JPH0772625A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To provide the positive radiation sensitive resin compsn. which has excellent efficiency of free radical formation at the time of image exposing and excellent exposed visible image characteristics and the exposed visible image characteristic in low exposing and lessens the deterioration of a plate with lapse of time after production. CONSTITUTION:This positive acting photosensitive resin compsn. contains the compd. expressed by the general formula and dyes which can make interaction with the photodecomposition product of this compd. In the formula, R<1>, R<2> respectively denote hydrogen atoms or 1 to 8C alkyl groups; X denotes a halogen atom; m denotes an integer from 1 to 3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive type photosensitive composition, and more particularly to a photosensitive composition which improves the visibility of exposed light under low exposure.

[0002]

BACKGROUND OF THE INVENTION It is widely known that an organic halogen compound generates a halogen free radical by light, and the halogen free radical, as a hydrogen abstracting agent, abstracts hydrogen from a hydrogen donor to generate an acid. Due to such characteristics, it is known that the organic halogen compound can be used as a printout agent in various image forming materials, particularly in a photosensitive lithographic printing plate. As such an organic halogen compound, use of o-naphthoquinonediazide-4-sulfonic acid halogenide is disclosed in JP-A-50-36209. However, the image-forming materials using these compounds have a drawback that their exposure visibility is deteriorated with time during storage after production. In order to solve such a drawback, vinyl-halomethyl-s-triazine compounds described in U.S. Pat. Nos. 3,954,475 and 3,987,037 and JP-A-48-36281 are used. Proposed. However, the above-mentioned known triazine compounds have a drawback that the free radical generation efficiency is not sufficient and a clear printout image cannot be obtained when used as a printout agent. In particular, in recent years, the sensitivity of the photosensitive composition has been increased, and since the exposure is low illuminance, a clear visible image cannot be obtained when the free radical generation efficiency is low, which causes a reduction in working efficiency. It becomes a fatal defect.

[0003]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to improve the visibility of an image when exposed to various image forming materials, particularly the visibility of an image in a low-exposure area, and to improve the visibility after the production of a plate. Another object of the present invention is to provide a photosensitive composition which does not deteriorate with time.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the inventor of the present invention contains a compound of the following general formula (I) and a dye capable of interacting with a photodegradation product of the compound. The present invention has been achieved by finding that the object of the present invention can be achieved by a positive photosensitive composition.

[0005]

[Chemical 2]

In the formula, R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X represents a halogen atom, and m represents an integer of 1 to 3.

The present invention will be described in more detail below. In the general formula (I) used in the present invention, the group represented by R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. Further, R ² is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom. Further, m is preferably 3. Specific examples of the compounds represented by the above general formula (I) which are particularly preferably used in the present invention are shown below.

[0008]

[Chemical 3]

The compound represented by the above general formula (I) is
It is preferably contained in the photosensitive composition of the present invention in the range of 0.02 to 10% by weight, particularly preferably in the range of 0.1 to 3% by weight. Furthermore, the above compounds can be used in combination with other free radical generators. The dye that can interact with the photolyzate of the compound of the general formula (I) used in the present invention reacts with a free radical or an acid,
Those that change the color tone are preferably used. here,
The term "changes in color tone" includes any of change from colorless to colored, change from colored to colorless or different color tone. More preferably, it forms a salt with an acid and changes the color tone.

