JPH05100422A - Photosensitive composition - Google Patents

Abstract

(57) [Summary] [Structure] A photosensitive composition comprising at least a quinonediazide compound, an alkali-soluble resin, a compound capable of generating an acid upon exposure to light, an organic dye, and a halogen compound having a specific skeleton. .. [Effect] Not only during normal exposure, but also during low exposure, it has excellent exposure visibility.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photosensitive composition applied to a 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 an exposure visible image property (also referred to as 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 performance. 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.
JP-A-63-137876 discloses a combination of a photoradical generator and a lactone compound, and JP-A-63-137876 discloses a combination of a photoradical generator and a xanthene compound.
In each of JP-A Nos. 36222 and 58-87553, a combination of a diazo compound and a pH indicator dye is disclosed in JP-A-53-36.
223, 53-133428, 61-151644
Nos. 62-24242 and 63-58440 disclose combinations of triazine compounds and pH indicator dyes, and JP-A-60-177340 discloses combinations of oxadiazole compounds and pH indicator dyes. JP-A-58-875
Nos. 54 and 59-121043 disclose combinations of quinonediazide compounds and pH indicator dyes.
12104, 60-239738, 61-1238.
The use of photochromic compounds is described in each of the 35 publications.

[0004]

However, the exposure visibility of the conventional combination of a photo-acid generator and a color-changing agent is still insufficient, and the exposure visibility at low exposure is very difficult to see. have.

[0005]

SUMMARY OF THE INVENTION The inventors of the present invention have made extensive studies in order to overcome these difficulties and obtain an excellent photosensitive composition. As a result, a photosensitive composition containing a specific photoconductor and a specific resin has been obtained. The present inventors have found that excellent visible light visibility can be obtained even at low light exposure by including a compound that generates an acid upon light exposure and a specific halogen compound in the product.

An object of the present invention is to provide a photosensitive composition which has an excellent visible image visibility even at low exposure while maintaining required performance such as sensitivity at a sufficient level. Therefore, the object of the present invention is represented by at least (a) a quinonediazide compound, (b) an alkali-soluble resin, (c) a compound that generates an acid upon exposure, (d) an organic dye and (e) a compound represented by the following general formula (I) Halogen compounds

[0007]

[Chemical 2]

(In the formula, each of R ^{1 to} R ³ represents a hydrogen atom, a halogen atom or a halogenated alkyl group, at least one of which represents a halogenated alkyl group, and X represents N or CH. It is easily achieved by a photosensitive composition containing a). Hereinafter, the present invention will be described in detail.

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. Examples of such a quinonediazide compound include those described in Japanese Patent Application No. 63-293107. In the present invention, the content of the quinonediazide compound is preferably 5 to 60% by weight, and particularly preferably 10 to 50% by weight, based on the entire photosensitive composition excluding the solvent.

In the present invention, the alkali-soluble resin represented by (b) may be any resin which can be mainly used as a binder, but novolac resins and vinyl-based polymer resins, US Pat. No. 3,751,257. Polyamide resins described in US Pat. No. 3,66.
Examples of the linear polyurethane resin described in JP-A-0,097, a phthalated resin of polyvinyl alcohol, an epoxy resin condensed from bisphenol A and epichlorohydrin, celluloses such as cellulose acetate and cellulose acetate phthalate, and a novolak resin. A vinyl polymer resin and a combination thereof are preferable examples. Examples of such alkali-soluble resins 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 90% by weight, and particularly preferably 20 to 90% by weight, based on the total solid content of the photosensitive composition.

In the present invention, compounds represented by (c) which generate an acid upon exposure include, for example, o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-36203 and JP-A-53-362223.
And trihalomethyl-2-pyrone described in JP-A No. 6-58, o-naphthoquinonediazide-4-sulfonic acid chloride described in JP-A-55-6244, and phenols or anilines having an electron-withdrawing substituent. Esterification products or amide compounds with compounds, JP-A-Sho 5
Examples thereof include halomethyl-vinyl-oxadiazole compounds and diazonium salts described in 5-77742. In the present invention, the content of the compound that generates an acid upon exposure is 0.2 to 1 based on the total solid content of the photosensitive composition.
It is preferably 0% by weight, particularly preferably 0.5 to 3% by weight.

In the present invention, represented as (d),
The organic dye changes its color tone by interacting with the photolysis product produced by exposing (c). There are two types of such organic dyes, one that develops color and the other that fades or changes color. As the organic dye that fades or discolors, various dyes such as diphenylmethane, triphenylmethane-based thiazine, oxazine-based, xanthene-based, anthraquinone-based, iminonaphthoquinone-based, and azomethine-based dyes are effectively used.

