JPS6088942A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To enable observation of a sharp visible image immediately after exposure by using a photosensitive composition contg. o-naphthoquinone diazide compd., a specified halomethyloxadiazole compd., and/or halomethyl-s-triazine compd., further a color changing agent, and a specified amt. of org. acid. CONSTITUTION:A photosensitive composition contains o-naphthoquinone diazide compd. (A), preferably, an ester of 1,2-naphthoquinone-2-diazido-5-sulfochloride with pyrogallol-acetone resin, preferably, in an amt. of 10-50wt% of the total compsn.; a halomethyloxadiazole compd. (B) producing halogen free radicals on irradiation of actinic rays, preferably, 2-trihalomethyl-5-vinyl-1,3,4-oxadiazoles, preferably, in an amt. of 0.1-20wt%; a color changing agent (C) changing tone on interreaction with the photodecomposed product, preferably, arylamines, preferably, in an amt. of 0.01-100pts.wt. per 1pt.wt. of the compd. (B); and an org. acid (D), preferably, in an amt. of 0.05-5wt% of the total compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a photosensitive composition suitable for manufacturing lithographic printing plates, letterpress printing plates, IC circuits, and photomasks.

More specifically, the present invention relates to a photosensitive composition containing an 0-naphthoquinonediazide compound and capable of producing a visible image immediately after at-treatment.

[Prior art]

It is known to use ester compounds or amide compounds of 0-naphthoquinonediazide sulfonic acid as photosensitive compositions. These compounds are particularly useful in lithographic printing plates because of their excellent performance.

Production of so-called presensitized plates (commonly referred to as PS plates) in which a photosensitive composition is layered on a support in advance, and as a photoresist for letterpress printing plates, IC circuits, photomasks, or printed wiring. Widely used industrially. However, photosensitive compositions using these o-naphthoquinone diazide compounds have the following drawbacks.

That is, when the yellow-colored photosensitive O-naphthoquinone diazide is exposed to light, it fades and becomes a colorless or pale yellow photodegradable component. Under the yellow safety lamp during exposure work, the original part and the unexposed part are separated after exposure. cannot distinguish between parts. This makes it difficult or impossible for the platemaker to know whether a given plate has been exposed or not, for example when work is interrupted in the process of exposing many printing plates at the same time. Similarly, for example, when making a lithographic printing plate, when exposing a large plate many times to light, as in the process of printing, the operator must confirm which part is the exposure method. Can not do it. This often leads to erroneous operations and is one cause of a significant decrease in work efficiency.

In order to improve these drawbacks, the following techniques are known for forming visible images on photosensitive compositions only by exposure.

For example, U.S. Patent Nos. 2,066,913 and 2,618
555, using various reducible salts mixed with diazo compounds, Japanese Patent Publication No. 40-220
Obtaining a visible image from a photosensitive diazo compound and an acid-base indicator disclosed in Publication No. 3 % Japanese Patent Publication No. 49-304
A product consisting of a photosensitive positive-acting diazo resin and a merocyanine dye as shown in Publication No. 1, Special Publication No. 40-2
A printing original plate previously photosensitized with O-naphthoquinone diazide as shown in Japanese Patent No. 1093, which contains an organic coloring material in the photosensitive layer that changes its color tone at pH 2.5 to 6.5 in the form of homogeneous particles; In the photosensitive copying layer containing O-naphthoquinonediacid sulfonic acid ester or amide disclosed in JP-A No. 50-36209, the photosensitive copying layer contains O-naphthoquinonediazide sulfonic acid ester or amide. O-naphthoquinonediazide-4-sulfonic acid halide (10 to 75%) and an organic compound with salt-forming ability as a dye (1 to 50%)
weight/? - Included within the range of cents, JP-A-55-62
Interacting with the ester compound of phenol and O-naphthoquinonediazide-4-sulfonic acid substituted with an electron-absorbing substituent shown in Publication No. 444@ and the photodecomposition product of the O-naphthoquinonediazide compound. Examples include those containing organic dyes that change the color tone depending on the color.

However, even with these improvements, the contrast of the visible image obtained by exposure was low, and the contrast further deteriorated due to changes in the photosensitive composition over time, making it unsuitable for practical use.