Specific examples of the dye used in the present invention include, for example, Victoria Pure Blue BOH (Hodogaya Kagaku), Oil Blue # 603 (Orient Chemical Co., Ltd.), Patent Pure Blue (Sumitomo Mikuni Kagaku), and Crystal Violet. , Brilliant green, ethyl violet, methyl violet, methyl green, erythrosin B, basic fuchsin, malachite green, oil red, m-cresol purple, rhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, cyano-p-diethylaminophenyl From triphenylmethane dyes such as acetanilide, diphenylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, or anthraquinone dyes Mentioned as examples of the dye which changes the color or differently colored shades. On the other hand, examples of dyes that change from colorless to colored include leuco dyes and, for example, triphenylamine, diphenylamine, o-chloroaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p'-
Bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p, p ', p "-tris-dimethylaminotriphenylmethane, p, p'-bis-dimethylaminodiphenylmethylimine, p, p', p" -Triamino-o-methyltriphenylmethane, p, p'-bis-dimethylaminodiphenyl-4-anilinonaphthylmethane, primary or typified by p, p ', p "-triaminotriphenylmethane Secondary arylamine dyes, particularly preferably triphenylmethane dyes,
Diphenylmethane dyes are effectively used, more preferably triphenylmethane dyes, particularly Victoria Pure Blue and ethyl violet. In the photosensitive composition of the present invention, the dye is preferably 0.05 to 1
0% by weight, particularly preferably 0.1 to 5% by weight.

On the other hand, the positive-working photosensitive compound used in the present invention is specifically an o-naphthoquinonediazide compound. Examples of the o-naphthoquinonediazide compound used in the present invention include Japanese Patent Publication No. 43-2840.
1,2-diazonaphthoquinone-5-sulfonic acid chloride or 1,2-diazonaphthoquinone-4-sulfonic acid chloride and pyrogallol
Those that are esters with acetone resins are preferred. Other suitable orthoquinonediazide compounds include U.S. Pat. Nos. 3,046,120 and 3,188,2.
Ester of 1,2-diazonaphthoquinone-5-sulfonic acid chloride or 1,2-diazonaphthoquinone-4-sulfonic acid chloride and phenol-formaldehyde resin described in JP-A No. 10-187242 and JP-A-2-
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-2-96761. Other useful o-naphthoquinonediazide compounds include those reported and known in numerous patents.

For example, Japanese Patent Laid-Open Nos. 47-5303, 48-63802, 48-63803, and 4
8-96575, 49-38701, 48
-13354, Japanese Patent Publication Nos. 37-18015, 41
-11222, 45-9610 and 49-1
7481, U.S. Pat. Nos. 2,797,213, 3,454,400, 3,544,323,
No. 3,573,917, No. 3,674,495
No. 3,785,825, British Patent Nos. 1,22
No. 7,602, No. 1,251,345, No. 1,2
No. 67,005, No. 1,329,888, No. 1,
Those described in various specifications such as 330, 932 and German Patent No. 854,890 can be cited.

Further, a polyhydroxy compound having a molecular weight of 1,000 or less and 1,2-diazonaphthoquinonesulfonic acid-5-
A compound obtained by the reaction with chloride or 1,2-diazonaphthoquinonesulfonic acid-4-chloride can also be preferably used. Specific examples of such compounds are described in JP-A Nos. 51-139402 and 58-15094.
No. 8, No. 58-203434, 59-165053.
No. 60, No. 12-14445, No. 60-134235.
Issue No. 60-163043, Issue No. 61-118744
Nos. 62-10645, 62-10646, 62-153950, 62-178562, JP-A-1-76047, and U.S. Pat. No. 3,102,809.
No. 3,126,281, No. 3,130,04
No. 7, No. 3,148,983, No. 3,184,3
No. 10, No. 3,188,210, No. 4,639,
Those described in each publication or specification such as No. 406 can be mentioned.

When synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2-1.2 equivalents of 1,2-diazonaphthoquinonesulfonic acid chloride with the hydroxyl group of the polyhydroxy compound, and further 0.3-1.0 equivalents. It is preferable to react. 1,2-diazonaphthoquinonesulfonic acid chloride is 1,2
-Diazonaphthoquinone-5-sulfonic acid chloride or 1,2-diazonaphthoquinone-4-sulfonic acid chloride can be used. Further, as a 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 may be used in the present invention. You can

