JP2001215688A - Photosensitive planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type photosensitive planographic printing plate less liable to form an unnecessary image of an edge part on a printing plate, ensuring good image visibility after exposure and good plate inspectability after development and having high sensitivity. SOLUTION: The photosensitive planographic printing plate has a photosensitive layer containing a photo-acid generating agent, o-naphthoquinone diazide and a compound whose absorption is varied by an acid. The absorbance of the photosensitive layer freed of the o-naphthoquinone diazide at 400 nm increases by >=0.03 after exposure. The photosensitive planographic printing plate is preferably obtained by disposing a middle layer containing a high molecular compound containing (a) a unit which interacts with an alumina layer and (b) a unit which interacts with a layer formed by treatment for imparting hydrophilic property on an aluminum substrate subjected to anodic oxidation and treatment for imparting hydrophilic property and then disposing the photosensitive layer on the middle layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate. In particular, it is intended to provide a positive photosensitive lithographic printing plate which is difficult to form an unnecessary image at the edge portion of a conventional plate making film, has high sensitivity, and has good visibility after exposure and good plate inspection after development. .

[0002]

2. Description of the Related Art A positive type photosensitive resin composition layer (hereinafter sometimes referred to as a photosensitive layer or a photosensitive layer) is provided on an aluminum support which has been previously grained and anodized. A photosensitive lithographic printing plate (hereinafter referred to as “positive type P
S version ". ) Is exposed through a positive transparent original to increase the solubility of the exposed portion in a developing solution,
When this is treated with a developer of a positive photosensitive resin composition, the exposed portions of the photosensitive layer are removed, exposing the hydrophilic surface of the support, and thus a positive image is formed. In this case, since light is scattered at the edge portion of the film, the amount of light is insufficient, and an unnecessary image of the portion is formed on the plate, and it is necessary to erase the image after development. For this reason, in recent years, a plate on which an image that needs to be erased is difficult to be formed has been desired.

In order to solve this problem, US Pat.
No. 1,516 discloses an aluminum support having a surface exhibiting a dark steel gray shade obtained by graining an aluminum plate with a wet abrasive such as a pumice slurry and then immediately anodizing in sulfuric acid. A positive PS plate using a body has been proposed. However, since the surface of the aluminum support of this positive PS plate has a low reflectance from the ultraviolet region to the visible light region, a printed image obtained at the time of image exposure becomes difficult to see, and the feeling formed after development is low. The contrast between the greasy image and the surface of the support is low, resulting in poor so-called plate inspection, and has a drawback of causing a problem in that correction work such as erasure or retouching is hindered.

In a system using a yellow dye as described in Japanese Patent Publication No. 7-43333, an unnecessary image on the edge portion of a film is hardly formed on a plate. Use of a dye causes a problem that sensitivity is significantly reduced. As a method for solving this, JP-A-2-226250, JP-A-4-3160
49, JP-A-59-142538, JP-A-58-875
Among the azo dyes described in JP-A-53-53, there is a method of adding a yellow dye in particular, but in these systems, the contrast between the image area and the non-image area after exposure is reduced due to the color development of the azo dye. Inferior.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for forming an unnecessary image on an edge portion of a film less easily than a conventional positive type photosensitive lithographic printing plate. An object of the present invention is to provide a positive photosensitive lithographic printing plate having good plate inspection properties after development and having high sensitivity.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object can be achieved by adding a predetermined amount of a photoacid generator and a compound whose absorption changes by an acid to a photosensitive layer. The present invention has been accomplished. That is, the present invention is as follows. (1) having a photosensitive layer containing a photoacid generator, o-naphthoquinonediazide, and a compound whose absorption is changed by an acid;
-400 nm of the photosensitive layer excluding naphthoquinonediazide
A photosensitive lithographic printing plate wherein the absorbance of the lithographic printing plate increases by 0.03 or more before and after exposure. (2) A polymer compound containing (a) a unit interacting with an alumina layer and (b) a unit interacting with a hydrophilic treatment layer is contained on an aluminum support subjected to anodizing treatment and hydrophilic treatment. The photosensitive lithographic printing plate according to (1), wherein the photosensitive layer is provided on an intermediate layer provided.

