxystyrene before treatment were consumed by modification. Synthesis Example 6 The same operations as in Synthesis Example 1 were repeated.

However, instead of 40 parts of hexamethylene diisocyanate,
33 parts of 3,3'-dimethoxy-4,l-biphenylene diisocyanate was used. 830 parts of a pale orange powder was obtained. In the urethane-modified polyhydroxystyrene thus obtained, 6.% of the hydroxyl groups in the polyhydroxystyrene before treatment were consumed by modification. Synthesis Example 7 800 parts of a copolymer of p-hydroxystyrene and styrene (component ratio 2:1, average molecular weight 7000) was mixed with 1 part of dioxane.
000 parts by volume, 30 parts of hexamethylene diisocyanate was added with stirring, and further a catalytic amount of triethylamine was added, and the mixture was gradually heated to 100 to 110° C., and reacted at this temperature for 3 hours.

The reaction mixture was then diluted with 20,000 parts by volume of water to form a precipitate, filtered through P, and dried to give a light brown powder of 780 parts by volume.
I got the department.

The resulting urethane-modified p-hydroxystyrene-styrene copolymer was measured for hydroxyl group equivalent in the copolymer by an acetylation method, and found to be 6.2% of the original hydroxyl group.
was being consumed. Synthesis Example 8 Poly-p-hydroxystyrene 800 in Synthesis Example 1
Using 800 parts of p-hydroxystyrene and maleic anhydride copolymer (component ratio 3:2, average molecular weight 6000) in place of 1 part, the reaction was carried out in the same manner to obtain 790 parts of light brown powder.

When the hydroxyl group content of this urethane-modified p-hydroxystyrene/maleic anhydride copolymer was measured by an acetylation method, it was found that 9% of the hydroxyl groups before treatment were consumed.

Synthesis Example 9 In Synthesis Example 7, hexamethylene diisocyanate 30
28 parts of 2,4-toluene diisocyanate was used instead of 1 part, and the reaction was carried out in the same manner to obtain 820 parts of light brown powder.

When the hydroxyl group content of this urethane modified p-hydroxystyrene-styrene copolymer was measured by an acetylation method, it was found that 7.6% of the initial hydroxyl groups were consumed.

Example 1 Corona discharge treated thickness 0.11! 1 of polyethylene terephthalate film was attached to the rotary coater, and the coater was heated to 75r. p. m. A photosensitive composition solution having the following composition was applied to the film while rotating the film.

Next, the coating film on the film was placed in a ventilation dryer at 80°C.
The solvent was completely evaporated and dried, thereby forming a film of the photosensitive composition on the film surface. The coating amount at this time was 8.0 f/Trl. A negative film was placed on top of this film, and the film was exposed for 2 minutes from a distance of 1 u using a 2KW ultra-high pressure mercury lamp.
．． It was immersed in a 0% aqueous sodium hydroxide solution to dissolve and remove the unexposed areas, and then developed. In this way, a clear dark green blurred image was obtained. The resolution of this film was good, with 175 lines per inch of 5% highlight halftone dots being accurately reproduced, and the edges of each halftone dot being sharp. The above-mentioned photosensitive composition film is very stable, and even if it is left at room temperature for 6 months, there is almost no change in its developability, and the initial development time (time required to dissolve and remove the unexposed area) is short. What was hot in 50 seconds will still be 50% hot even after 10 months of storage.
6 seconds, the time required for development was increased by only 6 seconds, which indicates that the storage stability of the photosensitive film of this example is good. The scratch resistance of the photosensitive film was also good.

For comparison, untreated polyhydroxystyrene (average molecular weight 3600) (Comparative Example 1), polyhydroxybromostyrene (average molecular weight 35001, 1.5 bromine groups present per unit molecule) (Comparative Example 2), and metacresol novolak When the same operations as in Example were repeated except that the resin (Comparative Example 3) was used instead of urethane-modified polyhydroxystyrene, there was no noticeable difference in image and resolution compared to Example 1. However, the scratch resistance of the photosensitive film was significantly poor. Furthermore, the latitude of development was also poor.

The above evaluation of abrasion resistance was carried out as follows.