Further, a compound capable of generating an acid upon irradiation with light,
A combination system with a compound having a -C-O-C group or a -C-O-Si group which dissociates with an acid can also be used in the present invention. For example, a combination of a compound capable of generating an acid by photolysis with an acetal or O, N-acetal compound (JP-A-48-89003) or an orthoester or amide acetal compound (JP-A-51-1207714).
No.), a polymer having an acetal or ketal group in the main chain (JP-A No. 53-133429), and an enol ether compound (JP-A No. 55-12995).
No.), N-acyl imino carbon compound (JP-A-55-126236), and a polymer having an orthoester group in the main chain (JP-A-56-17345).
No.) and a silyl ester compound (JP-A-60-
10247) and a silyl ether compound (JP-A-60-37549, JP-A-60-12144).
No. 6) and the like. The amount of the positive-working photosensitive compound (including the combination as described above) in the photosensitive composition of the present invention is 10 to 50% by weight, more preferably 15 to 40% by weight.

A binder resin is used in the photosensitive composition of the present invention, and an alkali-soluble resin is usually used.
As such a resin, various resins known in the art can be used, but in particular, a novolak resin, a vinyl polymer having a structural unit having a sulfonamide group in its molecular structure, and a structural unit having a phenolic hydroxyl group. A vinyl polymer having in the molecular structure is preferably used.
Examples of the novolak resin used in the present invention include resins obtained by condensing phenols and formaldehyde in the presence of an acid catalyst. Examples of the phenols include phenol, o-cresol, m-cresol, p-
Examples thereof include cresol, 3,5-xylenol, 2,4-xylenol, 2,5-xylenol, carvacrol, thymol, catechol, resorcin, hydroquinone, pyrogallol, phloroglucin, and bisphenol A.

The above phenol compounds may be used alone or in combination of two or more to condense with formaldehyde to obtain a resin. Of these, preferred novolak resins are resins obtained by copolycondensing at least one selected from phenol, m-cresol (or o-cresol) and p-cresol with formaldehyde, and examples thereof include phenol-formaldehyde resins. , M-
Cresol / formaldehyde resin, o-cresol /
Formaldehyde resin, phenol / p-cresol /
Formaldehyde copolycondensate resin, m-cresol / p
-Cresol-formaldehyde copolycondensate resin, o-
Cresol / p-cresol / formaldehyde copolycondensate resin, phenol / m-cresol / p-cresol / formaldehyde copolycondensate resin, phenol / o
-Cresol / p-cresol / formaldehyde copolycondensate resin and m-cresol / bisphenol A / formaldehyde copolycondensate resin. In the present invention, the novolak resin may be used alone,
Moreover, you may use it in combination of 2 or more type.

With respect to the molecular weight of the above novolak resin, those having a weight average molecular weight of 500 to 20,000 and a number average molecular weight of 200 to 5,000 are preferable. The molecular weight of the novolak resin is determined by gel permeation chromatography (polystyrene standard). Further, examples of the vinyl polymer having a structural unit having a sulfonamide group in the molecular structure used in the present invention include polymer compounds described in JP-A-2-866 and JP-A-5-150453. To be Further, the vinyl polymer having a structural unit having a phenolic hydroxyl group in the molecular structure used in the present invention is a polymer compound as described in JP-B-52-41050 and JP-A-51-34711. Is mentioned. These binder resins may be used alone or in combination of two or more. The content of these binder resins in the photosensitive composition is 5 to 95% by weight, preferably 5 to 85% by weight.

In the photosensitive composition of the present invention, as described in US Pat. No. 4,123,279,
Carbon number 3 ~, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin
It is preferable to use a condensate of phenol having an alkyl group of 8 as a substituent and formaldehyde in combination in order to improve the oil sensitivity of the image. Cyclic acid anhydrides, phenols, and organic acids are preferably added to the photosensitive composition of the present invention in order to enhance sensitivity. Examples of the cyclic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and 3,6-endooxy-Δ ⁴ -tetrahydroanhydride as described in US Pat. No. 4,115,128. Examples thereof include phthalic acid, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, and pyromellitic dianhydride.

