JPH0572729A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To improve storage stability and image developability only by exposure by incorporating a quinonediazido compound, an alkali-soluble resin, a compound to be allowed to produce an acid by exposure, and a p- phenylazodiphenylamine derivative. CONSTITUTION:For example, in the manufacture process of a printing plate and the like, the same plate is exposed in plural times by multi-face printing or repeating of printing to confirm exposure degree at the time of exposure. At that time, it is necessary to confirm the border line between the unexposed part and exposed part, and accordingly, this photosensitive composition is allowed to comprise the quinonediazido compound as a photosensitive component, the alkali-soluble resin as a binder, the compound to be allowed to produce an acid, and the compound having a p-phenylazodiphenyl skeleton, thus permitting superior image developability only by exposure in combination with sufficient storage stability to be ensured.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition applied to a positive-working photosensitive lithographic printing plate and a photoresist, and more particularly to a photosensitive composition capable of obtaining a visible image after exposure and before development.

[0002]

2. Description of the Related Art A photosensitive composition used for a printing plate or a photoresist is required to have a visible image property (or a printout property or a printout property). This is a property that a visible image can be obtained after exposure and before development.However, during the plate making process of a printing plate or when using a photoresist, the exposure amount can be confirmed at the time of exposure, and multiple exposures can be performed on the same plate multiple times by multi-sided printing or overprinting. This is necessary because it is possible to check the boundary between the exposed and unexposed areas when it is done.

Conventionally, various methods have been proposed to obtain this property. For example, JP-A-58-190947
No., 59-64835, 60-57340, 61-
183644, 62-49345, 62-5824
No. 1, 62-231251 discloses a combination of a photoradical generator and a leuco dye, which is disclosed in JP-A-50-6320.
Japanese Patent Laid-Open No. 63-137876 discloses a combination of a photo radical generator and a lactone compound, and Japanese Patent Laid-Open No. 61-137876 discloses a combination of a photo radical generator and a xanthene compound.
No. 6,222,58-87553 discloses combinations of diazo compounds and pH indicator dyes.
3, 53-133428, 61-151644, 6
The combination of a triazine compound and a pH indicator dye is disclosed in JP-A-6-24242 and 63-58440.
A combination of an oxadiazole compound and a pH indicator dye is disclosed in JP-A-58-87554.
No. 59-121043, a combination of a quinonediazide compound and a pH indicator dye is disclosed in JP-A-48-12.
No. 104, 60-239738, 61-123835
The use of photochromic compounds is described in each of the publications.

[0004]

However, these methods have problems in storage stability such that the visible image after exposure is discolored or erased during storage, and the visible image itself after exposure is not sufficient. However, there is a drawback of the conventional technique.

[0005]

The inventors of the present invention have made earnest studies to overcome such difficulties and obtain an excellent photosensitive composition. As a result, at least a quinonediazide compound was used as a photosensitive component and an alkali-soluble resin was used as a binder. In the photosensitive composition having the above composition, at least a compound capable of generating an acid upon exposure and a compound having a p-phenylazodiphenylamine skeleton are contained as an exposure visible image agent, whereby the excellent exposure visible image property provides sufficient storage stability. The inventors have found that they can be obtained as a result of the above, and have reached the present invention. That is, the object of the present invention is to provide a photosensitive composition having excellent storage stability. Another object of the present invention is to provide a photosensitive composition having excellent exposure visibility. Furthermore, another object of the present invention is to provide a photosensitive composition that is easy to use during use.

Accordingly, the object of the present invention is to provide at least (a) a quinonediazide compound, (b) an alkali-soluble resin, (c) a compound which produces an acid upon exposure, and (d) a p-phenylazodiphenylamine compound. It is easily achieved by the photosensitive composition characterized by containing.

The present invention will be described in detail below. In the present invention, the quinonediazide compound represented by (a) is preferably a compound having an o-benzoquinonediazide group or an o-naphthoquinonediazide group, and particularly preferably a compound having an o-naphthoquinonediazide group. As such a quinonediazide compound, Japanese Patent Application No. 63-29
Examples thereof include those described in Japanese Patent No. 3107.

In the present invention, the content of the quinonediazide compound is 5 to 6 based on the total amount of the photosensitive composition excluding the solvent.
0 wt% is preferable, and particularly preferably 10 to 50 wt%
Is. In the present invention, as the alkali-soluble resin represented by (b), any resin that can be mainly used as a binder may be used, but it is described in novolac resins and vinyl-based polymer resins, US Pat. No. 3,751,257. Polyamide resin, US Pat. No. 3,660,0
Examples of the linear polyurethane resin, phthalated resin of polyvinyl alcohol, epoxy resin condensed from bisphenol A and epichlorohydrin, celluloses such as cellulose acetate and cellulose acetate phthalate described in JP-A-97, novolak resin and vinyl. Preferred examples include polymer resins and combinations thereof. Examples of such an alkali-soluble resin include those described in Japanese Patent Application No. 63-293107. In the present invention, the content of the alkali-soluble resin is preferably 5 to 95% by weight, and particularly preferably 20 to 90% by weight, based on the total solid content of the photosensitive composition.

