JPS63287952A - Production of photosensitive printing plate material - Google Patents

Abstract

PURPOSE:To improve developability and to improve the strength of an image part by developing a photosensitive printing plate formed by coating of a specific photosoluble type photosensitive resin by a developing soln. having a specific compsn. CONSTITUTION:The photosensitive printing plate coated with the positive type photosensitive resin obtd. by esterifying a quinonediazide compd. at 0.4-0.9equiv. per 1 hydroxyl group equiv. of a novolak resin is subjected to imagewise exposing and is then developed by the developing soln. prepd. by dissolving ethylene glycol monophenyl ether or ethylene glycol monobenzyl ether, cationic surfactant, hydroxide of an alkali metal, silicate, reducing agent, tetrafluoroborate, and ethylenediaminetetraacetic acid or the salt thereof in water. Naphthoquinone-1.2-diazide-5-sulfonylchloride is preferably used as the quinonediazide compd. and alkyl naphthalene sulfonate is preferably used as the anionic surfactant, respectively. The good developability is obtd. by developing the above-mentioned photosensitive printing plate and the strength of the image part of the printing plate is enhanced by using such developing soln.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial application field The present invention provides a positive photosensitive material made by coating a photo-solubilizable photosensitive resin on the surface of a support such as aluminum foil or plastic film. The present invention relates to a method for developing a printing plate material, and particularly to a method for developing a photosensitive printing plate material with high image strength and good developability.

(b) Problems to be solved by conventional techniques and inventions Conventionally, photo-solubilizable photosensitive resins obtained by esterifying novolac resins and quinonediazide compounds have been used for positive photosensitive printing plate materials. In this type of photo-solubilizable photosensitive resin, the higher the proportion of novolak resin, the more easily it dissolves in a developer (alkaline aqueous solution containing mainly alkali metal hydroxide) after exposure. , developability is improved. From this perspective, currently,
Hydroxyl group 1 of novolak resin as photo-solubilized photosensitive resin
A compound obtained by esterifying a quinonediazide compound in an amount of less than 0.4 equivalents is used.

However, although this photo-solubilizable photosensitive resin has good developability, it has the drawbacks of low strength in the image area and poor printing resistance. In order to improve the strength of photo-solubilized photosensitive resins, it is possible to reduce the proportion of novolac resin and increase the proportion of quinonediazide compound, but such photo-solubilized photosensitive resins have poor developability. It is thought that this will lead to poor development.

Therefore, the present invention provides a photosensitive printing plate material with high image strength and good developability by developing a photosensitive printing plate material coated with a specific photo-solubilizable photosensitive resin with a specific developer. The purpose of the present invention is to provide a developing method.

(c) Means and operation for solving the problems, that is, the present invention provides a photosensitive printing plate material coated with a photo-solubilizable photosensitive resin obtained by esterifying a novolac resin and a quinone diazide compound. After exposure using the original,
In a method for developing a photosensitive printing plate material using a developer, the photo-solubilized photosensitive resin is obtained by esterifying a quinonediazide compound in an amount of 0.4 to 00 g equivalent to 1 equivalent of hydroxyl group of a novolac resin. A photo-solubilizable photosensitive resin is used, and as the developing solution (al ethylene glycol monophenyl ether or ethylene glycol monobenzyl ether) and (b) an anionic surfactant and (
C) using a developer prepared by dissolving alkali metal hydroxide, (d+ silicate, (e) reducing agent, (fl tetrafluoroborate, and (gl ethylenediaminetetraacetic acid or its salt) in water. This invention relates to a method for developing a photosensitive printing plate material.

First, the photo-solubilized photosensitive resin used in the present invention is obtained by esterifying a novolak resin and a quinonediazide compound, and the reaction ratio between the two is 0.4 quinonediazide compound per equivalent of hydroxyl group of the novolac resin. ~0
0g equivalent. When the amount of the quinonediazide compound is less than 0.4 equivalent, the strength of the photo-solubilized photosensitive resin decreases, which is not preferable.