Examples of phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol,
2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 4,4,4 "-trihydroxy-triphenylmethane, 4,4 ', 3", 4 " -Tetrahydroxy-3,5,3 ', 5'-tetramethyltriphenylmethane, etc. Examples of organic acids include those described in JP-A-6-58.
No. 0-88942 and Japanese Patent Application Laid-Open No. 2-96755. Sulfonic acids, sulfinic acids,
There are alkylsulfates, phosphonic acids, phosphinic acids, phosphoric acid esters, carboxylic acids, etc., and specifically,
p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethylsulfate, 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,
Examples thereof include 2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid. The ratio of the cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

Further, in order to increase the development latitude in the photosensitive composition of the present invention, JP-A-62-
No. 251740, nonionic surfactants described in JP-A-4-68355, JP-A-59-1
Amphoteric surfactants such as those described in JP-A No. 21044 and JP-A No. 4-13149 can be added.
Specific examples of the nonionic surfactant include polyoxyethylene polyoxypropylene block polymer, sorbitan tristearate, sorbitan monopalmitate,
Examples thereof include sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene sorbitan monooleate, and polyoxyethylene nonyl phenyl ether. Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine 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 type), etc. Is mentioned. Among these, it is particularly preferable to add a polyoxyethylene polyoxypropylene block polymer.
The proportion of the nonionic surfactant and the amphoteric surfactant in the photosensitive composition is preferably 0.05% to 15% by weight,
More preferably, it is 0.1 to 5% by weight.

The photosensitive composition of the present invention is dissolved in a solvent which dissolves the above-mentioned components and applied on a support. As the solvent used here, ethylene dichloride, 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, dimethylsulfoxide, dimethylacetamide,
There are dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, isopropanol, diethylene glycol dimethyl ether and the like, and these solvents may be used alone or as a mixture. The concentration (solid content) in the above components is 2 to 50% by weight.
Is. Further, the coating amount varies depending on the use, but in the case of a photosensitive lithographic printing plate, for example, the solid content is generally
0.5 to 3.0 g / m ² is preferable. Although the photosensitivity increases as the coating amount decreases, the physical properties of the photosensitive film deteriorate.

In the photosensitive composition of the present invention, a surfactant for improving coatability, such as JP-A-62-1 is used.
Fluorine-based surfactants such as those described in JP 70950 can be added. The preferable addition amount is 0.01 to 1% by weight of the total photosensitive composition, and more preferably 0.05 to 1% by weight.
0.5% by weight. When a lithographic printing plate is produced using the photosensitive composition of the present invention, an aluminum plate is preferable as the support. Aluminum plates include pure aluminum and aluminum alloy plates. Various aluminum alloys can be used, such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth,
An alloy of a metal such as nickel and aluminum is used. These compositions include some iron and titanium, as well as other negligible amounts of impurities.

The aluminum plate is surface-treated if necessary. For example, it is preferable that surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or the like, or anodization treatment be performed. Further, as described in U.S. Pat. No. 2,714,066, an aluminum plate grained and then immersed in an aqueous sodium silicate solution is described in U.S. Pat. No. 3,181,461. As described above, an aluminum plate subjected to anodizing treatment and then immersed in an aqueous solution of an alkali metal silicate is also preferably used. The anodizing treatment is, for example, phosphoric acid, chromic acid,
Conducted by passing an electric current through an aluminum plate as an anode in an electrolytic solution of an inorganic acid such as sulfuric acid, boric acid, etc., or an organic acid such as oxalic acid, sulfamic acid, etc., or an aqueous solution or non-aqueous solution of these salts, or a combination of two or more kinds. To be done. Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. These hydrophilization treatments are performed to make the surface of the support hydrophilic, in addition to prevent harmful reaction with the photosensitive composition provided thereon and to improve the adhesion to the photosensitive layer. It is given to improve.

