JPH05100421A - Photosensitive composition - Google Patents

Abstract

(57) [Summary] [Structure] A photosensitive composition comprising at least a quinonediazide sulfonate, an alkali-soluble resin, a compound capable of generating an acid upon exposure, and o-naphthoquinonediazide-6-
It contains a sulfonic acid halide and an organic dye. [Effect] It has excellent exposure visibility and excellent storage stability.

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,
59-64835, 60-57340, 61-18.
No. 3644, No. 62-49345, No. 62-58241
JP-A No. 62-231251 discloses a combination of a photo radical generator and a leuco dye, and JP-A No. 50-6320 discloses a combination of a photo radical generator and a lactone compound. JP-A-53-53 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 conventional combination of a photo-acid generator and a color-changing agent is insufficient in the visibility of exposed light, and / or the exposed visible image is colored or erased during storage. There was a difficulty that it would end up.

[0005]

Means for Solving the Problems As a result of intensive investigations by the present inventors to overcome such difficulties and obtain an excellent photosensitive composition, as a visible light exposure agent in a combination of a specific photosensitive component and a binder. The present inventors have found that the presence of a specific compound together with a compound that generates an acid upon exposure and an organic dye provides sufficient storage stability and that an excellent visible image property of exposure can be obtained, and has reached the present invention.

[0006] An object of the present invention is to provide a tourist composition which has excellent exposure and visible image quality and also has excellent storage stability. Therefore, the object of the present invention is at least (a) a quinonediazidesulfonic acid ester (b) an alkali-soluble resin (c) a compound that generates an acid upon exposure, (d) an o-naphthoquinonediazide-6-sulfonic acid halogenide and (e) ) It is easily achieved by a photosensitive composition containing an organic dye.

The present invention will be described in detail below. The quinonediazide sulfonic acid ester represented by (a) in the present invention is an o-benzoquinonediazide group or 0-
A compound having a naphthoquinonediazide group is preferable, and a compound having an o-naphthoquinonediazide group is particularly preferable. Examples of such quinonediazide sulfonates include those described in Japanese Patent Application No. 63-293107.

In the present invention, the content of the quinonediazide sulfonic acid ester is preferably 5 to 60% by weight, particularly preferably 10% by weight, based on the entire photosensitive composition excluding the solvent.
~ 50% by weight. 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 novolac resin, vinyl polymer resin, US Pat. No. 3,751,25
No. 7, polyamide resin, US Pat. No. 3,660,097, linear polyurethane resin, polyvinyl alcohol phthalated resin, bisphenol A and epichlorohydrin condensed epoxy resin, acetic acid Cellulose, cellulose such as cellulose acetate phthalate and the like can be mentioned, and novolac resin, vinyl polymer resin and combinations thereof can be mentioned as 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, examples of the compound (c) which generates an acid upon exposure to light include trihalomethyl-2-pyrone and trihalomethyl-triazine described in JP-A-53-36223, and JP-A-55-55. 777
42, halomethyl-vinyl-oxadiazole compounds, diazonium salts and the like. In the present invention, the content of the compound that 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, o represented as (d)
Examples of -naphthoquinonediazide-6-sulfonic acid halogenide include o-naphthoquinonediazide-6-sulfonic acid chloride, o-naphthoquinonediazide-6-sulfonic acid bromide, o-naphthoquinonediazide-6-sulfonic acid fluoride and the like. The content of o-naphthoquinonediazide-6-sulfonic acid halogenide used in the present invention is 0.1 to the total solid content of the photosensitive composition.
5% by weight is preferable, and 0.3 to 3% by weight is particularly preferable.
Is.

In the present invention, the organic dye represented by (e) changes its color tone by interacting with the photodecomposition product formed by exposing (c) of the above-mentioned compound of the present invention. 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 Industry Co., Ltd.], Oil Red 5B [Orient Chemical Industry Co., Ltd.], Oil Scar Red # 308 [Orient Chemical Industry Co., Ltd.]
Made] Red OG [Orient Chemical Industry Co., Ltd.], Oil Red RR [Orient Chemical Industry Co., Ltd.], Oil Green # 502 [Orient Chemical Industry Co., Ltd.], Spiron Red BEH Special [Hodogaya Chemical Industry Co., Ltd. )), M-cresol purple, cresol red, rhodamine B, rhodamine 6G, first acid violet R, sulforhodamine B, auramine,
4-p-diethylaminophenyliminonaphthoquinone,
2-Carboxanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carbostearylamino-4-p-dihydroxyoxyethylamino-phenyliminonaphthoquinone, p-methoxybenzoyl-p'-diethylamino-o'-methylphenylimino Acetanilide, cyano-p-diethylaminophenyliminoaceanilide, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone, etc. .

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, dibenzilaniline, 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, more preferably 0.02 to 5% 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 resin comprising a condensation product of a substituted phenol and an aldehyde as an oil sensitizer and / or the resin An o-naphthoquinone diazidostone phonate compound can be included.