Also, JP-A-54-74728 and JP-A-55-7
No. 10 methyl oxadiazole compound shown in JP-A No. 7742 or No. methyl s-h riazine compound shown in JP-A-55-52070 and JP-A-48-36281 and the compound. Photosensitive compositions containing a color-changing agent that changes the color tone by interacting with photodecomposition products have advantages such as being able to obtain clear visible images immediately after exposure and having excellent stability over time. It has become commonly used in recent years. These 10 methyloxadiazole compounds and halomethyl s
-G') Add the azine compound to the photosensitive composition m + 4 + If Hiroten 1. Therefore, some of the photosensitive composition was likely to remain in the non-image area after processing. In particular, when developing a lithographic printing plate by impregnating a developing solution with absorbent cotton, a sponge, etc. and rubbing the printing plate, the photosensitive composition may remain partially in the non-image area and spoil the appearance, and often cause scumming. 0 [Object of the Invention] Accordingly, an object of the present invention is to provide a photosensitive composition that provides a clear visible image immediately after exposure. Another object of the present invention is to provide a photosensitive composition that is less likely to leave a residue on non-image areas after development and less likely to cause scumming when used as a printing plate.

[Structure of the invention]

The present inventors have conducted various researches to achieve the above object, and as a result, they have come up with the present invention, the gist of which is (a)
) O-naphthoquinonediazide compound, (b) halomethyloxadiazole compound and/or 10-methyl s-h' which generates rhodane free radicals upon irradiation with actinic rays.
an azine compound, (C) a color change agent that changes its color tone by interacting with the photolysis product of (fi) above, and (d) an organic acid in an amount of 0.05 to 5 parts by weight based on the total composition. A photosensitive composition characterized by containing:

The present invention will be described in detail below. ◎ The 0-naphthoquinone diazide compound used in the present invention is 1,2-naphthoquinone-2-diazide-5-sulfonic acid described in Japanese Patent Publication No. 43-28403. Most preferred are esters of chloride and pyrogallol-acetone resin.

Other suitable orthonaphthoquinone diazide compounds include US Pat. [No. 146,120 and No. 3
, 188, 210, 1, 2-
There are esters of naphthoquinone-2-diazide-5-sulfonic acid chloride and phenol-formaldehyde resins. Other useful 0-naphthoquinonediazide compounds are known and reported in numerous patents, such as JP-A-47-5!103 and JP-A-48-638.
No. 02, No. 1973-63805, No. 9657-1972
No. 5, No. 49-38701, No. 13354, No. 48-1973
No. 41-11222, Japanese Patent Publication No. 45-9610, Japanese Patent Publication No. 49-17481, U.S. Patent No. 2.797
, No. 213, No. 3,454,400, No. 3,54
No. 4.325, No. 3.573,917, No. 3.674,495, No. 3,785.825, British Patent No. 1.227,60
No. 2, No. 1,251,545, No. 1,267.0
No. 05, No. 1.329.888, No. 1,330,
Examples include those described in various specifications such as No. 932 and German Patent No. 854.890.

The amount of the 0-naphthoquinonediazide compound in the photosensitive composition of the present invention is from 10 to 500 to 50% by weight, preferably from 20 to 400 to 40% by weight. As a halomethyloxadiazole compound that generates free radicals, JP-A-54-74
2-trihalomethyl-5 described in Publication No. 728
-vinyl-1,3,4-oxadiazole compounds are preferred. Other suitable halomethyloxadiazole compounds include 2-trino-lomethyl-5-aryl-1,5 described in JP-A-55-77742.
, 4-oxadiazole compounds. The methyl S-triazine compound (which generates dihalogen free radicals upon irradiation with actinic rays) used in the present invention is disclosed in JP-A No. 48
2,4-bis(trihalomethyl)-6-vinyl-s-triazine compounds described in JP-A No. 36281 and 2-
Aryl-4,6-bis(trihalomethyl)-s-)
1) Examples include azine compounds. These halodane free radical generating agents may be used alone or in combination of two or more.

The amount of the no-romethyloxadiazole compound and/or the no-romethyl S-triazine compound that generates dihalogen free radicals upon irradiation with actinic rays in the photosensitive composition of the present invention is 0.1 to 20% by weight. %, more preferably 0.5~
5. This is the weight section.

The color changing agent used in the present invention changes the color tone by interacting with the photodecomposition product of the above-mentioned no-romethyloxadiazole compound and/or no-romethyl s-)riazine compound, which is originally colorless. There are two types: those that change from a certain color to a colored state, and those that change color or decolorize from something that originally has a unique color.