Prior to graining the aluminum plate, if necessary, the surface rolling oil may be removed and the surface of the aluminum plate may be pretreated in order to expose a clean aluminum surface. For the former, solvents such as trichlene and surfactants are used. For the latter, a method using an alkali etching agent such as sodium hydroxide or potassium hydroxide is widely used. As the graining method, any of mechanical, chemical and electrochemical methods is effective. Mechanical methods include a ball polishing method, a blast polishing method, and a brush polishing method in which a water-dispersed slurry of an abrasive such as pumice is rubbed with a nylon brush. As a chemical method, JP-A-54-311 is used.
A method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid as described in Japanese Patent Publication No. 87 is suitable, and an electrochemical method is AC electrolysis in an acidic electrolytic solution such as hydrochloric acid, nitric acid or a combination thereof. Is preferred. Among such surface-roughening methods, the surface-roughening method combining mechanical surface-roughening and electrochemical surface-roughening as described in JP-A-55-137993 is particularly suitable for the oil-sensitive image. This is preferable because it has a strong adhesion to the support. Graining by the method as described above is performed by using the center line surface roughness (H
It is preferably applied in a range such that a) is 0.3 to 1.0 μ.

The grained aluminum plate is washed with water and chemically etched if necessary. The etching treatment liquid is usually selected from an aqueous solution of a base or acid that dissolves aluminum. In this case, the etched surface must not form a coating different from aluminum derived from the etching solution component. Examples of preferable etching agents include sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, dipotassium phosphate as basic substances; sulfuric acid, persulfuric acid as acidic substances. , Phosphoric acid, hydrochloric acid, and salts thereof, but salts having a lower ionization tendency than aluminum, for example, salts of zinc, chromium, cobalt, nickel, copper, etc. are not preferable because they form an unnecessary film on the etched surface.

Most preferably, these etching agents are used so that the dissolution rate of the aluminum or alloy used is 0.3 to 40 g / m ² per 1 minute of immersion time when the concentration and temperature of use are set. It may be higher or lower than this. The etching is carried out by immersing the aluminum plate in the above-mentioned etching solution or by coating the aluminum plate with the etching solution, and it is preferable that the etching amount is in the range of 0.5 to 10 g / m ² . As the above-mentioned etching agent, it is preferable to use an aqueous solution of a base because of its high etching rate. In this case, smut is generated, and thus desmutting is usually performed. As the acid used for the desmutting treatment, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, hydrofluoric acid or the like is used. If necessary, the etched aluminum plate is washed with water and anodized. Anodization can be performed by a method conventionally used in this field. Specifically, when a direct current or an alternating current is applied to aluminum in sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc., or an aqueous solution or a non-aqueous solution containing a combination of two or more thereof, the aluminum support An anodized film can be formed on the body surface.

The treatment conditions for the anodic oxidation cannot be unconditionally determined because they vary depending on the electrolytic solution used, but generally the concentration of the electrolytic solution is 1 to 80% by weight, and the liquid temperature is 5 to 70%.
C, current density 0.5-60 amps / dm ² , voltage 1-10
A range of 0 V and electrolysis time of 30 seconds to 50 minutes is suitable. Among these anodizing treatments, especially British Patent No. 1,412,
768, a method of anodizing in sulfuric acid at high current density, a method of anodizing in low concentrations of sulfuric acid as described in U.S. Pat.No. 4,211,619, and U.S. Pat.No. 3,511,661. The method of anodic oxidation using phosphoric acid as an electrolytic bath described in the specification is preferred. The aluminum plate which has been roughened as described above and further anodized may be subjected to a hydrophilic treatment, if desired. Preferred examples thereof include U.S. Pat.Nos. 2,714,066 and 3,181,46.
An alkali metal silicate as disclosed in No. 1,
For example, there is a method of treating with an aqueous solution of sodium silicate or potassium fluorozirconate disclosed in Japanese Patent Publication No. 36-22063 and polyvinyl sulfonic acid as disclosed in US Pat. No. 4,153,461.

An undercoat layer made of a water-soluble compound may be provided on the aluminum plate which has been roughened, anodized, and optionally hydrophilized as described above. As an example of such a water-soluble compound, Japanese Patent Publication No. 57-1
Combinations of water-soluble metal salts and hydrophilic cellulose disclosed in 6349 (eg, zinc chloride and carboxymethyl cellulose, magnesium chloride and hydroxyethyl cellulose, etc.), polyacrylamides disclosed in US Pat. No. 3,511,661, Polyvinylphosphonic acid disclosed in JP-B-46-35685, JP-A-60-149491
Amino acid and its salts (Na
Salts, alkali metal salts such as K salts, ammonium salts, hydrochlorides, oxalates, acetates, phosphates, etc.), JP-A-60-232998
Hydroxyl group-containing amines and salts thereof (hydrochlorides, oxalates, phosphates, etc.) disclosed in Japanese Patent Laid-Open Publication No.
Compounds or salts thereof having an amino group and a phosphonic acid group disclosed in 63-165183, (a) an amino group and (b) a phosphonic acid group, phosphinic acid disclosed in JP-A-3-261592. Examples thereof include compounds having one group or one phosphoric acid group or salts thereof, and aliphatic or aromatic phosphonic acids or phosphinic acids or salts thereof disclosed in Japanese Patent Application No. 3-10604. Of these, the compounds disclosed in JP-A-3-261592 and Japanese Patent Application No. 3-10604 are particularly preferable. Such water-soluble primer layer compounds preferably provided in the range of 1mg / m ² ~80mg / m ² in solid content.

The surface of the photosensitive layer provided as described above is preferably matted in order to shorten the vacuuming time during contact exposure using a vacuum baking frame and to prevent baking blur. Specifically, JP-A-50-125805 and JP-B-57-6
No. 582 and No. 61-28986, a method of providing a mat layer as described in JP-B No. 62-62337, and a method of heat-bonding a solid powder as described in JP-B No. 62-62337. . The developer for the photosensitive composition of the present invention is preferably an alkaline aqueous solution containing substantially no organic solvent, specifically, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, Aqueous solutions such as sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, aqueous ammonia are suitable. It is added so that the concentration thereof 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, sodium silicate, etc. is preferable because stains are less likely to occur during printing.
The composition of alkali silicate is [SiO ₂ ] / [M] = 0 in molar ratio.
5 to 2.5 (where [SiO ₂ ] and [M] represent the molar concentration of SiO _{2 and} the molar concentration of total alkali metals, respectively) and contain 0.8 to 8% by weight of SiO ₂ . A developing solution is preferably used. 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 preferred content of these compounds in the developer is 0.002 to 4% by weight, preferably 0.01 to 1% by weight.

In the developer, anionic surfactants and amphoteric surfactants such as those described in JP-A-50-51324 and JP-A-59-84241, and JP-A-59-75255 No. 60-111246, No. 60-213943, and the like, by incorporating at least one kind of nonionic surfactant, or JP-A-55-9.
Inclusion of a polyelectrolyte as described in JP-A Nos. 5946 and 50-142528 improves wettability with a photosensitive composition and enhances stability of development (development latitude). And can be preferably used.
The amount of such a surfactant added 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 the total alkali metal because insoluble matters are less generated in the developing solution, more preferably 90 mol% or more, and most preferably 100 mol%. Is the case.
Further, in the developer used in the present invention, some organic solvents such as alcohol, chelating agents described in JP-A-58-190952, and those described in JP-B-1-30139 are used. An antifoaming agent such as a metal salt or an organic silane compound can be added.

The light source used for the exposure includes a carbon arc lamp, a mercury lamp, a xenon lamp, a tungsten lamp, a metal halide lamp and the like. A photosensitive lithographic printing plate using the photosensitive composition of the present invention is disclosed in JP-A-54-8002.
Needless to say, the plate-making process may be carried out by the methods described in JP-A Nos. 55-115045 and 59-58431. That is, after the development processing, after washing with water, desensitizing treatment,
Alternatively, the desensitizing treatment may be performed as it is, or a treatment with an aqueous solution containing an acid, or a desensitizing treatment after the treatment with an aqueous solution containing an acid. Furthermore, in the developing step of this type of photosensitive lithographic printing plate, the aqueous alkali solution is consumed depending on the processing amount to reduce the alkali concentration, or the alkali concentration is reduced by air due to long-time operation of the automatic developer. Although the processing capacity decreases, at that time, the processing capacity may be recovered by using a replenisher as described in JP-A-54-62004. In this case, it is preferable to supplement by the method described in US Pat. No. 4,882,246. Further, the plate making process as described above is preferably carried out by an automatic processor as described in JP-A-2-7054 and JP-A-2-32357.

Further, when the photosensitive lithographic printing plate using the photosensitive composition of the present invention is imagewise exposed, developed, washed with water or rinsed, and then unnecessary image areas are erased, a special method is used. It is preferable to use an erasing liquid as described in 2-13293. Further, as a desensitizing gum which is optionally applied in the final step of the plate making process, Japanese Patent Publication No. 62-16834
No. 62-25118, No. 63-52600, JP-A No. 62-7595,
Those described in JP-A-62-11693 and JP-A-62-83194 are preferable. Furthermore, when the photosensitive lithographic printing plate using the photosensitive composition of the present invention is imagewise exposed, developed, washed with water or rinsed, erased if desired, and burned after washing, before burning. Nikkei Sho 61-2518
No. 55-28062, JP-A No. 62-31859, and JP-A No. 61-159655.

[0035]

The image-forming material using the photosensitive composition of the present invention is excellent in free radical generation efficiency upon imagewise exposure, and is excellent in visible visibility, particularly in low exposure. Little deterioration over time after the plate is manufactured.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the contents of the present invention are not limited thereto.

EXAMPLES The present invention will be described more specifically below with reference to examples. In addition, "%" in the examples means "% by weight" unless otherwise specified. Examples 1 to 9 and Comparative Examples 1 to 15 An aluminum plate having a thickness of 0.30 mm and a nylon brush and 40
The surface was grained using a 0-mesh aqueous suspension of pumice and then thoroughly washed with water. It was immersed in 10% sodium hydroxide at 70 ° C. for 60 seconds for etching, washed with running water, neutralized with 20% HNO ₃ and washed with water. This was subjected to electrolytic surface-roughening treatment in an aqueous 1% nitric acid solution under the condition of V _A = 12.7 V in an aqueous 1% nitric acid solution at an anode electricity of 160 coulomb / dm ² . The surface roughness was measured and found to be 0.6 μ (Ra indication). Subsequently, it was immersed in a 30% H ₂ SO ₄ aqueous solution and desmutted at 55 ° C. for 2 minutes, and then in a 20% H ₂ SO ₄ aqueous solution, the current density was 2 A / dm.
² anodized to a thickness of 2.7 g / m ² ,
A substrate was prepared. An 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 liquid (A) Aminoethylphosphonic acid 0.10 g Phenylphosphonic acid 0.15 g Triethanolamine 0.05 g β-alanine 0.10 g Methanol 40 g Pure water 60 g Thus, the substrate (I) was prepared. Next, 25 ml of the following photosensitive solution was applied onto this substrate (I) by rod coating.
/ M ^{2 and was} dried at 100 ° C for 1 minute to obtain a positive photosensitive lithographic printing plate. The coating amount after drying was about 1.7 g / m ² .

[Photosensitive Solution] Esterification product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (as described in Example 1 of US Pat. No. 3,635,709) 0.45 g Cresol-formaldehyde novolak resin (meta-para ratio; 6 to 4, weight average molecular weight 3,000, number average molecular weight 1,100, containing 0.7% unreacted cresol) 1.1 g m-cresol-formaldehyde novolac resin (weight average molecular weight 1,700, number average molecular weight 600, containing 1% of unreacted cresol) 0.3 g Condensation product of pyrogallol and acetone (weight average molecular weight 2,200, number average molecular weight 700) 0.1 g Poly [N- (P-amino Sulfonylphenyl) acryl amide-co-normal butyl acrylate-co-diethylene glycol monomethyl ether Crylate] (The molar ratio of each monomer is 40:40:20, weight average molecular weight 40,000, number average molecular weight 20,000) 0.2 g p-normal octylphenol-formaldehyde resin (described in US Pat. No. 4,123,279) 0.02 g Naphthoquinone diazide-1,2-diazide-4-sulfonic acid chloride 0.01 g

Tetrahydrophthalic anhydride 0.02 g Benzoic acid 0.02 g Pyrogallol 0.05 g Organohalogen compound (see Table 1) 0.02 g N- (1,2-naphthoquinone-2-diazide-4-sulfonyloxy) -cyclohexane -1,2-Dicarboxylic acid imide 0.01g Victoria Pure-Blue BOH [manufactured by Hodogaya Chemical Co., Ltd.] Dye in which the counter anion was changed to 1-naphthalenesulfonic acid 0.045g 1- [α-methyl-α- (4-Hydroxy-3,5-dihydroxymethylphenyl) ethyl] -4- [α, α-bis (4-hydroxy-3,5-dihydroxymethylphenyl) ethyl] benzene 0.04 g (Japanese Patent Application No. 4- 245049 Compound (X)) Megafac F-177 (Dainippon Ink and Chemicals, Inc. Fluorine-based surfactant) 0.01 g Ethyl ketone 20g Methanol 4.5g Propylene glycol monomethyl ether 0.3g Water 0.2g

The photosensitive lithographic printing plate thus prepared was passed through a transparent positive film in a vacuum baking frame for 1 m.
After exposure for 15 seconds or 1 minute from a distance of 3 kw with a metal halide lamp, the density difference ΔD between the exposed portion (non-image portion) and the unexposed portion (solid image) was measured with a Macbeth reflection densitometer. The results are shown in Table 1. The sensitivity is a step wedge made by Fuji Photo Film Co., Ltd. (the density difference between each step is 0.1
After 5) was baked onto the photosensitive lithographic printing plate by the above method, a 5.26% aqueous solution of potassium silicate (pH = 12.7) having a SiO ₂ / K ₂ O molar ratio of 1.74 at 25 ° C. for 30 seconds. ), The number of clear steps was 1 step for 15-second exposure and 5 steps for 1-minute exposure. Further, the same measurement was performed on a sample in which the photosensitive lithographic printing plate sample was stored at 60 ° C. and 80% humidity for 3 days. The results are shown in Table 1. Comparative examples of the organic halogen compounds (C1) to (C3) are disclosed in US Pat.
It is described in No. 3,954,475.

[0040]

[Chemical 4]

[0041]

[Table 1] ─────────────────────────────────── Organic halogen compounds Exposure Visibility Visual exposure Exposure after aging Visibility 15 second exposure 1 minute exposure 15 second exposure 1 minute exposure ──────────────────────────────────── Compound (1) of the present invention 0.15 0.27 0.15 0.26 Compound (2) of the present invention 0.16 0.28 0.15 0.27 Compound (3) 0.14 0.1 of the present invention 27 0.14 0.26 Compound (4) of the present invention 0.14 0.27 0.14 0.26 Compound (C1) of Comparative Example 0.05 05.23 0.02 0.11 Compound of Comparative Example ( C2) 0.06 0.24 0.02 0.12 Comparative Example Compound (C3) 0.05 05.24 0.03 0.12 ────────────────── ──────────────────

As is apparent from Table 1, the photosensitive lithographic printing plate using the photosensitive composition of the present invention has an exposure visible image property.
In particular, it is excellent in low exposure and has little deterioration even when it is aged under high temperature and high humidity.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03F 7/039 7/105

Claims (1)

[Claims] 1. A photosensitive composition which acts positively, comprising a compound represented by the following general formula (I) and a dye capable of interacting with a photodegradation product of the compound. Composition. [Chemical 1] In the formula, R ¹ and R ² are each a hydrogen atom or a carbon number of 1 to
8 represents an alkyl group, X represents a halogen atom, and m represents an integer of 1 to 3.