In the present invention, examples of the compound (c) which produces an acid upon exposure to light include, for example, Japanese Patent Laid-Open No.
No. 0-36209, o-naphthoquinonediazide-4-sulfonic acid halogenide, JP-A-53-3622.
No. 3, trihalomethyl-2-pyrone and trihalomethyl-triazine, o-naphthoquinonediazide-4-sulfonic acid chloride described in JP-A-55-6244, and a phenol having an electron-withdrawing substituent. And ester compounds or amide compounds with anilines, halomethyl-vinyl-oxadiazole compounds and diazonium salts described in JP-A-55-77742, and the like. In the present invention, the content of the compound which produces an acid upon exposure is preferably 0.2 to 10% by weight, and particularly preferably 0.5 to 3% by weight, based on the total solid content of the photosensitive composition.

In the present invention, p- represented as (d)
As the phenylazodiphenylamine compound, those having the following structures are preferable.

[0011]

[Chemical 1]

[Wherein R ¹ represents a hydrogen atom, a C ₁ -C ₅ alkyl group, an aryl group or an aralkyl group, and R ² -R ⁶ represent a hydrogen atom, a C ₁ -C ₅ alkyl group, an aryl group, An aralkyl group, a nitro group, or a sulfonic acid group or a salt thereof, represented by R ⁷ , R ⁸ , R ¹⁴ ,
R ¹⁵ represents a hydrogen atom, a C ₁ -C ₅ alkyl group, an aryl group or an aralkyl group, or R ⁷ and R
⁸ , R ¹⁴ and R ¹⁵ each may form a ring, the ring may have a substituent, and may be an aromatic ring. R ^{9 to} R ¹³ are each a hydrogen atom or C _{1 to} C ₅ alkyl group, aryl group, aralkyl group, sulfonic acid group or salt thereof, hydroxyl group or ester thereof, nitro group, or optionally substituted phenylazo group, or R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³
May form a ring with each other, the ring may have a substituent, and may be an aromatic ring. ] More specifically

[0013]

[Chemical 2]

And (1), (2), (3)
Is preferred. In the present invention, the content of the p-phenylazodiphenylamine compound is preferably 0.1 to 10% by weight, more preferably 0.1% by weight based on the total solid content of the photosensitive composition.
It is 5 to 2% by weight. The photosensitive composition used in the present invention may contain other additives in addition to the above materials, if necessary. For example, in the photosensitive composition used in the present invention, in order to improve the oil sensitivity of the photosensitive composition, a condensate of a substituted phenol and an aldehyde represented by the following general formula [II] is used as an oil sensitizer. And / or an o-naphthoquinonediazide sulfonic acid ester compound of the resin.

[0015]

[Chemical 3]

(Wherein R ₁ and R ₂ are each a hydrogen atom,
It represents an alkyl group or a halogen atom, and R ₃ represents an alkyl group having 2 or more carbon atoms or a cycloalkyl group. )
The content of the oil sensitizer is preferably 0.05 to 15% by weight based on the total solid content of the photosensitive composition, and particularly preferably 0.
It is 5 to 5% by weight.

An organic acid may be added to improve the sensitivity. Examples of such an organic acid include those described in Japanese Patent Application No. 63-293107.
In the present invention, the content of the organic acid is preferably 0.05 to 15% by weight, and particularly preferably 0.1 to 8% by weight, based on the total solid content of the photosensitive composition. The photosensitive composition, various solvents, for example, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, cellosolves such as ethyl cellosolve acetate, dimethylformamide,
By applying a coating material dissolved in a coating solvent such as dimethyl sulfoxide, dioxane, acetone, cyclohexanone or trichloroethylene to a suitable support, it can be put into practical use as a photosensitive lithographic printing plate or photoresist. The method for producing a photosensitive lithographic printing plate using an aluminum plate as a support will be described in detail below as an example.

When an aluminum plate is used as the support, surface treatment such as graining treatment, anodic oxidation treatment and, if necessary, sealing treatment is carried out. A known method can be applied to these treatments. Examples of the graining method include a mechanical method and an electrolytic etching method. Examples of the mechanical method include a ball polishing method, a brush polishing method, a liquid honing polishing method, and a buff polishing method. The above-mentioned various methods can be used alone or in combination depending on the composition of the aluminum material. A method of electrolytic etching is preferable.

Electrolytic etching is performed using phosphoric acid, sulfuric acid, hydrochloric acid,
It is carried out in a bath in which inorganic acids such as nitric acid are used alone or in a mixture of two or more kinds. After the graining treatment, if necessary, desmut treatment is performed with an aqueous solution of alkali or acid to neutralize and wash with water. The anodizing treatment is carried out by using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid and the like as an electrolytic solution, and electrolytically using an aluminum plate as an anode. The amount of anodized film formed is 1 to 50 mg /
dm ² is suitable, preferably 10-40 mg / dm ² . The amount of the anodic oxide film is determined by, for example, immersing an aluminum plate in a phosphoric acid chromic acid solution (phosphoric acid 85% solution: 35 ml, chromium oxide (VI): 20 g dissolved in 1 liter of water) to form an oxide film. It is determined by measuring the change in weight of the plate before and after the film is dissolved.