Further, the amount of the quinonediazide compound is 0. If the amount exceeds g equivalent, it becomes difficult to dissolve in the developer used in the present invention, resulting in poor development, which is not preferable.

In the present invention, the novolak resin is obtained by condensing phenols and formaldehyde, and the quinonediazide compound is a type of nitrogen derivative of quinone and has an acid group that can be esterified with the novolak resin. It is. The most commonly used quinonediazide compounds include naphthoquinone-1,2-diazide-5-sulfonyl chloride.

Next, the developer used in the present invention consists of (al ethylene glycol monophenyl ether or ethylene glycol monobenzyl ether), (bl anionic surfactant and (C
) An alkali metal hydroxide, an FDL silicate, (e) a reducing agent, (f) a tetrafluoroborate, and (g) ethylenediaminetetraacetic acid or its salt dissolved in water.

+8) The component ethylene glycol monophenyl ether or ethylene glycol monobenzyl ether may be used alone or in combination. This component fa) is for dissolving the photo-solubilizable photosensitive resin that has been decomposed by exposure.

The anionic surfactant as component (b) includes fatty acid salts, alkylbenzene sulfonates, alkyl sulfonates, alkylnaphthalene sulfonates, α-olefin sulfonates, dialkyl sulfosuccinates, α-sulfonated fatty acids. Salt, N-methyl-N-oleyl taurine, alkyl sulfate.

Polyoxyethylene alkyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether sulfate L, polyoxyethylene alkyl phenyl ether phosphate, naphthalene sulfonate formaldehyde condensate, naphthalene sulfone Among these, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl phenyl ether sulfates, and especially alkylnaphthalene sulfonates (in combination with an ether compound as an Al component, The anionic surfactant is suitable because it has a developing effect in a small amount.The anionic surfactant has the effect of improving the solubility of the ether compound (a) component in water, and the photo-solubilization type angry photoresistivity of the ether compound and other components. It acts to improve the permeability into the resin.

As the alkali metal hydroxide which is component (C), sodium hydroxide, lithium hydroxide, potassium hydroxide, rubidium dihydroxide, cesium hydroxide, and francium hydroxide can be used. This dissolves in water to become an alkaline aqueous solution, and serves to dissolve the photo-solubilizable photosensitive resin that has been decomposed by exposure. If a substance other than the alkali metal hydroxide, such as soda carbonate, is used in place of the alkali metal hydroxide, the effect of dissolving the photo-solubilizable photosensitive resin decomposed by exposure to light is poor, and it cannot be used in the present invention.

(As silicates that are dl components, potassium silicate, calcium silicate, sodium silicate, and lithium silicate.

Magnesium silicate etc. can be used. This has the effect of preventing corrosion of aluminum foil, which is generally used as a support for photosensitive printing plate materials. That is, the alkali metal hydroxide is strongly alkaline and has a corrosive effect on the aluminum foil support, and the silicate acts to alleviate this effect.

The reducing agent (e) is hydrogen iodide, hydrogen sulfide, sulfite, or lithium aluminum hydride.

Sodium sulfide, ammonium sulfide, ferric salts.

Stannic salts etc. can be used. This is because aluminum foil is generally used as a support for photosensitive printing plate materials.
It functions to prevent oxidation of the aluminum surface in the developer.

As the tetrafluoroborate which is the component (f), ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, etc. can be used. Since aluminum foil is generally used as a support for photosensitive printing plate materials, this is to act on the aluminum surface and create a clean surface.

(One component, ethylenediaminetetraacetic acid or its salt, is
It supplementally chelates the calcium and magnesium contained in the water in the developer, and has the effect of softening hard water.

The developer used in the present invention can be prepared by dissolving the above (al~(() components in water. Also, if desired, (
A developer may be prepared by dissolving a preservative, an alcohol such as benzyl alcohol or cyclohexanone, or a ketone in water together with the al~(gl component).

