JP3142193B2 - Photosensitive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition useful as a photosensitive layer of a photosensitive lithographic printing plate, and more particularly to a positive photosensitive composition containing a compound which dissociates an acid when irradiated with actinic rays. It is about.

[0002]

2. Description of the Related Art A photo-solubilizing composition comprising an o-quinonediazide compound and an alkali-soluble resin has extremely excellent performance, and has been widely used industrially as a lithographic printing plate production and as a photoresist. However, the photo-solubilized composition itself becomes photoless and colorless when the o-quinonediazide compound colored yellow is exposed to light, and a visible image with a low contrast can be obtained for the time being. Had a disadvantage that a visible image could not be recognized under a yellow safety light. This point can be improved by adding a pH indicator, a leuco dye, or a printing-out agent such as a spiropyran compound to the photosolubilized composition, and it is possible to obtain a visible image that can be clearly recognized even under a yellow safety light. . However, as described in JP-A-52-80022, in a photo-solubilizing composition to which a cyclic acid anhydride is added in order to enhance sensitivity and developability, this is not the case.
It was found that when a pH indicator, a leuco dye or a spiropyran compound was added, the effect was lost and a visible image could not be obtained by exposure.

On the other hand, Japanese Patent Application Laid-Open No. 50-36209 discloses an o-
A printing method for obtaining a visible image immediately after exposure by adding o-naphthoquinonediazide-4-sulfonic acid halide and an organic dye having a salt-forming ability to a photosolubilizing composition comprising a quinonediazide compound and a novolak resin is described. Have been. However, in the system to which o-naphthoquinonediazide-4-sulfonic acid halide is added, there is a problem that the image density decreases with the elapse of time and the contrast of printing-out decreases. O to increase printing contrast
In a system to which a large amount of -naphthoquinonediazide-4-sulfonic acid halide is added, there is a problem that the image density is remarkably lowered with the passage of time, and the sensitivity is significantly lowered. To remedy this drawback, Japanese Patent Application Laid-Open No. 53-8128 proposes to add o-naphthoquinonediazide-4-sulfonic acid halide in an amount of 2-8% by weight based on the total content of the o-quinonediazide compound. However, in this case, since the amount of o-naphthoquinonediazide-4-sulfonic acid halide added is small, the contrast of printing out is insufficient. In particular, there is a disadvantage that the contrast decreases with time.

JP-A-53-36223 and JP-A-63-58440 propose the addition of trihalomethyltriazine in order to improve the printing contrast. EP 0 505 903 describes the addition of triazine compounds of the general formula (I). However, these have excellent print-out properties immediately after exposure, but have the drawback that if left untouched, the print-out contrast will be lost. On the other hand, JP-A-55-126235 proposes addition of o-naphthoquinonediazide-4-sulfonic acid halide and trihalomethyltriazine. However, in this system, it is difficult to achieve both the printing property immediately after exposure and the printing property left after exposure. In recent years, Japanese Patent Application Laid-Open No. 3-225341
As described in Japanese Patent Application Laid-Open No. H10-209, there is an environmental problem due to the odor of the residual monomer during the steps of coating and drying the photosensitive lithographic printing plate and during plate making due to the phenol (cresol) monomer remaining in the resin. However, when the amount of the monomer component is reduced, the printing property left after exposure is deteriorated, and the sensitivity is lowered.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive composition having good printout properties immediately after exposure and left after exposure. Another object of the present invention is to provide a photosensitive composition having a low odor and a high sensitivity.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have accomplished the present invention. That is, the present invention provides, in a photosensitive composition comprising an o-naphthoquinonediazide compound and a resin which is insoluble in water and soluble in an aqueous alkali solution, (1) a color-changing agent which interacts with an acid to change the color tone. 0.3 to 5% by weight of (2)
0.2 to 7% by weight of o-naphthoquinonediazide-4-sulfonic acid halide in the total composition; and (3) a compound capable of dissociating an acid upon irradiation with actinic rays of the following general formula (I) in the total composition: Characterized in that 0.2 to 7% by weight of
The present invention relates to a photosensitive composition that obtains a high-contrast visible image after exposure.

[0007]

Embedded image

Hereinafter, the present invention will be described in detail. Examples of the color changing agent used in the present invention include a color changing agent which changes from a colorless state to a colored state due to the action of an acid generated during the photolysis of the compound represented by the general formula (I), and a color inherent in a specific color. Are discolored or bleached. Representative examples of the color changing agent 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: Diphenylamine,
Dibenzylaniline, 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.