[0007] In a conventional positive PS plate, when a sufficient actinic light is not irradiated due to sticking of a film, dust, or the like, an image remains in an unnecessary portion. In order to eliminate this phenomenon, use a high-sensitivity photosensitive layer or increase the amount of active light irradiation so that development can be performed even in areas where the light is weak, such as the part where the film is stuck or the part with dust. Needed. However, in a positive PS plate using a photosensitive substance such as o-naphthoquinonediazide, which does not absorb due to a photoreaction by irradiation with actinic light, an actinic light exceeding a necessary amount (hereinafter abbreviated as surplus light) is absorbed by other substances. The light is transmitted through the photosensitive layer in the unexposed area. For this reason, surplus light passing through the non-image portion of the film, which is an exposed portion, goes around to the photosensitive layer below the image portion of the film to which light should not originally hit, because it is reflected on the support. As a result, a phenomenon has occurred in which the area around the image area in contact with the non-image area is developed and the image area becomes thin. For this reason, all the small halftone dots disappeared, and the reproducibility of the minimum halftone dot deteriorated. In order to reduce this phenomenon, it was considered necessary to reduce the excess light transmitted through the exposed portion. For this purpose, a method is known in which a substance (for example, a yellow dye) that does not lose absorption of active light upon exposure is added (Japanese Patent Application Laid-Open No. 9-179290). However, this method has a problem that light is weakened even in an exposed portion that becomes a non-image portion, and the photosensitive layer has low sensitivity.

On the other hand, the photosensitive lithographic printing plate of the present invention has a photosensitive layer thickness of 400 excluding o-naphthoquinonediazide.
The photosensitive layer was made to contain a photoacid generator and a compound whose absorption changed by an acid so that the absorbance in nm increased by 0.03 or more before and after exposure. As a result, the light is not blocked as long as the light exposure immediately after the start of the exposure is small, but when the exposure proceeds and the photosensitive substance (o-naphthoquinonediazide) undergoes a photoreaction and the absorption stops, the light is absorbed by the photoacid generator and the acid. It has been found that the compound having a change in the absorption of light makes it possible to absorb light in the vicinity of 400 nm, thereby preventing the light from entering the image area. As a result, the minimum halftone dot can be obtained with a highly sensitive PS plate that effectively utilizes light. Furthermore, when a combination of a dye that changes color with an acid and a photoacid generator is used as a compound combination, the It was found that the print-out image obtained at the time of exposure was easy to see and the plate inspection after development was easy to come out.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the photosensitive lithographic printing plate of the present invention will be described in detail. First, a compound contained in the photosensitive layer of the photosensitive lithographic printing plate of the present invention, the absorption of which is changed by a photoacid generator and an acid will be described.

"Photoacid generator" The photoacid generator contained in the photosensitive layer of the photosensitive lithographic printing plate of the present invention is capable of generating and generating an acid when exposed to light during image exposure of the photosensitive lithographic printing plate. The acid is not particularly limited as long as it has a pka of 2 or less. For example, JP-A-50-36209 (U.S. Pat.
O-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-118-118, and trihalomethyl- described in JP-A-53-36223 (U.S. Pat. No. 4,160,671).
2-pyrone and trihalomethyltricidin;
Various o-naphthoquinonediazide compounds described in U.S. Pat. No. 62,444 (U.S. Pat. No. 2,038,801);
-77742 (U.S. Pat. No. 4,279,982) described in 2-Trihalomethyl-5-aryl-1,3,4-
Oxadiazole compounds and the like can be mentioned. If the pka of the generated acid is larger than 2, the discoloration is small and the effect of the present invention is reduced.

"Compound whose absorption is changed by acid" The compound whose absorption is changed by an acid contained in the photosensitive layer of the photosensitive lithographic printing plate of the present invention is a compound which absorbs light by the acid generated from the photoacid generator. Is not particularly limited as long as it shifts to short waves, but Victoria Pure Blue BOH, Methyl Violet BB Special, Crystal Violet Power, Rhodamine BH, Basic Cyanine 6GH,
Casillon Blue 2RLH, Diamond Green GH,
Malachite Green [Hodogaya Chemical Industry Co., Ltd.
Primocyanin BXconc. [Manufactured by Sumitomo Chemical Co., Ltd.] and those obtained by changing these counter ions to ions of an organic substance such as 1-naphthalenesulfonic acid.