The photosensitive film and F paper (Toyosawa paper After rubbing 2) together 50 times, the condition of the photosensitive film (coated film surface) was visually evaluated.

The evaluation criteria are as follows.

The pencil hardness was measured according to JIS K54OO paint general test method.

The development latitude of the above photosensitive coating is shown in Table 3 and in FIG.

In order to compare the development latitude, the photosensitive films obtained in the above-mentioned Example 1 and Comparative Examples 1 and 3 were used as the original Kodaku Photography Step Tablet Black 2 (Kodatsu Co., Ltd.), and a 2KW film was used. Contact baking was performed for 2 minutes at a distance of 1 meter using an ultra-high pressure mercury lamp, and then 1%
The film was developed using a sodium hydroxide aqueous solution and washed with water.

The development time is based on the time for the unexposed areas to be dissolved and removed (release time), and the development time is further extended as shown in Table 3 (
The remaining number of steps for each film was determined.

The results are shown in Table 3.

In the table, the development time extension ratio of 100% is twice the unexposed area removal time, and 200% is three times the development time extension ratio. As is clear from Table 3 and FIG. 1, the film of the photosensitive composition of the present invention using urethane-modified polyhydroxystyrene has a wide development latitude, and stable images can be obtained.

Example 2 A polyethylene terephthalate film having a thickness of 0.111 mm and subjected to corona discharge treatment was coated with the following photosensitive liquid.

The coating film was dried in the same manner as in Example 1 to obtain a photosensitive film. The coating amounts at this time were 8, 5 and 31/i. A negative film was superimposed on each of the photosensitive films thus obtained, and contact baking was performed for 12 minutes at a distance of 1 m from an ultra-high pressure mercury lamp of 2 W, followed by development with 1% sodium hydroxide.

A deep and colorful blurred image was obtained. The light-shielding properties at this time are shown in FIG. Curves A, B, and C in FIG. 2 show the light shielding properties against light of each wavelength when the coating amounts are 8f7/i, 5f/i, and 3f/i, respectively.

As is clear from FIG. 2, the photosensitive composition of the present invention has extremely high light-shielding properties against ultraviolet rays.

In the case of a photosensitive film with a coating amount of 8 f/A, as can be seen from curve A, in the ultraviolet region with a wavelength of 420 nm or less, it has an optical density of 2 or more, and even with a coating amount of 5 f/I, it shows sufficient light-shielding properties for practical use. There is. The light-shielding property of the photosensitive film of Example 1 was also as good as that of Example 2.

Example 3 A 1.0 mm thick zinc plate for photo-letter printing was polished with sandpaper, smoothed with a 5% acetic acid aqueous solution, thoroughly washed with water, and dried so that no water droplets remained.

A photosensitive composition solution having the following composition was applied onto this support using a doctor plate. A zinc plate coated with the above photosensitive liquid,
Dry in a ventilation dryer at 80°C to completely evaporate the solvent.
A film of the photosensitive composition was formed on the surface of a zinc plate.

A meshed negative film was placed on top of this, and the film was exposed to light for 90 seconds from a distance of 1 m using a 2 W ultra-high pressure mercury lamp, and then immersed in a 4% sodium metasilicate aqueous solution. The unexposed areas were dissolved and removed and developed. The photosensitive film exposed and developed in this way has sufficient mechanical strength as a resist even immediately after washing with water, so it is possible to immediately apply corrosion treatment to the zinc plate without post-processing such as burning. Ta. The film of this photosensitive composition is very stable, with almost no change in developability even after being left at room temperature for 6 months.In other words, the unexposed area removal time of this photosensitive film at the time of manufacture was 60 seconds. 1
Even after 0 months had passed, it was 68 seconds, an increase of only about 8 seconds.

Example 4 A 1% aqueous sodium hydroxide solution,
Next, the surface was smoothed with a 5% acetic acid aqueous solution, washed with water, and dried.

Next, a solution of a photosensitive composition having the following composition was applied to the aluminum plate using a roll coater. This photosensitive composition coating was dried in the same manner as in Example 1.

In this way, presensitized plate (PS version)
was gotten. This PS version showed no change in quality even after being stored in the dark for 6 months. Place this PS plate in a vacuum printing machine, place a meshed negative film on it, and
Exposure was performed for 1 minute from a distance of 1 m using a KW ultra-high pressure mercury lamp.

After exposure, the film was developed using a 0.5% aqueous sodium hydroxide solution in an automatic processor, and the unexposed areas were easily eluted and 5% highlight halftone dots with 175 lines per inch were accurately reproduced. This fully satisfied the requirements for high-grade offset printing. When this printing plate was attached to an offset printing machine and printed using commonly used printing ink and etchant, good prints were obtained, and the printing durability was even after printing more than 10,000 sheets on coated paper. It was so hot that no abnormality was observed. For comparison, poly-p-hydroxystyrene (average molecular weight 6,000) and poly-(p-hydroxyprom)styrene (average molecular weight 100,001
The urethane-modified poly(p-hydroxy-brome) used in Synthesis Example 3 contains approximately 1.5 bromine groups per unit molecule.
When styrene was used in place of styrene and the same operation as in this example was performed, all of the comparative photosensitive films showed that the mechanical strength of the exposed film surface was weak, and the printing durability was about 3000 sheets for coated paper. It was hot. Example 5 The same operation as in Example 4 was performed.

However, 2,6-bis(4'-azidobenzylidene)cyclohexanone was used in place of 6 parts of 2-(4''-azidophenyl)-6-methyl-benzothiazole.The resulting PS plate was similar to Example 4. Similar good results were obtained.Example 6 A corona discharge-treated polyethylene terephthalate film with a thickness of 0.1 m77! was mounted on a rotary coating machine.
This coating machine is 65r. p. m. A solution of a photosensitive composition having the following composition was applied while rotating.

The resulting photosensitive coating film was dried in a ventilation dryer at 80° C. to completely evaporate the solvent and form a film of the photosensitive composition on the film surface.

The coating amount was 77/7r1'. A meshed negative film was layered on this photosensitive film, exposed for 2 minutes from a distance of 1 m using a 2KW ultra-high pressure mercury lamp, and then developed by immersing it in a developer having the composition shown below.

As a result, unexposed areas were easily removed, and a deep reddish-orange image was obtained after washing with water and drying.

The color density of the image was 2.0. The resolution of the image was also good, with 175 lines per inch of highlight halftone dots accurately reproduced, and the halftone dots of each density percentage had sharp edges. When the image after development was observed under a microscope, it was found that 2μ
Parallel lines with an interval of are completely separated. In order to compare this photosensitive film and the silver salt lithium film, positive films were made from the same original, and a lithographic printing plate was made on a positive aluminum PS plate under the same exposure and development conditions.
When a printing test was conducted, it was found that the photosensitive film of this example did not have thicker halftone dots, especially in the shadows, and had a brighter tone compared to the silver-salt lithium film. . The shelf life of the raw plate obtained in this example was good, with 6
When stored at room temperature for several months, almost no changes were observed in developability, color density, and resolution.

Example 7 The procedure of Example 6 was repeated.

However, instead of the urethane-modified polyhydroxystyrene obtained in Synthesis Example 4, the urethane-modified polyhydroxystyrene obtained in Synthesis Example 5 was used. As in Example 5, a deep reddish-orange image with good resolution was obtained. Example 8 6.0 parts of the resin obtained in Synthesis Example 7 was used instead of 5.0 parts of the resin used in the photosensitive composition of Example 1 (urethane-modified polyhydroxystyrene obtained in Synthesis Example 1). However, as in Example 1, a clear dark green positive image with good resolution was obtained.

Example 9 4.0 parts of the resin obtained in Synthesis Example 8 was used instead of 4.0 parts of the resin used in the photosensitive composition of Example 2 (urethane-modified polyhydroxystyrene obtained in Synthesis Example 3). However, as in Example 2, a dark green positive image was obtained, and both resolution and light shielding properties were good.

Example 10 5.0 parts of the resin obtained in Synthesis Example 7 was used in place of 5.0 parts of the resin (urethane-modified polyhydroxystyrene obtained in Synthesis Example 2) used in the photosensitive composition of Example 3. As a result, a photosensitive liquid for photolithographic printing having good resolution, corrosion resistance, and storage stability similar to that of Example 3 was obtained.

Example 11 Resin used in the photosensitive composition of Example 3 (urethane-modified polyhydroxystyrene obtained in Synthesis Example 2)
When 5.0 parts of the resin obtained in Synthesis Example 9 was used instead of 5.0 parts, a photosensitive liquid for photolithographic printing having the same good performance as in Example 3 was obtained.

[Brief explanation of drawings]

FIG. 1 is a graph showing the relationship between the development time and the number of remaining steps (sensitivity) for the photosensitive composition of the present invention (curve A) and other photosensitive compositions of the present invention (curves B and C). 2 is a graph showing the light absorption properties of the photosensitive composition of the present invention.

Claims (1)

[Claims] 1. An aromatic azide compound and the following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (However, in the above formula, R
represents a hydrogen or halogen atom) and a hydroxystyrene polymer containing at least 65 mol% of hydroxystyrene polymerized units represented by hydrogen or a halogen atom, wherein 3 to 15% equivalent of the hydroxyl groups in the hydroxystyrene polymer are diisocyanate compounds. 1. A photosensitive composition characterized by being combined with and modified with urethane. 2 The diisocyanate compound has the general formula (II) OC
N-A-NCO (II), where A is an alkylene group of the following general formula (III): -(CH_2)_n-(III) (However, n in the above formula is an integer of 2 to 6. ), toluylene group, 4,4'-diphenylmethane group of the following general formula (IV): ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (IV) (However, B in the above formula is a hydrogen atom, a halogen atom, a methyl or methoxy group), xylylene group, biphenylene group of the following formula (V): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V)
(However, B in the above formula is the same as defined above) or a naphthylene group. 3. The photosensitive composition according to claim 1, wherein the hydroxystyrene polymer is polyhydroxystyrene. 4. The photosensitive composition according to claim 1, wherein the hydroxystyrene polymer is polyhydroxychlorostyrene or polyhydroxybromostyrene. 5 5 to 1 of the hydroxyl groups in the hydroxystyrene polymer
2. The photosensitive composition according to claim 1, wherein 0% equivalent is modified by the diisocyanate compound. 6 The hydroxystyrene polymer has 1000 to 2
The photosensitive composition according to claim 1, having an average molecular weight of 0,000. 7. The photosensitive composition according to claim 1, wherein the urethane-modified hydroxystyrene polymer and the aromatic azide compound are contained in a ratio of 100 parts by weight to 5 to 50 parts by weight. 8 The diisocyanate compound is trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate,
metaxylylene diisocyanate, metaxylidene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dichloro-4,4'-diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy- 4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,4
2. The photosensitive composition according to claim 1, which is '-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, or 1,5-naphthalene diisocyanate. 9 The aromatic azide compound is 4,4-diazidostilbene, 4,4'-diazidochalcone, 4,4'-diazidobenzophenone, 2,6-bis(4'-azidobenzylidene)cyclohexanone, 6- Azide-2-(4'
-azidostyryl)benzimidazole, 3,3'-dimethoxy-4,4'-diazidobiphenylene, 1-azidopyrene, 1,6-diazidopyrene, 2-(4'-methoxyanilino)-5-azidobenzoic acid methyl ester,
2-anilino-5-azidobenzoic acid, 2-(4'-azidophenyl)-[naphtho-1', 2'-4, 5-oxazole], or 2-(4'-azidophenyl)-6-
The photosensitive composition according to claim 1, which is methylbenzothiazole. 10 The hydroxystyrene polymer is the (I)
Hydroxystyrene compounds of the formula and styrene, α-methylstyrene, chloromethylstyrene, vinyl ethers, vinyl ketones, acrolein, acrylonitrile, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamide, N. N-
Dimethylacrylamide, N-morphoylacrylamide, diene compounds, divinylbenzene, isoprene,
The photosensitive composition according to claim 1, which is a copolymer with at least one compound selected from the group consisting of butadiene, cyclopentadiene, and maleic anhydride.