[0009] Further, as the discoloring agent which originally has an inherent color and is discolored or decolorized by the photolysis product of the free radical generator, diphenylmethane, triphenylmethane, thiazine, oxazine System, xanthene system,
Various dyes such as anthraquinone-based, iminonaphthoquinone-based, azomethine-based, and azo-based dyes are effectively used. Examples of these are as follows. Brilliant Green, Eosin, Ethyl Violet, Erythrosin B,
Methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein, methyl violet 2B, quinaldine red, rose bengal, methanil yellow, thymol sulfophthalein, xylenol blue , Methyl orange, orange
IV, diphenylthiocarbazone, 2,7-dichlorofluorescein, paramethyl red, congo red, benzopurpurine 4B, α-naphthyl red, nile blue 2B, nile blue A, phenacetaline, methyl violet, malachite green, parafuchsin, oil Blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Pink # 312 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industry Co., Ltd.), Oil Scarlet # 308 [Orient Chemical Industry Co., Ltd. )
Oil 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.), Victoria Pure Blue BOH
[Hodogaya Chemical Industry Co., Ltd.], Victoria Pure Blue Naphthalenesulfonate, m-cresol purple, cresol red,

Rhodamine B, rhodamine 6G, fast acid violet R, sulforhodamine B, auramine, 4-p-diethylaminophenylimino naphthoquinone, 2-carboxyanilino-4-p-diethylaminophenylimino naphthoquinone, 2-carbostearyl Amino-4-p-dihydroxyethyl-amino-phenyliminonaphthoquinone, 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-pyrazolone, 2,4-dinitro-5-chloro-2'-acetamino-4'-diethylamino-5'-
Methoxyazobenzene.

The leucotriphenylmethane dye among the color changing agents used in the present invention is generally easily oxidized. Therefore, when using these dyes, it is effective to include a certain kind of stabilizer. Examples of the stabilizer for this purpose include amines, zinc oxide and phenols described in U.S. Pat.No. 3,042,575, sulfur compounds described in U.S. Pat. No. 3,042,516, and alkali metal iodides described in U.S. Pat. No. 3,042,518. Compounds, organic acids, organic acid anhydrides described in US Pat. No. 3,082,086 and triaryl compounds of antimony, arsenic, bismuth and phosphorus described in US Pat. No. 3,377,167 are effective. It is preferable to add the discoloring agent in an amount of 0.3 to 5% by weight based on the whole composition. At 0.3% by weight or less, the image density is low, and at 5% by weight or more, the discoloring agent remains on the substrate after development. In the photosensitive composition of the present invention,
o-Naphthoquinonediazide-4-sulfonic acid halide is an essential component. Examples of the o-naphthoquinonediazide-4-sulfonic acid halide used in the present invention include o-naphthoquinonediazide-4-sulfonic acid chloride and o-naphthoquinonediazide-4-sulfonic acid fluoride. The addition amount of o-naphthoquinonediazide-4-sulfonic acid halide is 0.2 with respect to the total amount of the composition.
~ 7% by weight. When the amount is less than 0.2% by weight, there is no effect as a printing-out agent, and when the amount is more than 7% by weight, the sensitivity is significantly reduced.

In the present invention, the triazine compound of the general formula (I) is also an essential component. Further, another triazine compound or trihalomethyl compound may be used in combination. Specific examples include triazine compounds described in JP-A-63-58440 and trihalomethyl compounds described in JP-A-55-126235. The addition amount of the triazine compound of the general formula (I) is 0.2 to 7% by weight based on the total amount of the composition. When the amount is less than 0.2% by weight, the contrast of printing out is deteriorated, and when it is more than 7% by weight, the sensitivity is remarkably reduced.
Especially from the viewpoint of balance of printout contrast and sensitivity
It is preferable to add 0.25 to 3% by weight. When used in combination with other trihalomethyl compounds described above,
The triazine compound of the general formula (I) must be added in an amount of 20% by weight or more based on other trihalomethyl compounds. If it is less than that, the effect of the present invention cannot be obtained.

Hereinafter, an example of using the photosensitive composition of the present invention as a photosensitive layer of a photosensitive lithographic printing plate (PS plate) will be described.
The present invention will be described in detail step by step. The aluminum plate used for the PS plate is a plate-like body such as pure aluminum or an aluminum alloy containing aluminum as a main component and containing a small amount of a different atom. This heteroatom includes silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of foreign atoms in the alloy is at most 10% by weight or less. Aluminum which is suitable for the present invention is pure aluminum. However, since pure aluminum is difficult to produce due to refining technology, it is preferable that the content of foreign atoms be as low as possible. In addition, any aluminum alloy having the above-described content can be said to be a material applicable to the present invention. As described above, the composition of the aluminum plate applied to the present invention is not specified, and conventionally known and publicly available materials can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.5 mm. Prior to the surface roughening treatment of the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant or an alkaline aqueous solution is performed to remove rolling oil on the surface.

The photosensitive lithographic printing plate of the present invention may be one that can be used on only one side or one that can be used on both sides by the same treatment. Since the same applies to both surfaces, the case of one surface will be described below. Examples of the surface roughening method include a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of chemically selectively dissolving the surface. As a method of mechanically roughening the surface, a ball polishing method, a brush polishing method, a blast polishing method,
A known method called a buff polishing method or the like can be used. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can be used. The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment as necessary.