Specific examples of the sealing treatment include boiling water treatment, steam treatment, sodium silicate treatment, and dichromate aqueous solution treatment. In addition to this, the aluminum plate support may be subjected to undercoating treatment with a water-soluble polymer compound or an aqueous solution of a metal salt such as fluorinated zirconic acid. A photosensitive lithographic printing plate is obtained by coating the above-mentioned photosensitive composition on the above-mentioned support, but the coating amount is generally 0.5 to 3.5 g / m as solid content although it varies depending on the use.
A range of ² is suitable.

As a coating method, generally known roll coaters, slide hopper type coaters, gravure coaters, whaler coaters, wire bar coaters and the like can be used. A lithographic printing plate can be obtained by exposing and developing the photosensitive lithographic printing plate thus obtained according to a conventional method.

[0022]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. Examples 1 to 3 An aluminum plate (material 1050, temper H16) having a thickness of 0.24 mm was placed in a 5% sodium hydroxide aqueous solution at 60 ° C. for 1 hour.
After performing degreasing treatment for minutes, electrolytic etching treatment was performed in a 0.5 mol / l hydrochloric acid aqueous solution under the conditions of temperature: 25 ° C., current density: 60 A / dm ² , treatment time: 30 seconds. Then, after desmutting treatment in a 5% aqueous sodium hydroxide solution at 60 ° C. for 10 seconds, in a 20% sulfuric acid solution, temperature: 20 ° C., current density: 3 A / dm ² , treatment time: 1 minute Anodizing treatment was performed. Furthermore, hot water sealing treatment was performed with hot water at 30 ° C. for 20 seconds to prepare an aluminum plate as a support for a lithographic printing plate material.

A coating solution of a photosensitive composition having the following composition was applied to the aluminum plate prepared as described above using a spin coater and dried at 90 ° C. for 4 minutes to give a photosensitive layer having a film thickness of 2.2 g / m 2.
A positive photosensitive lithographic printing plate of No. ² was obtained.

[Photosensitive Composition Coating Liquid] Naphthoquinone (1,2) -diazide- (2) -4-sulfonyl chloride and pyrogallol-acetone resin (Mw
= 2,000) esterification product (condensation rate 30%) ...
………… 15 parts ・ Phenol and m- and p-mixed cresol (phenol: m-cresol: p-cresol = 20: 48: 3)
(2, weight ratio) and copolycondensation resin of formaldehyde (“SK-156”, manufactured by Sumitomo Duren Co., Ltd.) ……………… 8
5 parts-Ester compound of novolak resin (Mw = 1800) synthesized from p-tert-octylphenol and formaldehyde and naphthoquinone- (1,2) -diazide- (2) -5-sulfonic acid chloride (condensation rate 50
%) ……………… 1 part ・ 3,4-dimethoxybenzoic acid ……………… 5 parts ・ 2-trichloromethyl-5- [β- (2-benzofuryl) vinyl] -1,3,4-oxa Diazole …………
… Part 1 ・ p-Phenylazodiphenylamine compound …………
… 1 part (listed in Table 1) ・ Methyl cellosolve …………… 800 parts On the photosensitive lithographic printing plate thus obtained, a step tablet (No. 2 manufactured by Eastman Kodak Co., density difference 0.15 each) 21 steps of gray scale)
400 mJ / cm ^{2 using a} 1 kW metal halide lamp ("Idle Fin 2000" manufactured by Iwasaki Electric Co., Ltd.) as a light source
After exposure, the visibility of the boundary between the exposed and unexposed areas was visually evaluated. The evaluation results are shown in Table 1.

Comparative Example A photosensitive lithographic printing plate was prepared, exposed and evaluated in the same manner as in Example 1 except that leuco crystal violet was used instead of the p-phenylazodiphenylamine compound. The evaluation results are shown in Table 1.

[0026]

[Table 1]

1) Storage at 40 ° C. and 80% humidity for 7 days 2) The numbers of the present invention are those described in the above specific examples. From the results shown in Table 1, it can be seen that the photosensitive composition of the present invention is excellent in storage stability and is also excellent in exposure visibility.

[0028]

INDUSTRIAL APPLICABILITY The photosensitive composition of the present invention is excellent in storage stability and has excellent exposure visibility, so that it can be used when applied to a printing plate or a photoresist more than conventional photosensitive compositions. It has excellent properties and is industrially useful.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideyuki Nakai No. 1 Sakura-cho, Hino-shi, Tokyo Konica stock company (72) Inventor Takeo Akiyama No. 1 Sakura-cho, Hino-shi, Tokyo Konica stock company (72) Inventor Tomoyuki Matsumura 1st Sakura-cho, Hino City, Tokyo Konica Stock Company

Claims (1)

[Claims] 1. A photosensitive material containing at least (a) a quinonediazide compound, (b) an alkali-soluble resin, (c) a compound that generates an acid upon exposure to light, and (d) a p-phenylazodiphenylamine compound. Composition.