JPH0572730A - Photosensitive composition - Google Patents

Abstract

(57) [Summary] [Structure] A photosensitive composition comprising a quinonediazide compound, an alkali-soluble resin, a compound capable of generating an acid upon exposure, p
-Having an aminoazobenzene skeleton, the maximum absorption wavelength λ
Compounds with _max of 450 nm or less, and absorption maximum wavelength λ
It is characterized by containing at least a visible development agent having a _max of 550 nm or more and 650 nm or less. By using the photosensitive composition of the present invention,
It is possible to obtain a positive-working photosensitive lithographic printing plate, a photoresist and the like which are excellent in exposure visibility and development visibility at the same time.

Description

Detailed Description of the Invention

[0001]

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 specifically to a photosensitive composition having good exposure visibility and development visibility. Regarding

[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. These can be roughly divided into a bleaching system in which a portion exposed to light is bleached and a bleaching system in which color is developed.
Examples of fading systems include JP-A-53-36223, 53.
-133428, 61-151644, 62-24
A combination of a triazine compound and a pH indicator dye in JP-A Nos. 242 and 63-58440, JP-A-60-1773.
40 combination of oxadiazole compound and pH indicator dye, JP-A-58-87554, 59-1210.
There is a combination of a quinonediazide compound and a pH indicator dye in each publication of No. 43. Further, examples of the color-developing system include JP-A Nos. 58-190947, 59-64835 and 60-5.
No. 7340, No. 61-183644, No. 62-49345
Nos. 62-58241 and 62-231251, combinations of photoradical generators and leuco dyes; JP-A-50-6320, combinations of photoradical generators and lactone compounds; There is a combination of a photoradical generator and a xanthene compound in Japanese Patent No. 137876, and a combination of an organic halogen compound and an arylamine compound in Japanese Patent Publication Nos. 51-8330 and 54-4257.

Comparing these bleaching system and color developing system, in the case of the bleaching system, since the color is not completely erased by light, only the density difference from the dark color to the light color is compared, but in the case of the color developing system,
Differences in density and hue appear. Therefore, a color-developing system is advantageous in terms of exposure visibility.

[0005]

However, when a positive-type sensitizer is used, the exposed portion is removed, so that a light-colored portion remains in the color-developing system, which is disadvantageous in viewability of development. .. On the other hand, in the color-developing system, when another dye for developing visible image is mixed, the lightness of the plate is generally lowered and the exposure image is deteriorated.

That is, in the photosensitive composition, it has been difficult to achieve both visible development and visible exposure.

[0007]

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. It has been found that the object of the present invention can be achieved by using a compound capable of generating an acid upon exposure, a compound having a p-aminoazobenzene skeleton, and a specific development visible image agent in combination as an exposure visible image agent.

That is, an object of the present invention is to provide an excellent positive type photosensitive composition which can judge the suitability of the exposure amount during use and can easily set the proper exposure amount. Another object of the present invention is to provide a positive photosensitive composition having excellent development visibility. Still another object of the present invention is to provide a photosensitive composition such as a positive type lithographic printing plate, a photoresist and the like, which has excellent exposure visibility and development visibility.

Accordingly, the object of the present invention is at least (a) a quinonediazide compound, (b) an alkali-soluble resin, (c) a compound which produces an acid upon exposure, (d)
It has a p-aminoazobenzene skeleton and has a maximum absorption wavelength λ.
It is easily achieved by a photosensitive composition comprising a compound having a _max of 450 nm or less, and (e) a development visible agent having a maximum absorption wavelength λ _max of 550 nm or more and 650 nm or less.

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.
The thing etc. which are described in 3-293107 gazette are mentioned.

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, JP-A No. 5/1985
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 by (d)
Has an aminoazobenzene skeleton and has a maximum absorption wavelength λ _max
The compound having a structure of 450 nm or less is preferably a compound having the following structure.

[0014]

[Chemical 1]

[Wherein R ¹ and R ² are a hydrogen atom and C, respectively]
_{1 to} C _{5 represents} an alkyl group, an aryl group or an acetyl group, and R ³ , R ⁴ , R ¹⁰ and R ¹¹ are each a hydrogen atom and C ₁ to C _{1.
5 represents} an alkyl group, an aryl group or an aralkyl group, or R ³ and R ⁴ , R ¹⁰ and R ¹¹ may form a ring, and the ring may have a substituent, The ring may be an aromatic ring.