The above-mentioned substituted phenols are preferably R ₁ , R ₂ ,
R ₃ has up to 3 substituents, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or a halogen atom, and R ₃ represents an alkyl group having 2 or more carbon atoms or a cycloalkyl group. To be done. The content of the oil sensitizer is preferably 0.05 to 15% by weight based on the total solid content of the photosensitive composition,
Particularly preferably, it is 0.5 to 5% 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 above-mentioned photosensitive composition comprises various solvents such as cellosolves such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, dimethylformamide, dimethylsulfoxide,
By applying a coating material dissolved in a coating solvent such as dioxane, acetone, cyclohexanone, trichloroethylene or the like on 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 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. 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 m
g / dm ² is suitable, and preferably 10-40 mg /
dm ² . The amount of the anodic oxide film is, for example, an aluminum plate and a phosphoric acid chromic acid solution (phosphoric acid 85% solution: 35 m).
1, chromium oxide (VI): 20 g was dissolved in 1 l of water) to dissolve the oxide film, and the weight change before and after film dissolution of the plate was 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, a generally known roll coater, slide hopper type coater, gravure coater, whaler coater, wire bar coater or 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.

[0023]

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 5% sodium hydroxide aqueous solution at 60 ° C. for 1 minute, and then 0.5 mol / l Temperature in hydrochloric acid aqueous solution; 25 ° C, current density; 60
The electrolytic etching treatment was performed under the conditions of A / dm ² , treatment time; 30 seconds. Then, after desmutting at 60 ° C. for 10 seconds in a 5% aqueous sodium hydroxide solution,
Temperature in 20% sulfuric acid solution; 20 ° C, current density; 3A /
Anodizing treatment was performed under the conditions of dm ² , treatment time; 1 minute. Furthermore, hot water sealing treatment was performed for 20 seconds with hot water at 30 ° C. to produce an aluminum plate as a support for a lithographic printing plate material. The photosensitive composition coating liquid having the following composition was applied to the aluminum plate prepared as described above using a spin coater,
After drying at 90 ° C for 4 minutes, the photosensitive layer thickness is 2.2 g / m ^2.
To obtain a positive photosensitive lithographic printing plate.

[0024]

[Photosensitive composition coating liquid]

-Naphthoquinone (1,2) -diazide- (2) -4-
Sulfonyl chloride and pyrogallol-acetone resin (M
w = 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", Sumitomo Duren Co., Ltd.) ... 85
Part ・ Novolak resin synthesized from p-tert-octylphenol and formaldehyde (Mw = 1800)
And naphthoquinone- (1,2) -diazide- (2) -5-
Ester compound with sulfonic acid chloride (condensation rate 50
%) ・ ・ ・ ・ 1 part ・ 3,4-dimethoxybenzoic acid ・ ・ ・ ・ 5 part ・ 2-trichloromethyl-5- [β- (2-bezozofuryl) vinyl] -1,3,4-oxadiazole ...
・ 1 part ・ o-naphthoquinonediazide-6-sulfonyl chloride ・ ・ ・ ・ 1 part ・ Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) ・ ・ ・ ・ ・ ・ 0.9 part ・ Methyl cellosolve ・ ・ ・ ・ ・ ・ 800 parts

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
j / cm ² exposure and the difference in density between the exposed and unexposed areas were 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, the better the exposure visibility. The above results are shown in Table 1.

[0026]

Comparative Example 1 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that o-naphthoquinonediazide-6-sulfonyl chloride was used in place of o-naphthoquinonediazide-5-sulfonyl chloride, and exposure was evaluated. Similarly, the evaluation results are shown in Table 1.

[Comparative Example 2] A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that o-naphthoquinonediazide-6-sulfonyl chloride was used, and the exposure was evaluated. The evaluation results are shown in Table 1.

[0027]

[Table 1]

In the table, ⊚ indicates that the exposure visibility is very excellent, ∘ indicates that the exposure visibility is superior, Δ indicates that the exposure visibility is visible, and x indicates that the exposure visibility is insufficient. It means that.

From the results shown in Table 1, it can be seen that the use of the composition of the present invention makes it possible to obtain a photosensitive lithographic printing plate having the sufficient storage stability and the excellent exposure visible image property which are the objects of the present invention.

[0030]

EFFECTS OF THE INVENTION The photosensitive composition of the present invention described above is excellent in storage stability and has excellent visible image visibility.
A photosensitive lithographic printing plate and a photoresist can be obtained.

 ─────────────────────────────────────────────────── ─── 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. At least (a) a quinonediazide sulfonic acid ester (b) an alkali-soluble resin (c) a compound capable of generating an acid upon exposure to light (d) an o-naphthoquinonediazide-6-sulfonic acid halogenide and (e) an organic dye A photosensitive composition comprising: