JPH07199464A - Positive photosensitive composition - Google Patents

Abstract

PURPOSE:To provide a positive, photosensitive planographic plate or a photoresist excellent in sensitivity and exposed picture visibility by permitting the absorbance of a composition itself to meet a specific expression. CONSTITUTION:This positive photosensitive composition contains a 1, 2- naphtoquinonediazide-4-sulfonic acid ester compound of a novolak resin containing polyhydric phenol; an alkaline-soluble resin; a compound that produces an acid when exposed; and a pigment having an absorption maximum in the range 550-650nm and decolored by acids. The composition meets the expression before an image is exposed. Any resin that is usable as a binder can be used as the alkaline-soluble resin, and novolak resins, vinyl polymer resins or combinations of them are preferably used as the alkaline-soluble resin. The compound producing acid when exposed is a trihalomethyl-triazine, or halomethyl-vinyl-oxadiazole, compound, etc. The pigment is a diphenylmethane pigment or an indoaniline pigment, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive composition applied to a photosensitive lithographic printing plate, a photoresist or the like. More specifically, the present invention relates to a positive photosensitive composition having high sensitivity and excellent exposure visibility.

[0002]

2. Description of the Related Art Conventionally, a 1,2-naphthoquinonediazide sulfonic acid ester compound of a polyhydric phenol-containing novolak resin has been used for the purpose of improving the sensitivity of a positive photosensitive composition (for example, JP-A-55). -76346
Nos. 59-86046, 59-88734 and 59-88735). However, since the positive type photosensitive composition is subjected to multiple exposures on the same plate in the plate making process of a printing plate or when a photoresist is used, the exposure amount is confirmed, or in the case of multifaceted printing or weighting, Since it is necessary to confirm the boundary between the exposed portion and the unexposed portion, it is required that a visible image be obtained after exposure and before development. for that reason,
Usually, a dye having an absorption maximum in the range of 550 to 650 nm and discolored by an acid is added as an exposure visible image agent, but the above compound, particularly a 1,2-naphthoquinonediazide-4-sulfonic acid ester compound is added. If used,
There has been a problem that this exposed visible image property is deteriorated. Therefore, when the amount of the exposed visible image agent is increased, the sensitivity is lowered in turn. Therefore, a highly sensitive positive compound using a 1,2-naphthoquinonediazide-4-sulfonic acid ester compound of a polyhydric phenol-containing novolac resin is used. Type photosensitive compositions have not been realized.

[0003]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that a polyhydric phenol-containing novolak satisfying a certain specific condition in relation to the exposure visible image agent used. It was found that a positive-type photosensitive composition excellent in both exposure visibility and sensitivity can be found by using a composition mainly composed of a resin 1,2-naphthoquinonediazide-4-sulfonic acid ester compound, and the present invention provides the same. Arrived

That is, an object of the present invention is to provide a high-sensitivity positive-working photosensitive composition which does not suffer from the above-mentioned problem of deterioration of the visible image visibility. Thus, the object of the present invention is a positive photosensitive composition, which comprises (a) a 1,2-naphthoquinonediazide-4-sulfonic acid ester compound of a polyhydric phenol-containing novolac resin, and (b) an alkali-soluble resin. , (C) a compound capable of generating an acid upon exposure, and (d) having an absorption maximum in the range of 550 to 650 nm,
Further, it is easily achieved by a positive photosensitive composition containing a dye that changes color with an acid and satisfying the above formula [I] before image exposure.

The present invention will be described in detail below. In the present invention, the 1,2-naphthoquinonediazide-4-sulfonic acid ester compound of the polyhydric phenol-containing novolac resin represented by (a) is at least a polyhydric phenol and an aldehyde and / or a ketone as a structural unit. The obtained novolak resin is reacted with a 1,2-naphthoquinonediazide-4-sulfonic acid compound such as 1,2-naphthoquinonediazide-4-sulfonic acid chloride.

Examples of the polyphenols include catechol, resorcin, hydroquinone, phloroglucin,
Examples include pyrogallol, 1,2,4-trihydroxybenzene and the like, or a mixture thereof. Resorcin and pyrogallol are preferable, and pyrogallol is particularly preferable. Examples of the aldehydes and ketones include formaldehyde, acetaldehyde, benzaldehyde, methyl ethyl ketone and acetone, and preferably acetone.

The reaction between the novolak resin and the 1,2-naphthoquinonediazide-4-sulfonic acid compound is not particularly limited, but, for example, according to the conventional method previously proposed by a part of the present inventors, an excessive amount of After reacting in the presence of a basic reagent, a method of purifying the obtained product to remove by-products, or a 1,2-naphthoquinonediazide-4-sulfonic acid compound in a polyhydric phenol-containing novolac resin And the like in the presence of a nucleophile.
The 1,2-naphthoquinonediazide-4-sulfonic acid ester compound of the polyhydric phenol-containing novolac resin obtained by these methods has a low absorbance at 500 nm.

In the present invention, the content of (a) is generally 5 to 60% by weight, preferably 10 to 50% by weight, based on the total solid content of the photosensitive composition. 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, and examples thereof include novolac resins and vinyl-based polymer resins described in JP-A-2-137850, and US Polyamide resin described in US Pat. No. 3,751,257, linear polyurethane resin described in US Pat. No. 3,660,097, phthalated resin of polyvinyl alcohol, bisphenol A and epichlorohydrin Examples of the resin include condensed epoxy resins, celluloses such as cellulose acetate and cellulose acetate phthalate, and novolak resins, vinyl polymer resins, and combinations thereof.

In the present invention, the content of (b) is generally 5 to 90% by weight, 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-50-36209, JP-A-53-36223. And trihalomethyl-2-pyrone and trihalomethyl-triazine described in JP-A-55-6244, and phenols or anilines having an electron-withdrawing substituent and o-naphthoquinonediazide-4-sulfonic acid chloride described in JP-A-55-6244. Ester compound or amide compound of JP-A-55-7774
Examples thereof include halomethyl-vinyl-oxadiazole compounds and diazonium salts described in JP-A-2.

In the present invention, the content of (c) is generally 0.2 to 10% by weight, preferably 0.5 to 3% by weight, based on the total solid content of the photosensitive composition. Is.
In the present invention, represented as (d), 550 to 650 nm
Examples of dyes that have an absorption maximum between and that are discolored by an acid include, for example, diphenylmethane dyes, triphenylmethane dyes, thiazine dyes, oxazine dyes,
Examples thereof include xanthene dyes, anthraquinone dyes, iminonaphthoquinone dyes, azomethine dyes, indoaniline dyes and the like.

Specifically, brilliant green, ethyl violet, methyl green, crystal violet, 2,7-dichlorofluorescein, methyl violet, malachite green, Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.), Oil Blue # 60.
3 (manufactured by Orient Chemical Industry Co., Ltd.), 4-p-diethylaminophenyliminonaphthoquinone and the like.

The photosensitive composition of the present invention satisfies the above formula [I] as the absorbance of the composition itself. Formula [I]
If the above condition is not satisfied, the number of clear steps and / or the visible image quality upon exposure may be insufficient, and it may not be put to practical use. The photosensitive composition used in the present invention may contain other additives, if necessary, in addition to the above materials. For example, in the photosensitive composition used in the present invention, in order to improve the oil sensitivity of the photosensitive composition, a substituted phenol represented by the following general formula [II] and an aldehyde are used as an oil sensitizer. A resin comprising a condensate and / or an o-naltoquinonediazide sulfonic acid ester compound of the resin may be contained.

[0013]

[Chemical 1] (In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group or a halogen atom, and R ³ represents an alkyl group or a cycloalkyl group having 2 or more carbon atoms.) The content of the oil-sensitizer is The total solid content of the volatile composition,
It is generally 0.05 to 15% by weight, preferably 0.5 to 5% by weight.

Further, an organic acid can be added to improve the sensitivity. Examples of such an organic acid include those described in JP-A-2-137850. In the present invention, the content of the organic acid is generally 0.05 to 15% by weight, 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, dimethylsulfoxide, dioxane, acetone,
By applying a coating material dissolved in a coating solvent such as cyclohexanone or trichloroethylene to a suitable support, it can be put to practical use as a photosensitive lithographic printing plate, a photoresist or the like. Hereinafter, as an example, a method for producing a photosensitive lithographic printing plate using an aluminum plate as a support will be described in detail.

When an aluminum plate is used as the support, surface treatment such as graining treatment, anodizing 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 mechanical methods 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. 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 sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc. as the electrolytic solution, one or two.
Electrolysis is performed using a solution containing at least one kind of aluminum plate as an anode. The amount of anodized film formed is 1 to 5
9 mg / dm ² is suitable, preferably 10-40 m
It is g / 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
ml, chromium oxide (VI): 20 g dissolved in 1 liter of water) to dissolve the oxide film, 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 fluorozirconic acid. A photosensitive lithographic printing plate can be obtained by coating the above-mentioned photosensitive composition on the above-mentioned support, but the coating amount is generally 0.5 to 3.5 as a solid content although it varies depending on the use.
A range of g / m ² is suitable.

As a coating method, a generally known roll coater ke slide hopper system coater, gravure coater, whaler coater, wire bar coater or the like can be used. The photosensitive lithographic printing plate thus obtained can be exposed and developed according to a conventional method to obtain a lithographic printing plate.

[0019]

EXAMPLES The present invention will be described in more detail below with reference to synthetic examples, examples and comparative examples. However, the present invention is not limited to these synthetic examples, examples and comparative examples as long as the gist thereof is not exceeded. Not something. [Synthesis Example] (Photoreceptor 1) 20 ml of acetone, 10 ml of 1,4-dioxane, and a polycondensation resin of pyrogallol and acetone ( _MW = 3) were placed in a 100 ml three-necked flask equipped with a stirrer and a reflux condenser. , 000) 1.6
6 g and 1.61 g of 1,2-naphthoquinonediazide-4-sulfonic acid chloride were added to complete the solution. 2 to this
Milliliter pyridine was added, and the mixture was heated under reflux for 5 hours with stirring. This reaction mixture was added to 150 ml of a 1% hydrochloric acid aqueous solution, and the precipitated resin was collected by filtration, washed with water and dried,
A photoconductor 1 was obtained.