The blending ratio of the components (al to (g)) in the developer used in the present invention is as follows: 100 parts (1 part by weight, same hereinafter) of the ether compound as the +al component and 50 parts of the anionic surfactant.
-tsoo part, 50 to 200 parts of alkali metal hydroxide
50 to 400 parts of silicate, 50 to 150 parts of reducing agent, 1 to 6 parts of tetrafluoroborate, and 0.5 to 3 parts of ethylenediaminetetraacetic acid or its salt. Among these, the more preferred blending ratio of the anionic surfactant is around 1000 parts, and the more preferred blending ratio of the alkali metal hydroxide is around 100 parts. The developing solution contains ether compound 10 as component (a).
It is used after being diluted with about 2,000 to 500 parts of water per 0 parts.

Anionic surfactant, alkali metal hydroxide.

Although the blending ratio of silicates, etc. to the ether compound (al component) is not critically determined, if the amount of the anionic surfactant becomes less than 500 parts, the main effect of the anionic surfactant, i.e., the ether compound The effect of improving the solubility in water and the effect of improving the permeability of ether compounds and alkali metal hydroxides into the solubilized photosensitive resin tend to be insufficient; If the amount is too high, there is less tendency to have a positive effect on the development action.

The alkali metal hydroxide, together with the ether compound (a) component, exerts a direct action to dissolve the photo-solubilized photosensitive resin that has been decomposed by exposure to light, and when the amount is less than 50 parts, the decomposed photo-solubilized resin is dissolved. The ability to melt the type photosensitive resin tends to be reduced and the development speed tends to be slow. If the amount is more than 200 parts, there is a tendency to corrode the support such as aluminum foil and there is also a risk of damaging the image area.

If the amount of silicate is less than 50 parts, the effect of alleviating the strong alkalinity of the alkali metal hydroxide will be reduced, and if it is more than 400 parts, the alkali metal hydroxide will conversely dissolve the decomposed photo-solubilizable photosensitive resin. There is a tendency to inhibit performance.

If the reducing agent is less than 50 parts, it will have a poor effect in preventing oxidation of the aluminum surface that is the support, and if it is more than 150 parts, it will reduce the aluminum surface, and the hydrophilic function of the pre-anodized aluminum surface will be impaired. There is a tendency to generalize.

If the amount of tetrafluoroborate is less than 1 part, the cleaning effect on the aluminum surface of the support is poor, and if it is more than 6 parts, the aluminum surface tends to be corroded too much.

If the amount of ethylenediaminetetraacetic acid or its salt is less than 0.5 part, it will have a poor effect of softening the water in the developer, and if it is more than 3 parts, it will act adversely on other components, such as aluminum metal hydroxides and silicates. A tendency arises.

As explained above, the present invention involves exposing a photosensitive printing plate material coated with the above-mentioned specific photo-solubilizable photosensitive resin, and then exposing it to light using the above-mentioned specific developer. It is developed.

(D) Examples Example 1 4.9 g of novolak resin and 10.8 g of naphthoquinone-1,2-diazide-5-sulfonyl chloride (0.85 equivalent per 1 equivalent of hydroxyl group of novolak resin) were added to 90 g of dioxane. Dissolve and heat to 40°C while stirring.
When 40 g of a 10% aqueous solution of sodium carbonate is gradually added, a white precipitate is formed. After stirring this for about 2 hours, the precipitate turns into a sticky oil. The supernatant is removed using a decanting method, approximately 10 times the amount of water is added, and the mixture is vigorously stirred to turn the oil into a powder. It was filtered, and the precipitate was washed with methanol and dried at 40-50°C to obtain 11.78 g (yield: 82.3%) of a photo-solubilized photosensitive resin.

This photo-solubilizable photosensitive resin was coated on an aluminum foil support to prepare a photosensitive printing plate material. A positive image film was superimposed on this photosensitive printing plate material and exposed for 40 seconds from a distance of 1 m using an ultra-high pressure mercury lamp.

Then, the exposed photosensitive printing plate material was placed in the following developer solution at room temperature (
20'C) was immersed for 20 seconds and washed with water to obtain a printing plate.