As the electrolyte used for the anodic oxidation treatment of the aluminum plate, any electrolyte can be used as long as it forms a porous oxide film.
Phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is used, and the concentration of the electrolyte is appropriately determined depending on the type of the electrolyte. Since the anodizing treatment conditions vary depending on the electrolyte used, they cannot be specified unconditionally. Generally, however, the concentration of the electrolyte is 1 to 80% by weight, the solution temperature is 5 to 70 ° C, and the current density is 5 to 60 A / dm. ^2. It is appropriate that the voltage is in the range of 1 to 100 V and the electrolysis time is 10 seconds to 50 minutes.

Among these anodizing treatments, in particular, the method of anodizing at a high current density in sulfuric acid described in British Patent No. 1,412,768 and US Pat. No. 4,211,619
Anodizing in a low concentration of sulfuric acid as described in the specification is preferred. Most preferably, a current density of 5-20% in an electrolyte containing 5-20% by weight of sulfuric acid and 3-15% by weight of aluminum ions at a temperature of 25-50 ° C.
This is a method of anodizing with a direct current of A / dm ² . The amount of the anodized film is suitably 0.5 to 10 g / m ^2, but more preferably in the range of 1.0~6.0g / m ^2. The anodic oxide film is 0.
When the amount is less than 5 g / m ² , the printing durability is insufficient, and the non-image portion of the lithographic printing plate is easily damaged.
The so-called "scratch stain" in which ink adheres to the scratched portion is likely to occur.

The aluminum plate which has been roughened and anodically oxidized as described above may be subjected to a hydrophilization treatment if necessary. A preferred example is US Pat. No. 2,714,066.
And aqueous solutions of alkali metal silicates (e.g. sodium silicate) as disclosed in U.S. Pat.
A method of treating with an aqueous solution of potassium fluorozirconate disclosed in JP-B-36-22063 (= U.S. Pat. No. 2,946,683) or an aqueous solution of polyvinyl phosphonic acid as disclosed in U.S. Pat. No. 4,153,461. A method of treating with hot water or steam as disclosed in JP-A-59-114100;
No. 950 discloses a method of treating with an aqueous solution of nitrous acid or a salt thereof or an aqueous solution of sulfonic acid or a salt thereof.

The aluminum plate thus treated is
Before coating the photosensitive layer, a method of undercoating hydrophilic cellulose containing a water-soluble metal salt for the purpose of reducing residual color, or sodium aryl sulfonate as described in GB 2,098,627 And polyacrylamide disclosed in U.S. Pat. No. 3,511,661, JP-B-46-35885.
And amino acids and salts thereof (eg, alkali metal salts such as Na salt and K salt, ammonium salts, hydrochlorides, oxalates, and acetic acids). Salts and phosphates), amines having a hydroxyl group and their salts (hydrochloride, oxalate, phosphate, etc.) disclosed in JP-A-60-232998, JP-A-63-165183. And a method for undercoating a compound having an amino group and a phosphonic acid group or a salt thereof disclosed in JP-A-3-261542, a method for undercoating a phosphonic acid disclosed in Japanese Patent Application No. 3-10604, and It is preferable to apply a method of combining the undercoating and the like.

On the aluminum support coated with the hydrophilic compound thus obtained, a photosensitive layer comprising a known positive photosensitive composition is provided to obtain a photosensitive lithographic printing plate. As the composition for the photosensitive layer, any one can be used as long as its solubility or swelling property in a developer changes before and after exposure. Hereinafter, typical ones will be described. As the photosensitive compound of the positive photosensitive composition,
An o-quinonediazide compound is exemplified, and a representative example thereof is an o-naphthoquinonediazide compound. Examples of the o-naphthoquinonediazide compound include JP-B-43-28.
An ester of 1,2-diazonaphthoquinonesulfonic acid chloride and pyrogallol-acetone resin described in JP-A-403-403 is preferred from the viewpoint of plate cleaner resistance. Other suitable orthoquinone diazide compounds include the esters of 1,2-diazonaphthoquinone-5-sulfonic acid chloride and phenol-formaldehyde resin described in U.S. Pat.Nos. 3,046,120 and 3,188,210. , Japanese Unexamined Patent Publication No.
There are esters of 1,2-diazonaphthoquinone-4-sulfonic acid chloride and phenol-formaldehyde resin described in JP-A-96163, JP-A-2-96165, and JP-A-2-96661. Other useful o-naphthoquinonediazide compounds include those reported and known in numerous patents. For example, JP-A-47-5303 and JP-A-48-63
No. 802, No. 48-63803, No. 48-96575
Nos. 49-38701, 48-13354, JP-B-37-18015, 41-11222, and 4
Nos. 5-9610, 49-17481, U.S. Pat.Nos. 2,797,213, 3,454,400, and 3,544,323
No. 3,573,917, No. 3,674,495, No. 3,785,
825, UK Patents 1,227,602, 1,251,345,
Nos. 1,267,005, 1,329,888, 1,330,932
And German Patent No. 854,890.