(Photoreceptor 2) In a 100 ml three-necked flask equipped with a stirrer, 20 ml of 1,4-dioxane, a polycondensation resin of pyrogallol and acetone (M
_W = 3,000) 1.66 g and 1,2-naphthoquinonediazide-4-sulfonic acid chloride 1.61 g were added to complete the solution. 4-dimethylaminopyridine /
A mixed solution of 1,4-dioxane = 0.77 g / 15 ml was gradually added dropwise and reacted at 25 ° C. for 3 hours.

This reaction mixture was added to 150 ml of a 1% aqueous hydrochloric acid solution, and the precipitated resin was collected by filtration, washed with water and dried to obtain a photoreceptor 2. (Example 1) An aluminum plate (material 1050, temper H16) having a thickness of 0.24 mm was degreased in a 5% aqueous sodium hydroxide solution at 60 ° C for 1 minute, and then 0.5 mol / mol.
In a liter hydrochloric acid aqueous solution, temperature 25 ℃, current density 60
Electrolytic etching was performed under the conditions of A / dm ² and a treatment time of 30 seconds. Then, in a 5% aqueous sodium hydroxide solution,
20% after desmutting at 60 ℃ for 10 seconds
The anodization treatment was performed in a sulfuric acid solution at a temperature of 20 ° C., a current density of 3 A / dm ² , and a treatment time of 1 minute. Furthermore, 9
A hot water sealing treatment was performed with hot water at 0 ° C. for 20 seconds to prepare an aluminum plate as a support for a lithographic printing plate material.

On the aluminum plate produced as described above,
A photosensitive composition coating solution having the following composition was applied 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 /
An m ² positive type photosensitive lithographic printing plate was prepared.

(Photosensitive composition coating liquid) Photoreceptor 1 Phenol and m, p-mixed cresol (phenol,
m-cresol, p-cresol = 20: 48: 32,
Molar ratio) with formaldehyde and a copolycondensation resin · p-ter-octylphenol and formaldehyde than synthesized novolak resin (M _W = 1,800) and naphthoquinone - (1,2) - diazide - (2) -5- Ester compound with sulfonic acid chloride (condensation rate 50
%) 2-Trichloromethyl-5- [β- (2-benzofuryl) vinyl] -1,3,4-oxadiazole-Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.)
-Methyl cellosolve A step tablet (No. 2, Eastman Kodak Co., Ltd., 21-step gray scale with a density difference of 0.15 each) was brought into close contact with the obtained photosensitive lithographic printing plate, and 1
A kW metal halide lamp ("Idle Fin 2000" manufactured by Iwasaki Electric Co., Ltd.) was used as a light source and exposed for 30 seconds, and the visibility of the boundary between the exposed portion and the unexposed portion was visually evaluated.

After exposure, Konica Corporation developing solution "SD
Plate development with a 6-fold diluted solution of "R-1" at 25 ° C for 45 seconds,
The number of clear steps was visually evaluated. Table of these evaluation results
Shown in 1. (Comparative Example 1) A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the photoconductor 2 was used in place of the photoconductor 1, and after exposure, development and evaluation. The evaluation results are shown in Table-1.

(Comparative Example 2) 2-Trichloromethyl-5-
Comparative Example 1 except that the amount of [β- (2-benzofuryl) vinyl] -1,3,4-oxadiazole was increased to 3 parts.
A photosensitive lithographic printing plate was prepared in the same manner as above, exposed, developed and evaluated. The evaluation results are shown in Table-1.

[0026]

[Table 1] In Table-1, Abs (500nm) / Abs (615nm) is the absorption maximum wavelength (615n) of the dye in the photosensitive layer at the absorbance at 500nm.
The value obtained by dividing the absorbance in m) is shown.

[0027]

By using the photosensitive composition of the present invention, it is possible to obtain a positive-working photosensitive lithographic printing plate, a photoresist or the like which is excellent in sensitivity and visibility of exposure and has an extremely great industrial value.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location G03F 7/028 H01L 21/027 (72) Inventor Daisuke Kanazawa 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryoh Kasei Co., Ltd. Research Institute (72) Inventor Shinichi Matsubara 1 Sakura-cho, Hino City, Tokyo Konica Stock Company (72) Inventor Katsuhiko Higashino 1-sakura City, Hino City, Tokyo Konica Stock Company (72) Invention Nori Kojima No. 1 Sakura-cho, Hino City, Tokyo Konica Stock Company

Claims (1)

[Claims] 1. A positive photosensitive composition comprising: (a) a 1,2-naphthoquinonediazide-4-sulfonic acid ester compound of a polyhydric phenol-containing novolac resin, (b) an alkali-soluble resin, and (c) exposure. And (d) a compound having an absorption maximum in the range of 550 to 650 nm and containing a dye that is discolored by an acid, and satisfying the following formula [I] before image exposure: And a positive photosensitive composition. [Equation 1]