In the photosensitive layer of the photosensitive lithographic printing plate of the present invention, the content of the photoacid generator and the compound whose absorption is changed by an acid depends on the exposure conditions, the thickness of the photosensitive layer, and the content of o-naphthoquinonediazide described later. Since it varies depending on the type, the content of o-naphthoquinonediazide, and the usage of other additives, it cannot be specified unconditionally. However, the absorbance at 400 nm of the photosensitive layer excluding o-naphthoquinonediazide before and after the exposure is 0.1. It should be set appropriately so as to increase by 03 or more. Examples of the o-naphthoquinonediazide contained in the photosensitive layer of the photosensitive lithographic printing plate of the present invention include 1,2-diazonaphthoquinonesulfonic acid chloride and pyrogallol described in JP-B-43-28403.
Those which are esters with an acetone resin are preferred.

[0013] Other suitable o-naphthoquinonediazides include 1,2,3,2,3,4,5,6,7,8,7,8,7,8,7,8,7,8,7,8,9
There are esters of diazonaphthoquinone sulfonic acid chloride with phenol formaldehyde resin.

[0014] Other useful o-naphthoquinonediazides include those reported and known in numerous patents. For example, Japanese Patent Application Laid-Open No. 47-5303,
JP-A-48-63802, JP-A-48-63803, JP-A-48-96575, JP-A-49-38701, JP-A-48-13354, and JP-B-37-180.
No. 15, No. 41-11222, No. 45-96
No. 10, JP-A-49-17481, JP-A-5-1
1444, JP-A-5-19477, JP-A-5-19478, JP-A-5-107755, U.S. Pat. Nos. 2,797,213 and 3,45.
No. 4,400, No. 3,544,323, No. 3,5
No. 73,917, No. 3,674,495, No. 3,
785,825, British Patent No. 1,227,602,
Nos. 1,251,345 and 1,267,005
No. 1,329,888, No. 1,330,93
No. 2, German Patent No. 854,890, and the like.

Further, as other o-naphthoquinonediazide, those obtained by reacting a polyhydroxy compound having a molecular weight of 1,000 or less with 1,2-diazonaphthoquinonesulfonic acid chloride can be used. For example, JP-A-51-139402 and JP-A-58-1509.
No. 48, No. 58-203434, No. 59-1
JP-A-65053, JP-A-60-121445, JP-A-6
Nos. 0-134235, 60-16343, 61-118744, 62-10645
JP-A-62-10646 and JP-A-62-1539
Nos. 50, 62-178562 and 64-7
No. 6047, U.S. Pat. Nos. 3,102,809, 3,126,281, and 3,130,047,
No. 3,148,983, No. 3,184,310
No. 3,188,210, No. 4,639,40
No. 6, etc. or those described in the specification.

When 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. More preferably, the reaction is performed in an amount of 0.3 to 1.0 equivalent. As the 1,2-diazonaphthoquinonesulfonic acid chloride, 1,2-diazonaphthoquinone-5-sulfonic acid chloride is preferable, but 1,2-diazonaphthoquinone-sulfonic acid chloride is preferred.
4-sulfonic acid chloride can also be used. Also, the obtained o-naphthoquinonediazide is a mixture of various kinds of 1,2-diazonaphthoquinonesulfonic acid ester groups having different positions and introduced amounts, but all the hydroxyl groups were converted to 1,2-diazonaphthoquinonesulfonic acid esters. The proportion of the compound in the mixture (the content of the completely esterified compound) is preferably 5 mol% or more, more preferably 20 to 99 mol%.

The amount of o-naphthoquinonediazide in the photosensitive layer of the photosensitive lithographic printing plate of the present invention is 10 to 80% by weight, preferably 15 to 50% by weight, more preferably 20%.
~ 35% by weight.

In the photosensitive layer of the photosensitive lithographic printing plate of the present invention,
In addition to the photoacid generator, the compound whose absorption is changed by an acid, and o-naphthoquinonediazide, other components may be contained. For example, the photosensitive layer preferably contains a resin which is soluble in water and insoluble in water as a binder.

As such resins soluble in alkaline water, there are novolak resins having this property. For example, phenol formaldehyde resin, m-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-, m- / o
And cresol formaldehyde resin such as mixed formaldehyde resin. In addition, resol type phenol resins are also suitably used, and a phenol / cresol (m-, p-, o- or a mixture of m- / p-, m- / o-) mixed formaldehyde resin is preferable. In particular, JP-A-61-
Phenolic resins described in Japanese Patent No. 217034 are preferred.

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 be used. These alkali-soluble polymer compounds have a weight average molecular weight of 50.
0-100,000 and number average molecular weight of 200-60,0
00 is preferred.