The particularly preferred o-naphthoquinonediazide compound in the present invention is a compound obtained by reacting a polyhydroxy compound having a molecular weight of 1,000 or less with 1,2-diazonaphthoquinonesulfonic acid chloride. Specific examples of such compounds are described in JP-A-51-139402,
No. 58-150948, No. 58-203434, No. 59-165053, No. 60-112445, No. 6
0-134235, 60-16043, 61
-118744, 62-10645, 62-1
Nos. 0646, 62-153950, 62-178
No. 562, No. 64-76047, U.S. Pat.
No. 9, No. 3,126,281, No. 3,130,047, No. 3,14
No. 8,983, No. 3,184,310, No. 3,188,210, No.
Examples described in each gazette or specification such as 4,639,406 can be mentioned.

In synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2 to 1.2 equivalents of 1,2-diazonaphthoquinonesulfonic acid chloride with respect to the hydroxyl group of the polyhydroxy compound. .3 ~
More preferably, the reaction is carried out at 1.0 equivalent. 1,2-diazonaphthoquinonesulfonic acid chloride includes 1,2-diazonaphthoquinonesulfonic acid chloride.
Diazonaphthoquinone-5-sulfonic acid chloride or 1,2-diazonaphthoquinone-4-sulfonic acid chloride can be used. The obtained o-naphthoquinonediazide compound is a mixture of various compounds having different positions and introduced amounts of 1,2-diazonaphthoquinonesulfonic acid ester groups, but all of the hydroxyl groups are converted to 1,2-diazonaphthoquinonesulfonic acid ester. The proportion of the compound in the mixture (content of the completely esterified compound) is preferably 5 mol% or more, more preferably 20 to 99 mol%. When 1,2-diazonaphthoquinonesulfonic acid chloride and a pyrogallol-acetone resin are used as a photosensitive material, the sensitivity generally decreases, but the printing-out system of the present invention is sufficient to compensate for the decrease in sensitivity.

As the photosensitive compound which acts positively without using an o-naphthoquinonediazide compound, for example, a polymer compound having an orthonitrocarbinol ester group described in JP-B-56-2696 is also used in the present invention. can do. Further, a compound that generates an acid by photolysis and a —C—O—C group or —C dissociated by the acid.
A combination system with a compound having an -O-Si group can also be used in the present invention. For example, a combination of a compound that generates an acid by photolysis with an acetal or an O, N-acetal compound (Japanese Patent Application Laid-Open No. 48-89003), a combination with an orthoester or amide acetal compound (Japanese Patent Application Laid-Open No.
20714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-133429).
No.), a combination with an enol ether compound (Japanese Unexamined Patent Publication No.
-12995), a combination with an N-acylimino carbon compound (JP-A-55-126236), and a combination with a polymer having an orthoester group in the main chain (JP-A-56-1).
No. 7345), a combination with a silyl ester compound (JP-A-60-10247) and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-12).
No. 1446).

The amount of these positive-acting photosensitive compounds (including the above combinations) in the photosensitive composition of the present invention is suitably from 10 to 50% by weight, and more preferably from 15 to 50% by weight. 40% by weight. Although the o-quinonediazide compound alone constitutes the photosensitive layer, it is preferable to use a resin soluble in alkaline water as a binder together with this kind of resin. As such a resin soluble in alkaline water, there is a novolak resin having this property.
-Cresol formaldehyde resin, p-cresol formaldehyde resin, o-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, o- or m
-/ P- or m- / o-mixture) and cresol formaldehyde resins such as mixed formaldehyde resins. In addition, resol type phenol resins are also preferably used, and phenol / cresol (m
-, P-, o- or m- / p-, m- / o-). Mixed formaldehyde resins are preferred, and phenol resins described in JP-A-61-217034 are particularly preferred. .

Also, a phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, an acrylic resin containing a phenolic hydroxyl group as disclosed in JP-A-51-34711, and JP-A-2-866. Various alkali-soluble polymer compounds such as an acrylic resin having a sulfonamide group described in (1) and a urethane resin can also be used. These alkali-soluble polymer compounds have a weight average molecular weight of 50.
Those having a number average molecular weight of 200 to 60,000 and 0 to 20,000 are preferred. These alkali-soluble polymer compounds may be used alone or in combination of two or more, and are used in an amount of 80% by weight or less of the total composition.
Further, as described in U.S. Pat.No. 4,123,279, t-butylphenol formaldehyde resin,
It is preferable to use a condensate of phenol having a C3-8 alkyl group as a substituent, such as octylphenol formaldehyde resin, with formaldehyde in order to improve the oil sensitivity of the image. It is preferable to use a phenol (cresol) resin having less residual monomer components in view of environmental measures against odor. The amount of the residual monomer component is preferably less than 4.0% by weight in the coated photosensitive layer. Above that, the odor increases. The odor less than 3.0% by weight is almost eliminated, which is more preferable. On the other hand, when the amount of the residual monomer is reduced, the odor is improved, but the printability left after exposure is deteriorated, and the sensitivity is lowered. The bakeout system of the present invention is sufficient to compensate for these disadvantages.