Ethylene glycol monophenyl ether 10g Sodium alkylnaphthalene sulfonate 60g Sodium hydroxide 5g Sodium silicate (water glass; No. 3, solid content 50%) 5
g Sodium sulfite 5g Potassium tetrafluoroborate 0.2g Ethylenediaminetetraacetic acid 011g Water
When the obtained printing plate was printed on high-quality paper using a Heidel ORD printing machine, more than 50,000 copies of clear printed matter could be printed. Therefore, it can be seen that the developability is good and the strength of the image area formed on the printing plate is high.

Example 2 Novolac resin6. Og and 10.8 g of naphthoquinone-1,2-diazido-5-sulfonyl chloride (0.70 equivalent per equivalent of hydroxyl group of novolak resin) were dissolved in 90 g of dioxane, and the solution was heated at 40°C with stirring.
When 40 g of a 10% aqueous solution of sodium carbonate is gradually added, a white precipitate is formed. After stirring this for about 2 hours, the precipitate turns into a sticky oil. The supernatant is removed using a decanting method, approximately 10 times the amount of water is added, and the mixture is vigorously stirred to turn the oil into a powder. It was separated by filtration, and the precipitate was washed with methanol and dried at 40 to 50'C to obtain 12.86 g (yield: 83.9%) of a photo-solubilized photosensitive resin.

This photo-solubilizable photosensitive resin was coated on an aluminum foil support to prepare a photosensitive printing plate material. A positive image film was superimposed on this photosensitive printing plate material and exposed for 40 seconds from a distance of 1 m using an ultra-high pressure mercury lamp.

Then, the exposed photosensitive printing plate material was immersed in the following developer for 20 seconds at room temperature (20'C) and washed with water to obtain a printing plate.

Ethylene glycol monophenyl ether 10g Sodium alkylnaphthalene sulfonate 50g Sodium hydroxide 10g Potassium silicate
3g lithium aluminum hydride 0.3g sodium tetrafluoroborate
1g Sodium ethylenediaminetetraacetate 0
．． 3g water
When 500 g of the obtained printing plate was printed on high-quality paper using a Heidel KORD printing machine, more than 50,000 copies of clear printed matter could be printed. Therefore, it can be seen that the developability is good and the strength of the image area formed on the printing plate is high.

Example 3 8.5 g of novolak resin and 10.8 g of naphthoquinone-1,2-diazide-5-sulfonyl chloride (0.4 g equivalent per 1 equivalent of hydroxyl group of novolak resin) were dissolved in 90 g of dioxane, and this was dissolved in 90 g of dioxane. 40°C without stirring
When 40 g of a 10% aqueous solution of sodium carbonate is gradually added, a white precipitate is formed. After stirring this for about 2 hours, the precipitate turns into a sticky oil. The supernatant is removed using a decanting method, approximately 10 times the amount of water is added, and the mixture is vigorously stirred to turn the oil into a powder. It was separated by filtration, and the precipitate was washed with methanol and dried at 40 to 50°C to obtain 17.24 g (yield: 97.7%) of a photo-solubilized photosensitive resin.

This photo-solubilizable photosensitive resin was coated on an aluminum foil support to prepare a photosensitive printing plate material. A positive image film was superimposed on this photosensitive printing plate material and exposed for 40 seconds from a distance of 1 m using a 4KW ultra-high pressure mercury lamp.

Then, the exposed photosensitive printing plate material was placed in the following developer solution at room temperature (
20°C) for 20 seconds and washing with water to obtain a printing plate.

Ethylene glycol monobenzyl ether 10g α-sulfonated fatty acid sodium 70g Sodium hydroxide 20g Sodium silicate (water glass: No. 3, solid content 50%) 5
g Sodium sulfite 7g Potassium tetrafluoroborate 0.4g Ethylenediaminetetraacetic acid 0.1g Water
When 300 g of the obtained printing plate was printed on high-quality paper using a Heidel KORD printing machine, more than 50,000 copies of clear printed matter could be printed. Therefore, it can be seen that the developability is good and the strength of the image area formed on the printing plate is high.