R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each a hydrogen atom, a C ₁ -C ₅ alkyl group, an aryl group, an aralkyl group, a nitro group, a halogen atom, a hydroxyl group or its ester, and a sulfonic acid. A group or an ester thereof, a carboxylic acid group, a salt thereof or an ester thereof, or substitution at positions adjacent to each other of R ₅ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , and R ⁸ and R ^9. May form a ring with each other, and the ring may be an aromatic ring. More specifically

[0017]

[Chemical 2]

[0018]

[Chemical 3]

And the like, particularly (16), (17),
The compound of (18) is preferable. In the present invention, the content of the p-phenylazodiphenylamine compound is preferably 0.1 to 10% by weight, particularly preferably 0.5 to 2% by weight, based on the total solid content of the photosensitive composition. In the case of a compound having a maximum absorption wavelength of more than 450 nm, there is a tendency to have a problem of visible image development.

In the present invention, examples of the visible developing agent having a maximum absorption wavelength λ _max represented by (e) of 550 nm or more and 650 nm or less include (a) AIZEN SPILON VIOLET C-
RH (manufactured by Hodogaya Chemical Co., Ltd.) (B) AIZEN Victoria Blue BH
(Hodogaya Chemical Co., Ltd.) (C) AIZEN Victoria Blue BO
H (manufactured by Hodogaya Chemical Co., Ltd.) (d) NK-68 (manufactured by Japan Photosensitive Dye Research Institute Co., Ltd.) (e) Malachite Green (f) Stains-all (ki) Ethyl Violet (ku) Brilliant Green Among them, the compound (H) is particularly preferable. The content of the developer visualizing agent maximum wavelength lambda _{ma x} of the absorption of 550nm or more 650nm or less in the present invention, the total solid content of the photosensitive composition, preferably 0.1 to 10% by weight, particularly preferably It is 0.5 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.

[0022]

[Chemical 4]

(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 performed. 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.

[0029]

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 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- 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 ・ Compound with p-aminoazobenzene skeleton …………
… 1 part (listed in Table 1) ・ Development visible image agent ……………… 0.7 part (listed in Table 1) ・ Methyl cellosolve …………… 800 parts On the photosensitive lithographic printing plate thus obtained , Step tablet (Eastman Kodak No. 2, 21-step gray scale with a density difference of 0.15 each) is adhered,
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. Also, the exposed plate is treated with an SDR-1 developer (Konica Corporation).
After development (25 ° C., 45 s) with a 6-fold diluted solution (manufactured by Mfg. Co., Ltd.), the visible image development property was visually evaluated. The evaluation results are shown in Table 1.

Comparative Example In Example 1, instead of the compound (16) having a p-aminoazobenzene skeleton,

[0033]

[Chemical 5]

Similarly, a photosensitive lithographic printing plate was prepared using
It was exposed and evaluated. The evaluation results are shown in Table 1.

Comparative Example 2 In Example 3, quinaldine red (λ _max / nm = 520) was used in place of the visible development agent (K).
Similarly, using (B), a photosensitive lithographic printing plate was prepared, exposed and evaluated. The evaluation results are shown in Table 1.

Comparative Example 3 A photosensitive lithographic printing plate was prepared, exposed and evaluated in the same manner as in Example 1 except that the compound (16) having a p-aminoazobenzene skeleton was not added. The evaluation results are shown in Table 1.

Comparative Example 4 A photosensitive lithographic printing plate was prepared, exposed and evaluated in the same manner as in Example 3 except that the developing visible agent (K) was not added.
The evaluation results are shown in Table 1.

[0038]

[Table 1]

From the results shown in Table 1, it can be seen that by using the photosensitive composition of the present invention, the visible image visibility and the visible image development which are the objects of the present invention are good.

[0040]

By using the photosensitive composition of the present invention, it is possible to obtain a positive-working photosensitive lithographic printing plate, a photoresist, etc., which are excellent in exposure visibility and development visibility at the same time, and are industrially valuable. Is extremely large.

 ─────────────────────────────────────────────────── ─── 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 compound having at least (a) a quinonediazide compound, (b) an alkali-soluble resin, (c) a compound capable of generating an acid upon exposure, (d) a p-aminoazobenzene skeleton, and having a maximum absorption wavelength λ _max of 450 nm. The following compounds and (e) absorption maximum wavelength λ _max of 550 nm or more and 650
A photosensitive composition comprising a visible development agent having a wavelength of nm or less.