It is preferable to add a cyclic acid anhydride, an organic acid or the like to the photosensitive composition of the present invention in order to increase the sensitivity. U.S. Pat.
115,128 Pat phthalic anhydride, as described in, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloro Maleic anhydride, α-phenyl maleic anhydride, succinic anhydride, pyromellitic anhydride and the like.

As the organic acids, JP-A-60-8894
2, sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphinic acids, phosphoric esters, carboxylic acids, and the like described in JP-A No. 2-96755 and JP-A-2-96755. p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid,
Phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 1,4-cyclohexene-2,2- Examples thereof include dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid. The above cyclic acid anhydrides,
The ratio of the organic acids in the photosensitive composition is 0.05 to 1%.
Preferably 5% by weight, more preferably 0.1 to 5% by weight
It is.

Further, in the photosensitive composition of the present invention, in order to widen the latitude of development, Japanese Patent Application Laid-Open No.
Non-ionic surfactants described in JP-A-251740 and JP-A-4-68355;
An amphoteric surfactant as described in JP-A-9-121044 and JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene sorbitan monooleate, polyoxyethylene nonyl phenyl ether, and the like. Specific examples of the activator include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, Amogen K (trade name, Daiichi Kogyo Co., Ltd.)
N-tetradecyl-N, N-betaine type), 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, Levon 15 (trade name, Sanyo Kasei Co., Ltd., alkylimidazoline) Is mentioned. The proportion of the nonionic surfactant and the amphoteric surfactant in the photosensitive composition is preferably 0.05% to 15% by weight, more preferably 0.1% to 5% by weight. In the photosensitive composition of the present invention, a printing-out agent for obtaining a visible image immediately after exposure, a dye as an image coloring agent, and other fillers can be added.

The photosensitive lithographic printing plate of the present invention can be obtained by dissolving the above-mentioned components in a solvent capable of dissolving and applying the solution to a support. As the solvent used here, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2
-Propanol, 1-methoxy-2-propyl acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate,
Dimethyl sulfoxide, dimethylacetamide, dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, isopropanol,
There are diethylene glycol dimethyl ether and the like, and these solvents are used alone or as a mixture. And
The concentration (solid content) in the above components is 2 to 50% by weight. In addition, the amount of application varies depending on the application, but, for example, when it comes to photosensitive lithographic printing plates, in general, the solid content is 0.5 to 0.5.
3.0 g / m ² is preferred. As the amount of coating decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

The photosensitive composition of the present invention may contain a surfactant for improving coating properties, for example, JP-A-62-17.
A fluorine-based surfactant as described in JP-A-0950 can be added. A preferable addition amount is 0.01 to 1% by weight of the total photosensitive composition, more preferably 0.05 to 1% by weight.
~ 0.5% by weight. The surface of the photosensitive layer provided as described above is preferably matted in order to shorten the time for evacuation during contact exposure using a vacuum printing frame and to prevent printing blur. Specifically, Japanese Patent Laid-Open No. 50-12580
No. 5, JP-B-57-6582 and JP-A-61-28986. A method of providing a mat layer as described in JP-B-57-65886 and JP-B-62-62337. And the like.

The developer for the photosensitive composition of the present invention comprises:
Alkaline aqueous solutions substantially free of organic solvents are preferred, specifically sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, Aqueous solutions such as ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, aqueous ammonia, etc. are suitable, and their concentration is 0.1 to 10% by weight. %, Preferably 0.5 to 5% by weight. Among these, a developer containing an alkali silicate such as potassium silicate, lithium silicate, and sodium silicate is preferable because stain during printing is less likely to occur, and the composition of the alkali silicate is [SiO ₂ ] / molar ratio. [M] = 0.5 to 2.5 (where [SiO ₂ ] and [M] indicate the molar concentration of SiO _{2 and} the molar concentration of the total alkali metal, respectively), and the SiO ₂ is defined as 0.5. 8
A developer containing 〜8% by weight is preferably used. In addition, water-soluble sulfites such as sodium sulfite, potassium sulfite, and magnesium sulfite, resorcin, methylresorcin, hydroquinone, and thiosalicylic acid can be added to the developer. The content of these compounds in the developer is preferably 0.002 to 4% by weight, and more preferably 0.01 to 1% by weight.