Specific examples of these are as follows. Ie Brilliant Green,
Eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein, methyl violet 2B, quinaldine red, rose bengal, metanil yellow , Thymol sulfophthalein,
Xylenol blue, methyl orange, orange IV,
Diphenylthiocarbazone, 2,7-dichlorofluorescein, paramethyl red, congo red, benzopurpurin 4B, α-naphthyl red, Nile blue 2
B, Nile blue A, phenacetaline, methyl violet, malachite green, parafuchsin, Victoria pure blue BOH [Hodogaya Chemical Co., Ltd.], oil blue # 603 [Orient Chemical Co., Ltd.], oil pink # 312 [Orient Chemical Industrial Co., Ltd.], Oil Red 5B [Orient Chemical Co., Ltd.], Oil Scarlet # 308 [Orient Chemical Co., Ltd.]
Made], Oil Red OG [Orient Chemical Industry Co., Ltd.
Made], Oil Red RR [Orient Chemical Industry Co., Ltd.]
], Oil Green # 502 [manufactured by Orient Chemical Industry Co., Ltd.], Spiron Red BEH Special [manufactured by Hodogaya Chemical Co., Ltd.], m-cresol purple, cresol red, rhodamine B, rhodamine 6G, first acid violet R, sulfo. Rhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carbostearamino-4-p-dihydrooxyethylamino-phenyliminonaphthoquinone, p- Methoxybenzoyl-
p'-diethylamino-o'-methylphenyliminoacetanilide, cyano-p-diethylaminophenyliminoacetanilide, 1-phenyl-3-methyl-4-
p-diethylaminophenylimino-5-pyrazolone,
1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone and the like.

As the organic dye that develops color, arylamines can be mentioned. Aryl amines suitable for this purpose include so-called leuco dyes in addition to simple aryl amines such as primary and secondary aromatic amines, and examples thereof include the following. Diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-
Phenylenediamine, p-toluidine, 4,4'-biphenyldiamine, o-chloroaniline, o-bromoaniline, 4-chloro-o-phenylenediamine, o-bromo-N, N-dimethylaniline, 1,2,3 -Triphenylguanidine, naphthylamine, diaminodiphenylmethane, aniline, 2,5-dichloroaniline, N-methyldiphenylamine, o-toluidine, p, p'-tetramethyldiaminodiphenylmethane, N, N-dimethyl-p-phenylenediamine, 1 , 2-dianilinoethylene, p, p ', p "-hexamethyltriaminotriphenylmethane, p, p'-tetramethyldiaminotriphenylmethane, p, p'-tetramethyldiaminodiphenylmethylimine, p, p ′, P ″ -triamino-o-
Methyltriphenylmethane, p, p ′, p ″ -triaminotriphenylcarbinol, p, p′-tetramethylaminodiphenyl-4-anilinonaphthylmethane, p,
p ′, p ″ -triaminotriphenylmethane, p,
p ', p "-hexapropyltriaminotriphenylmethane.

The proportion of the above organic dye in the photosensitive composition is preferably 0.01 to 10% by weight,
It is more preferably used in an amount of 0.02 to 5% by weight. In the present invention, (e) is a halogen compound represented by the general formula (I), and specific examples thereof include 2,4,6-tris-trichloromethyl-S-triazine 2-chloro-4-trichloromethyl. Pyrimidine 2,4,6-tribromomethyl-S-triazine 2-chloro-4-tribromomethylpyrimidine The compound can be obtained as a commercially available product, and is described in J.
O. C. (1961) 26 4419 .

In the present invention, the content of the halogen compound is preferably 0.2 to 10% by weight, more preferably 0.5 to 3% by weight, based on the total solid content of the photosensitive composition.
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 resin comprising a condensation product of a substituted phenol and an aldehyde as an oil sensitizer and / or the resin An o-naphthoquinone diazide sulfonic acid ester compound can be included.

The substituted phenol is preferably R ¹ ,
It has up to three substituents of R ^2, R ^3, R ¹ and R ²
Is a hydrogen atom, an alkyl group or a halogen atom, and R ³ is an alkyl group having 2 or more carbon atoms or a cycloalkyl group. The content of the sensitizer is 0.05 to 15% by weight based on the total solid content of the photosensitive composition.
Is preferable, and particularly preferably 0.5 to 5% by weight.