Comparative Example 1 16.0 g of Novolank resin and naphthoquinone-1,2-
10.8 g of diazide-5-sulfonyl chloride (0.26 equivalent to 1 equivalent of hydroxyl group in Novolank resin) was dissolved in 90 g of dioxane, and the solution was heated at 40° without stirring.
When 40 g of a 10% aqueous solution of sodium carbonate is slowly added at C, a white precipitate forms. After stirring this for about 2 hours, the precipitate turns into a sticky oil. The supernatant is removed using a decanting method, approximately 10 times the amount of water is added, and the mixture is vigorously stirred to turn the oil into a powder. It was filtered, and the precipitate was washed with methanol and dried at 40 to 50°C to obtain 25.0 g (yield: 98.7%) of a photo-solubilized photosensitive resin.

This photo-solubilizable photosensitive resin was coated on an aluminum foil support to prepare a photosensitive printing plate material. A positive image film was superimposed on this photosensitive printing plate material and exposed for 40 seconds from a distance of 1 m using a 4KA ultra-high pressure mercury lamp.

Then, the exposed photosensitive printing plate material was placed in the following developer solution at room temperature (
20°C) for 20 seconds and washing with water to obtain a printing plate.

Ethylene glycol monobenzyl ether 10g Sodium α-sulfonated fatty acid 70g Sodium hydroxide 20g Sodium silicate (water glass; No. 3, solid content 50%) 5g Sodium sulfite 7g Potassium tetrafluoroborate 0.4g Ethylenediaminetetraacetic acid 0.1g Water
When the 300g obtained printing plate was printed on high-quality paper using a Heidel ORD printing machine, clear prints were initially obtained, but after printing more than 30,000 copies, the characters on the prints became unclear.

Therefore, it can be seen that the strength of the image area formed on the printing plate is lower than that of Examples 1 to 3.

Comparative Example 2 A photosensitive printing plate material obtained by applying the previously dissolved photosensitive resin obtained in Examples 1 to 3 was exposed in the same manner as in Example, and a commercially available developer (Ohka Kogyo ■ The film was developed in the same manner as in the example using PL-101, manufactured by Kogyo Co., Ltd.

When the obtained printing plate was printed on high-quality paper using a Heidel KORD printing machine, the background was heavily smeared and printing was impossible. Therefore, it can be seen that the previously dissolved type photosensitive resin, which had poor developability and was decomposed by exposure, could not be sufficiently removed.

(e) As is clear from the detailed description of the invention, the method for developing the photosensitive printing plate material according to the present invention involves developing a specific pre-solubilized photosensitive resin with a specific developer after exposure. This provides the effects of good developability and high strength of the image area formed on the printing plate.

Claims (3)

[Claims] (1) A photosensitive printing plate material coated with a photo-solubilizable photosensitive resin obtained by esterifying a novolac resin and a quinone diazide compound is exposed using a prescribed original, and then developed using a developer. In the method for developing a photosensitive printing plate material, the photo-solubilized photosensitive resin is a photo-solubilized type obtained by esterifying a quinone diazide compound in an amount of 0.4 to 0.9 equivalents per equivalent of hydroxyl group of a novolak resin. A photosensitive resin is used, and the developer includes (a) ethylene glycol monophenyl ether or ethylene glycol monobenzyl ether, (b) an anionic surfactant, (c) an alkali metal hydroxide, and (d) a silicate. and (e)
A method for developing a photosensitive printing plate material, comprising using a developer prepared by dissolving a reducing agent, (f) a tetrafluoroborate salt, and (g) ethylenediaminetetraacetic acid or a salt thereof in water. (2) Naphthoquinone-1 as a quinonediazide compound,
A method for producing a photosensitive printing plate material according to claim (1), using 2-diazide-5-sulfonyl chloride. (3) A method for developing a photosensitive printing plate material according to claim (1), in which an alkylnaphthalene sulfonate is used as an anionic surfactant.