Further, in the developer, JP-A-50-5132
4, JP-A-59-84241 and JP-A-59-84241, and JP-A-59-75255, JP-A-60-111246 and JP-A-60-213943. JP-A-55-95946, by incorporating at least one nonionic surfactant as described in Japanese Patent Publications
As described in JP-A-56-142528, a polymer electrolyte is contained to enhance wettability to a photosensitive composition and development stability (development latitude). Are preferably used. The addition amount of such a surfactant is preferably 0.001 to 2% by weight, and particularly preferably 0.003 to 0.5% by weight. Further, as the alkali metal of the alkali silicate, it is preferable that potassium is contained in an amount of 20 mol% or more in all the alkali metals, since the generation of insolubles in the developer is small, and more preferably 9%.
0 mol% or more, most preferably 100 mol% of potassium
Is the case. Further, the developing solution used in the present invention may contain some organic solvents such as alcohols and
Chelating agent described in JP-B-2, JP-B-1-30
An antifoaming agent such as a metal salt or an organic silane compound described in JP-A-139-139 may be added. Light sources used for exposure include a carbon arc lamp, a mercury lamp, a xenon lamp, a tungsten lamp, and a metal halide lamp.

The photosensitive lithographic printing plate of the present invention is disclosed in
JP-A-8002, JP-A-55-115045 and JP-A-59-15045.
It goes without saying that the plate-making process may be performed by the method described in each of the publications of No. 58431. That is, after the development processing,
A desensitization treatment after washing with water, a desensitization treatment as it is, a treatment with an aqueous solution containing an acid, or a treatment with an aqueous solution containing an acid may be followed by a desensitization treatment. Furthermore, in the development process of this type of photosensitive lithographic printing plate, the alkali aqueous solution is consumed depending on the processing amount, and the alkali concentration is reduced, or the alkali concentration is reduced by air due to long-time operation of the automatic developing solution. Although the processing capacity is reduced, the processing capacity may be restored by using a replenisher as described in JP-A-54-62004. In this case, it is preferable to replenish by the method described in U.S. Pat. No. 4,882,246. It is preferable that the above plate making process is performed by an automatic developing machine as described in JP-A-2-7054 and JP-A-2-32357.

In the case where the photosensitive lithographic printing plate of the present invention is subjected to image exposure, development, washing or rinsing, and then unnecessary image portions are erased, it is described in JP-B-2-1293. It is preferable to use such an erasing liquid. Examples of the desensitized gum which is applied as required in the final step of the plate making process include JP-B-62-16834, JP-B-62-25118, JP-B-63-52600 and JP-A-6-52600.
Nos. 2-7595, 62-11693 and 62-83
What is described in each gazette of No. 194 is preferable. Furthermore, when the photosensitive lithographic printing plate of the present invention is subjected to image exposure, development, washing or rinsing, erasing if desired, and burning after washing with water, before burning, Japanese Patent Publication No. 61-2518 is used. And JP-A-55-28062, JP-A-62-31859, and JP-A-61-159655.

[0034]

The photosensitive composition of the present invention has good printout properties immediately after exposure and left after exposure. In addition, it has low odor and high sensitivity.

[0035]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, "%" indicates "% by weight" unless otherwise specified.

Examples 1 and 2 and Comparative Examples 1 to 8 A 0.30 mm thick aluminum plate was
The surface was sand-grained using a 0-mesh pumistone aqueous suspension, and then thoroughly washed with water. After etching by dipping in 10% sodium hydroxide at 70 ° C. for 60 seconds, the substrate was washed with running water, neutralized with 20% HNO ₃ , and washed with water. This was subjected to electrolytic surface roughening treatment in a 1% aqueous nitric acid solution at an anode electricity of 160 coulomb / dm ² using a sinusoidal alternating waveform current under the condition of V _A = 12.7 V. When the surface roughness was measured, it was 0.6 μ (Ra indication). After immersion in a 30% H ₂ SO ₄ aqueous solution and desmutting at 55 ° C. for 2 minutes, a current density of 2 A / dm in a 20% H ₂ SO ₄ aqueous solution.
Thickness at ² is anodized so as to 2.7 g / m ^2,
A substrate was prepared. The undercoat liquid (A) having the following composition was applied to the surface of the substrate thus treated, and dried at 80 ° C. for 30 seconds. The coating amount after drying was 30 mg / m ² . Undercoat solution (A) Aminoethylphosphonic acid 0.10 g Phenylphosphonic acid 0.15 g β-alanine 0.10 g Methanol 40 g Pure water 60 g The substrate (I) was thus prepared. Next, the following photosensitive liquid was applied onto the substrate (I) and dried at 100 ° C. for 1 minute to obtain a positive photosensitive lithographic printing plate. The amount of coating after drying is
It was 1.7 g / m ² .

[Photosensitive solution] Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709). 75 g Cresol-formaldehyde novolak resin (meta-para ratio; 6: 4, weight average molecular weight 3,000, number average molecular weight 1,100, containing 0.7% of unreacted cresol) 2.10 g P-normal octylphenol-formaldehyde resin ( 0.02 g ・ tetrahydrophthalic anhydride 0.10 g ・ benzoic acid 0.15 g ・ bakeout agent See Table 1 ・ Victoria pure blue naphthalene sulfonate 0.055 g ・Megafac F-177 (manufactured by Dainippon Ink and Chemicals, Inc.) Sobuchiruketon solution) 0.05g · Methyl ethyl ketone 28.0 g

The dye was added in such an amount that the image density became 0.98. Unreacted cresol in the obtained photosensitive layer was 0.4%. The photosensitive lithographic printing plate thus prepared was exposed through a transparent positive film through a transparent positive film from a distance of 1 m with a 3 kw metal halide lamp for 50 seconds, and then exposed to SiO ₂ /
It was developed and evaluated with a 5.26% aqueous solution of sodium silicate (pH = 12.7) having a molar ratio of Na ₂ O of 1.74. Table 1 shows the results. In addition, each printing-out agent used is as showing in following structural formula.