A sensitizer may be added to the photosensitive composition of the present invention, if necessary. Examples of the sensitizer include benzophenone, anthracene, diethylthioxanthone, Michler's ketone and the like. Benzophenone is particularly effective. In the present invention, the content of the sensitizer is preferably 0.2 to 10% by weight based on the total solid content of the photosensitive composition,
It is particularly preferably 0.5 to 3% by weight.

An organic acid may be added to improve the sensitivity. Examples of such organic acids 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 performed. A known method can be applied to these treatments. Examples of the graining treatment method include a mechanical method and an electrolytic etching method. Examples of the mechanical method include ball polishing, brush polishing, liquid honing polishing, and buff polishing. The above-mentioned various methods can be used alone or in combination depending on the composition of the aluminum material. The 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 kinds of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid or the like as an electrolytic solution and using an aluminum plate as an anode for electrolysis. The amount of anodized film formed is 1 to 50 mg
/ Dm ² is suitable, preferably 10-40 mg / d
m ² . The amount of the anodic oxide film is, for example, a chromic acid phosphoric acid solution (85% phosphoric acid solution: 35 ml)
Chromium oxide (VI): 20 g is dissolved in 1 liter of water), the oxide film is dissolved, and the weight change before and after film dissolution of the plate is measured.

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 an undercoating treatment with an aqueous solution of a water-soluble polymer compound or 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.

[0024]

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. Example 1 A 0.24 mm thick aluminum plate (material 1050, temper H16) was degreased in a 5% aqueous sodium hydroxide solution at 60 ° C. for 1 minute, and then in a 0.5 mol / l hydrochloric acid aqueous solution. At a temperature of 25 ° C., a current density of 60 A / dm ² , and a treatment time of 30 seconds.
Then, in a 5% aqueous solution of sodium hydroxide at 60 ° C., 10
After desmutting for 2 seconds, the temperature was 20 ° C., the current density was 3 A / dm ² , the treatment time was 1 in a 20% sulfuric acid solution.
The anodic oxidation treatment was performed under the condition of 1 minute. 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 photosensitive composition coating solution 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-, 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.)
・ ・ ・ 85 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-oxadiazole ・ ・ ・ ・
・ ・ ・ ・ ・ Part 1 ・ Tris-trichloromer-S-triazine
・ ・ ・ ・ ・ ・ ・ ・ Part 1 ・ Victoria Pure-BOH (Hodogaya Chemical Co., Ltd.)
Manufactured) ・ ・ ・ ・ 0.9 parts ・ Methyl cellosolve ・ ・ ・
.... 800 copies

On the photosensitive planographic printing plate thus obtained, a step tablet (No.
2、21 steps of gray scale with 0.15 density difference)
2kW metal halide lamp (Iwasaki Electric Co., Ltd.)
Made by "Idol Fin 2000") as light source, 400m
A normal exposure of J / cm ² and a low exposure of 200 mJ / cm ² were performed, and the density difference between the exposed area and the unexposed area was visually evaluated under a yellow light. Further, measurement was performed using a densitometer (Macbeth densitometer RD-918 manufactured by Kollmorgen) to obtain an absolute value ΔD of the density difference between the exposed portion and the unexposed portion. The larger the ΔD is, the better the exposure visibility is. The above results are shown in Table 1.

Example 2 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that 2-chloro-4-trichloromethyl-pyrimidine was used instead of tris, trichloromethyl-S-triazine, and exposure was evaluated. Similarly, the evaluation results are shown in Table 1.

Comparative Example 1 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that tris and trichloromethyl-S-triazine were excluded, and exposure was evaluated. The evaluation results are shown in Table 1.

[0030]

[Table 1]

[0031]

INDUSTRIAL APPLICABILITY The photosensitive composition of the present invention has an excellent visible image visibility which is effective not only during normal exposure but also during low exposure.

 ─────────────────────────────────────────────────── ─── 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 (72) Inventor Toshitsugi 1st Sakura-cho, Hino City, Tokyo Konica Stock Company

Claims (1)

[Claims] 1. At least (a) a quinonediazide compound, (b) an alkali-soluble resin, (c) a compound that produces an acid upon exposure, (d) an organic dye, and (e) a halogen compound represented by the following general formula (I). [Chemical 1] (In the formula, R ^{1 to} R ³ are each a hydrogen atom, a halogen atom,
Or a halogenated alkyl group, at least one of which represents a halogenated alkyl group, and X represents N or CH).