Typical examples of color changing agents belonging to the former type include arylamines. Arylamines suitable for this purpose include simple arylamines such as primary and secondary aromatic amines, as well as so-called leuco dyes, examples of which include the following:

Diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine, 4゜47-biphenyldiamine, O-chloroaniline, o-bromoaniline, 4
-chloro-0-phenylenediamine, O-promo N,
N-dimethylaniline, 1,2.5-h liphenylguanidine, naphthylamine, diaminodiphenylmethane,
Aniline, 2,5-dichloroaniline, N-methyldiphenylamine, o-toluidine, 9*p'-tetramethyldiaminodiphenylmethane, N,N-di'y-
p-phenylenediamine, 1,2-dianilinoethylene, pl p'j p'-hexamethyltriaminotriphenylmethane, pl p' -tetramethyldiaminotriphenylmethane% pH)'-tetramethyldiaminodiphenylmethylimine , 9+ p'+p'-triamino-0-methyltriphenylmethane% pl 9
' * G'' -triaminotriphenylcarbinol, Do O' -tetramethylaminodiphenyl-4-
Anilinonaphthylmethane, pl p' + p' -)
Liaminotriphenylmethane, pl p'l p'-hexapropyltriaminotriphenylmethane.

In addition, examples of color-changing agents that originally have a unique color and whose color changes or decolors due to the photodecomposition products of the O-su7-toquinone diphosphate compound include diphenylmethane, triphenylmethane-based thiazine, and oxazine-based thiazine. , xanthine-based, anthraquinone-based, iminonaphthoquinone-based, and azomethine-based dyes can be effectively used.

Examples of these include: Brilliant Green, Eosin, Ethyl Violet, Erythrosin B, Methyl Green, Crystal Violet, Pesic Tsuksin, Phenolphthalein, 1,3-Diphenyl Triazine, Alizoline Red S1 Thymolphthalein, Methyl Violet 2B, Quinaldine Red, Rose bengal, methanil yellow, thymol sulphur
j-i7thalein, quinonol blue, methyl orange, orange ■, y phenylthiocarbazone, 2.
7-dichlorofluorescein, 9-methyl red, Congo red, benzopurpurin 4B, α-naphthyl knot, Nile blue 28. Nile Blue A1 Phenacetaline, Methyl Violet, Malachite Green, Baratuxin, Oil Blue φ603 [Orient Chemical Co., Ltd.], Oil funkkai 312 [Orient Chemical Co., Ltd. 1) #), Oil Red 5s (Orient Chemical Co., Ltd.)
a) #), Oil Blue Let*30B (Orient Chemical Industry Co., Ltd.), Oil Red OG (Orient Chemical Industry Co., Ltd.), Oil Red RR (Orient Chemical Industry Co., Ltd.), Oil Blue Na 502 [Orient Chemical Industry Co., Ltd. M], Spiron Red BEH Special [
manufactured by Hodogaya Chemical Industry Co., Ltd.], m-Ruzornokfur,
ReV/-Ruret, Rhodamine 8, Rhodamine 6G, Fast Acid Violet R1 Sulforhodamine B
1 auramine, 4-p-diethylaminophenylimino naphthoquinone, 2-calgexyanilino a-p-diethylaminophenylimino naphthoquinone, 2-calgeste acylamino-4-p-dihydroxyethylamino-phenylimino naphthoquinone, 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-vilazolone.

The color changing agent as described above is used in an amount of about 0.01 parts to about 100 parts by weight, preferably 0.1 parts to 100 parts by weight, based on 1 part by weight of the halomethyloxadiazole compound and/or halomethyl S-)riazine compound. It is used in 10 heavy scenes.

The organic acid used in the present invention includes P in water at 25°C.
Ka is preferably 3.0 or less, more preferably 1.0 or less. Examples of organic acids such as
Sulfonic acids, sulfinic acids, alkyl fm In
Among them, sulfonic acids and sulfinic acids can be used effectively.

Specific examples include ti,p-)luenesulfonic acid, dodecylbenzenesulfonic acid, mesitylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, m-benzenedisulfonic acid, o-toluenesulfinic acid, and benzylsulfinic acid. , methanesulfinic acid, phenylphosphonic acid, methylphosphonic acid, chloromethylphosphonic acid, dimethylphosphinic acid, diphenyl phosphate, diphenyl phosphite, ethyl sulfate, and the like. In addition, carboxylic acids and phenols in which a is small for P such as trichloroacetic acid, trichloroacetic acid, 2,6-dichlorobenzoic acid, and picric acid can also be used. Such organic acids may be used alone or in combination of two or more, and the amount of such organic acids may be 0.05 to 5, preferably 0.05 to 5, based on the total photosensitive composition.
If the amount of the organic acid used in the present invention is too small, the effect of the present invention cannot be obtained, and on the other hand, if the amount added is too large, the visible image after exposure becomes difficult to see. However, the image area is more likely to be damaged during development.