[0039]

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[0040]

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[0041]

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[0042]

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[0043]

[Table 1] 焼 Bakeout properties Bakeout agent and amount added (g ) Immediately after exposure 3 days after exposure ─────────────────────────────────── Example 1 A 0.04 + B 0.01 0.20 0.18 〃 2 A 0.01 + E 0.03 + B 0.01 0.20 0.18 比較 Comparative example 1 A 0.04 0.17 0.10 〃 2 B 0.01 0.10 0.09 〃 3 C 0.04 + B 0.01 0.18 0.14 ４ 4 D 0.04 + B 0.01 0.20 0.14 〃 5 E 0.04 + B 0.01 0.19 0.16 〃 6 F 0.04 + B 0.01 0.14 0.14 〃 7 G 0.04 + B 0.01 0.16 0.16 〃 8 H 0.04 + B 0.01 0.16 0.16 ───────────────────────────────────

The print-out property is represented by [unexposed area density-exposed area density] under the above exposure conditions. The larger the value, the better the bakeout property. If the numerical values are different from each other by 0.02, the difference will be obvious visually. That is, when the value is 0.02 higher, the contrast of printing out is clearly improved. As shown in Table 1, it can be seen that the photosensitive lithographic printing plate of the present invention has good printing properties.

Example 3, Comparative Examples 9 to 10 An undercoat solution (B) having the following composition was applied to the surface of a substrate treated in the same manner as in Examples 1 and Comparative Examples 1 to 8, and dried at 100 ° C. for 50 seconds. The coating amount after drying was 15 mg / m ² . Undercoat solution (B) β-alanine 0.10 g Methanol 20 g Pure water 80 g In this way, a substrate (II) was prepared.

Next, the following photosensitive solution was applied onto the substrate (II) and dried at 100 ° C. for 1 minute to obtain a positive photosensitive lithographic printing plate. The coating amount after drying was 1.7 g / m ² . [Photosensitive solution of Example 3] The same photosensitive solution as that of Example 1 was used. [Photosensitive solution of Comparative Example 9] The same photosensitive solution as that of Comparative Example 3 was used. [Photosensitive solution of Comparative Example 10] Cresol used in Example 3
Formaldehyde novolak resin (meta-para ratio: 6: 4, weight average molecular weight 3000, number average molecular weight 1100,
Unreacted cresol (containing 0.7%) was replaced with a cresol-formaldehyde novolak resin having the same composition and the same molecular weight containing 10% of unreacted cresol. The photosensitive lithographic printing plate thus obtained was prepared in Example 1,
Evaluation was performed in the same manner as in Comparative Examples 1 to 8. Table 2 shows the results.

[0047]

[Table 2] 焼 Burn- out printing agent remaining in photosensitive layer Cresol Exposure Exposure sensitivity Odor (g) Monomer (%) Immediately after 3 days (seconds) ──────────────────────────────── ─── Example 3 A 0.04 + B 0.01 0.4 0.20 0.18 50 ○ ────────────────────────────────── ─ Comparative Example 9 C 0.04 0.4 0.17 0.14 70 ○ Comparative Example 10 C 0.04 6.0 0.17 0.17 50 × ───────────────────────────── ──────

The sensitivity was represented by the time when the density difference was 0.15 under the above exposure conditions and the five steps of the gray scale were completely blank. The smaller the value, the higher the sensitivity. As described above, when a novolak resin having a low cresol monomer content is used, the odor is eliminated, but the sensitivity is reduced and the printability with time after exposure is reduced (Comparative Examples 9 and 10). The use of printing-out agents A and B can compensate for a reduction in sensitivity and a reduction in printing-out properties with time after exposure.

Example 4, Comparative Examples 11 and 12 An undercoat liquid (C) having the following composition was applied to the surface of a substrate treated in the same manner as in Example 1 and Comparative Examples 1 to 8, and dried at 100 ° C. for 50 seconds. The coating amount after drying was 10 mg / m ² . Undercoating liquid (C) β-alanine 0.10 g methanol 90 g pure water 10 g Thus, a substrate (III) was prepared.

Next, the following photosensitive solution was applied onto the substrate (III) and dried at 100 ° C. for 1 minute to obtain a positive photosensitive lithographic printing plate. The coating amount after drying was 1.7 g / m ² . [Photosensitive solution]-Cresol-formaldehyde novolak resin (meta-para ratio: 6: 4, weight-average molecular weight 3000, number-average molecular weight 1100, containing 0.7% of unreacted cresol) 2.10 g-p-n-octylphenol-formaldehyde resin (As described in U.S. Pat. No. 4,123,279) 0.02 g ・ Tetrahydrophthalic anhydride 0.10 g ・ Photosensitive material Refer to Table 3 ・ Printing agent 〃 ・ Victoria pure blue naphthalenesulfonic acid 0.055 g ・ Megafax F-177 (20% by weight of a fluorine-based surfactant in methyl isobutyl ketone solution manufactured by Dainippon Ink and Chemicals, Inc.) 0.05 g ・ Hydroxymethylphenol compound [the following structural formula (III)] 0.07 g ・ Methylethylketone 30. 0g

[0051]

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The photosensitive lithographic printing plate thus obtained was similarly evaluated. The image was easily damaged by a plate cleaner by immersing it in an ultra plate cleaner (available from Dainichi Seika) for 10 minutes and examining the degree of scratching with a sponge. The results are shown in Table 3 below.

[0053]

[Table 3] ───────────────────────────────────Print- out plate cleaner Photosensitive material Print-out agent Exposure Immediately after (g) (g) of the image at the exposure sensitivity 3 days later (sec) Easiness of damage ───────────────────────────── ────── Example ^* 0.80 A 0.05 + 0.21 0.19 40 Good 4 B 0.02 ────────────────────────────── ───── Comparative Example ^* 0.80 H 0.05 + 0.17 0.17 50 Good 11 B 0.02 ─────────────────────────────── ──── Comparative example ^* 0.80 H 0.05 + 0.17 0.17 40 Bad 12 B 0.02 ──────────────────────────────── ─── * = Esterified product of naphthoquinone-1,2-diazide-5-sulfonyl chloride and pyrogallol-acetone resin = Esterified product of naphthoquinone-1,2-diazide-5-sulfonyl chloride and cresol-formaldehyde resin

As described above, naphthoquinone-
When an esterified product of 1,2-diazide-5-sulfonyl chloride and pyrogallol-acetone resin is used, the image is more easily damaged when an ultraplate cleaner is used than when an esterified product of cresol-formaldehyde resin is used. Is better, but the sensitivity is lower (Comparative Examples 11 and 12). However, when the printing-out agents A and B are used, a reduction in sensitivity can be compensated and good printing-out properties can be obtained.

Example 5, Comparative Example 13 The following photosensitive liquid was applied to the substrate (IV) treated in the same manner as in Example 1, Comparative Examples 1 to 8. [Photosensitive solution]-Esterified product of 2,3,4-trihydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonyl chloride (esterification ratio: 90 mol%) 0.45 g-Consists of the following structural formula (III) Polymer compound (corresponding to JP-A-1-35872, Example 4) 0.77 g

[0056]

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-Cresol-formaldehyde resin (meta form 60%, para form 40% residual cresol 2.0% weight average molecular weight 4000) 0.33 g-Bakeout agent See Table 4-Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) ) Dye) 0.015 g ・ MegaFac F-177 (Fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.004 g ・ Dimethylformamide 4 g ・ 1-Methoxy-2-propanol 9 g ・ Methyl ethyl ketone 7 g

[0058]

[Table 4] Bake-out agent bake-out property (g) Immediately after exposure 3 days after exposure ───── ────────────────────── Example 5 A 0.04 + B 0.02 0.20 0.18 Comparative Example 13 G 0.04 + B 0.02 0.14 0.14 ──────── ───────────────────

As described above, it can be seen that the photosensitive lithographic printing plate of the present invention has good printing properties.

Continuation of front page (56) References JP-A-53-8128 (JP, A) JP-A-3-225343 (JP, A) JP-A-3-228056 (JP, A) JP-A-3-259259 (JP) JP-A-2-96755 (JP, A) JP-A-60-88942 (JP, A) JP-A-3-235955 (JP, A) JP-A-3-235953 (JP, A) 4-69661 (JP, A) JP-A-4-69658 (JP, A) JP-A-6-148885 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/00 503 G03F 7/004 503 G03F 7/004 507 G03F 7/022

Claims (2)

(57) [Claims] 1. A photosensitive composition comprising an o-naphthoquinonediazide compound and a resin which is insoluble in water and soluble in an aqueous alkali solution, comprises (1) a color-changing agent which interacts with an acid to change the color tone. 0.3 to 5% by weight of the composition, (2) 0.2 to 7% by weight of the o-naphthoquinonediazide-4-sulfonic acid halide in the total composition, and (3) actinic ray of the following general formula (I) Irradiates the compound that dissociates the acid in the total composition
A photosensitive composition which obtains a high-contrast visible image after exposure, characterized in that it is added in an amount of 0.2 to 7% by weight. Embedded image 2. The method according to claim 1, wherein the resin insoluble in water and soluble in the aqueous alkali solution is a novolak resin, and phenol and cresol are less than 4.0% by weight in the photosensitive composition. Photosensitive composition.