It is preferable to include an alkali-soluble resin in the composition of the present invention. By containing an alkali-soluble resin, the film strength is increased and the printing durability is improved. Suitable alkali-soluble resins include phenolic resins, specifically phenol formaldehyde resins.
Lo-cresol formaldehyde 111] Lm-cresol formaldehyde resin and the like. Other known alkali-soluble resins such as pheno-k'R-\-silene resin, polyhydroxystyrene, and polyhalodanized hydroxystyrene may also be included.

Such alkali-soluble resin is used in an amount of 90% by weight or less of the total composition. A dye can be added to the composition of the present invention as a KJII acid anhydride coloring agent to increase sensitivity.

Examples of the cyclic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, as described in US Pat. No. 4,115,128; 3.
6-nindooxy-Δ-tetrahydrophthalic anhydride,
Examples include tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenyl anhydride 7242m, m-hydrosuccinic acid, and pyromellitic acid. By containing these cyclic acid anhydrides in an amount of 1 to 153% in the total composition, the sensitivity can be increased up to about 3 times.

In addition to the above-mentioned color change agents, other dyes can also be used as image colorants. Suitable dyes including the color change agents mentioned above include oil-soluble dyes and basic dyes.

Specifically, Oil Pin Funa 512, Oil Green BG
, Oil True SOS.

Oil Pruner 603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industry Co., Ltd.), Crystal Violet (
CI42555), methyl violet (C14253)
5), Rhodamine B (CI45170B), Malachite Green (CI42000), Methylene Blue (CI5)
2015). By containing these image coloring agents in an amount of 0.1 to 5% by weight based on the total weight of the composition, the image after development becomes easier to see.

The composition of the present invention may contain additives for increasing the ink receptivity of image areas when used in lithographic printing plates, such as JP-A No. 5
pt@rt-butylphenol formaldehyde resin+, pn-octylphenol formaldehyde resin, etc. described in JP 0-125806 may be added. Furthermore, a surfactant such as a nonionic fluorine-based surfactant may be added to the composition of the present invention to improve coating properties. In addition, the composition of the present invention may contain known matting agents such as talc powder, glass powder, clay, starch, wheat flour, corn flour, polyethylene powder, polypropylene powder, and crosslinked vinyl polymer powder. can. Inclusion of a matting agent improves vacuum adhesion and film strength.

The composition of the present invention is prepared by dissolving or dispersing each of the above-mentioned components in a solvent and coating it on a support. The solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether,
Examples include ethylene glycol monoethyl ether, 2-methoxyethyl acetate, toluene, ethyl acetate, and water, and these solvents may be used alone or in combination. The concentration (solid content) of the above components is 2 to 50% by weight. In addition, the coating amount is generally 0.5 to 3 as solid content.
, 0 P/m2 is preferred. As the coating amount decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

When producing a lithographic printing plate using the photosensitive composition of the present invention, the support may be a hydrophilized aluminum plate, such as a silicate-treated aluminum plate, an anodized aluminum plate, a grained aluminum plate, or a silicate plate. Aluminum plates, etc. that have been worn, etc., other zinc plates, etc.
Stainless steel plates, chromium-treated steel plates, hydrophilized plastic films and paper can also be used.

The developing solution for the photosensitive composition of the present invention includes sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, sodium diphosphate, ammonium triphosphate, Aqueous solutions of inorganic alkaline agents such as ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. are suitable, and their concentration is 0.1 to 10% by weight.
, preferably in an amount of 0.5 to 5% by weight.

Moreover, a surfactant and an organic solvent such as alcohol can be added to the alkaline aqueous solution as necessary.

〔Example〕

Next, the present invention will be explained in more detail by giving examples. In the following examples, all cents are by weight unless otherwise specified.

Example 1 A 25 aluminum plate with a thickness of 0.248 was immersed for 3 minutes in a 10% aqueous solution of tertiary sodium phosphate kept at 80°C to degrease it, grained with a nylon brush, and then soaked in a 5% aqueous solution of sodium aluminate. Etching was performed for about 10 seconds, and then desmutting was performed using a 5% aqueous solution of sodium sulfate.

This aluminum plate was heated at a current density of 2A/d in 20% sulfuric acid.
m2 for 2 minutes and aluminum plate (1
) was created.

Apply the following photosensitive liquid to this aluminum plate (1) and
It was dried at 0C for 2 minutes to produce a photosensitive lithographic printing plate.

1. Esterified product of 2-naphthoquinone-2-diazide-5-sulfonyl chloride and cresol-formaldehyde resin 0.9051'-m-cresol-formaldehyde resin 1.9? 2-Trichloromethyl-5-(p-methoxystyryl)-1,3°4-oxadiazole (compound described in Example 1 of JP-A-54-74728) o, o3y Crystal violet [1,05? Organic acid in the present invention (listed in Table 1) xt 7-talic anhydride 0.2 fP 2-methoxyethyl acetate 20? Ethylene dichloride 10? Water 3P In addition, as a comparative example, a photosensitive solution obtained by removing 2-trichloromethyl-5-(9-methoxystyryl)-1.3.4-oxadiazole and the organic acid from the above photosensitive solution was applied in the same manner. A lithographic printing plate was prepared. The coating weight after drying was 2.11/m2 in each case. Each of these photosensitive lithographic printing plates was heated with 2 W metal halide lamps.
It was exposed for 40 seconds through a transparent original image at a distance of m.

The optical density of the exposed and unexposed areas of the photosensitive layer was measured using a Macbeth reflection densitometer. The results are shown in Table 1. The image obtained by exposure appears sharper as the difference (Δ0) between the optical density of the exposed area and that of the unexposed area is larger.

Also, after exposing in the same way as above through a positive transparent original image,
4. Rub it with a sponge soaked in sodium timetasilicate aqueous solution and develop to remove uneven development in non-image areas (hand development unevenness).
I looked into it. In Table 1, cases in which almost no unevenness occurs are marked with an O, and cases in which unevenness occurs are marked with an X.

Also, after exposing in the same way as above through a positive transparent original image,
The image was immersed in an aqueous sodium metasilicate solution at 25° C. for 5 minutes and developed to examine the degree of damage to the image @ area. In Table 1, those with a small degree of damage are marked with an O mark, those with a large degree of damage are marked with an x mark, and those in between are marked with a Δ mark.

From Table 1, the photosensitive composition of the present invention can provide an excellent printing plate that provides a clear visible image upon exposure, has little unevenness in hand appearance, and is less likely to cause damage to the image area during development. I understand.

Example 2 The following photosensitive liquid was applied to the aluminum plate (1) used in Example 1 in the same manner as in Example 1 to produce a photosensitive lithographic printing plate.

1. Esterified product of 2-naphthoquinone-2-diazido-5-sulfonyl chloride and pyrogallol-acetone resin (synthesized by the method described in Example 1 of US Pat. No. 3,635,709) 0. 75) m-Cresol formaldehyde resin 2.10y- p-Normal octylphenol formaldehyde resin o, osy 2.4-bis(trichloromethyl)-6-p-methoxystyryl-5 monotriazine (% Implemented in 1989-36281) Compound described in Example 1) o, osy Oil Blue ◆605 [manufactured by Orient Chemical Industry Co., Ltd.] 0.05P Organic acid in the present invention (as described in Table 2) 0.03y- Ethylene glycol monoethyl ethyl 10y - Methyl ethyl ketone 21 Water 2? The coating weight after drying was 2.5 f/m2 in each case. Each of these photosensitive planographic printing plates was exposed in the same manner as in Example 1, and the density difference between the exposed and unexposed areas (
The ease with which hand unevenness occurs was examined in the same manner as in Example 1, and then printed on a printing press to examine whether scumming occurred. The results are shown in Table 2.

It is clear from Table 2 that the photosensitive composition of the present invention provides an excellent printing plate.

Claims (1)

[Claims] (a3 o-naphthoquinonediazide compound, (b) halomethyloxazazole compound and/or halomethyl S-triazine compound that generates halogen free radicals upon irradiation with actinic rays, (c) photodecomposition product of (b) above) A photosensitive composition characterized in that it contains a color change agent that changes its color tone by interacting with it, and (d) an organic acid in an amount of 0.05 to 5% by weight based on the total composition.