The alkali-soluble high molecular compound is 1
They may be used alone or in combination of two or more, and are used in an amount of 80% by weight or less, preferably 30 to 75% by weight, more preferably 50 to 65% by weight of the total composition. This range is preferable from the viewpoints of developability and printing durability. Further, as described in U.S. Pat. No. 4,123,279, phenol having a C3-8 alkyl group as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin, and formaldehyde are used. It is preferable to use a condensate with the above in view of improving the oil sensitivity of the image.

It is preferable that a cyclic acid anhydride, a phenol, or an organic acid is added to the photosensitive layer in order to enhance the sensitivity. As the cyclic acid anhydride, U.S. Pat.
Phthalic anhydride as described in 15,128 Pat, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride Chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like. 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 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 proportion of phenols and organic acids in the photosensitive layer is
0.05 to 15% by weight is preferable, and more preferably,
0.1 to 5% by weight.

In order to widen the development latitude, a nonionic surfactant such as that described in JP-A Nos. 62-251740 and 4-68355 is incorporated in the photosensitive layer. And amphoteric surfactants described in JP-A-59-121044 and JP-A-4-13149. 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, Ammogen K (trade name, manufactured by Dai-ichi Kogyo Co., Ltd., N-tetradecyl-N, N-betaine type), 2- Alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, Levon 15 (trade name, manufactured by Sanyo Chemical Co., Ltd., alkylimidazoline system) and the like. The proportion of the nonionic surfactant and amphoteric surfactant in the photosensitive layer is preferably 0.05 to 15% by weight, and more preferably 0.1 to 15% by weight.
1 to 5% by weight.

The photosensitive lithographic printing plate of the present invention can be obtained by dissolving the components of the respective photosensitive layers in a solvent capable of dissolving and coating the solution on a support described later. As the solvent used here, γ-butyrolactone, 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, dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, isopropanol, diethylene glycol dimethyl ether, etc. These solvents are used alone or as a mixture. The concentration (solid content) in the above components is suitably 2 to 50% by weight.

The coating amount is 0.5 g / m ^{2 to} 2.5 g
/ M ² is preferred. When the amount is less than 0.5 g / m ² , the printing durability deteriorates. If it is more than 2.5 g / m ² , tone reproducibility deteriorates.

In the photosensitive lithographic printing plate of the present invention, when the photosensitive layer is coated, a surfactant for improving the coating property is described, for example, in JP-A-62-170950. Such a fluorine-based surfactant can be added. A preferable addition amount is 0.0% of all the photosensitive layer components.
1 to 1% by weight, more preferably 0.05 to 0.5% by weight
It is. The surface of the photosensitive layer provided as described above,
In order to shorten the evacuation time during contact exposure using a vacuum furnace and to prevent burning, matting is preferred. Specifically, Japanese Patent Application Laid-Open No. 50-125805, Japanese Patent Publication No. No. 6,582,61-28986, a method for providing a mat layer as described in
And a method of thermally fusing a solid powder as described in JP-A-62337.

In the photosensitive lithographic printing plate of the present invention, the support for coating the photosensitive layer is not particularly limited as long as it has a hydrophilic surface, but an aluminum plate or the like is preferable. As the aluminum plate, there is a plate-like body such as pure aluminum or an aluminum alloy containing aluminum as a main component and containing a trace amount of a different atom. This foreign atom
There are silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The synthetic composition has a heteroatom content of 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 aluminum contains as little foreign atoms as possible. In addition, any aluminum alloy having the above-described heteroatom content can be said to be a material that can be used in the present invention. Thus, the aluminum plate used in the present invention is:
The composition is not particularly limited, and those of conventionally known and public materials can be appropriately used. Preferred materials are JISA 1050, 1100, 12
00, 3003, 3103, and 3005 materials. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm. Prior to the surface roughening treatment of the aluminum plate, a degreasing treatment, for example, a treatment with a surfactant or an alkaline aqueous solution for removing rolling oil on the surface is performed as necessary.

The aluminum plate used for the photosensitive lithographic printing plate of the present invention is preferably one whose surface has been subjected to anodizing treatment and hydrophilic treatment. In addition,
The aluminum plate is subjected to a surface roughening treatment prior to the anodizing treatment. Methods for roughening the surface of the aluminum plate include a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically selectively dissolving the surface. As the mechanical method, a known method called a ball polishing method, a brush polishing method, a blast polishing method, a buff polishing method, or the like can be used. In addition, 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. Also, Japanese Patent Application Laid-Open No. 54-63902
As disclosed in Japanese Unexamined Patent Publication (Kokai) No. H11-284, a method in which both are combined can also be used. The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment as required, and then subjected to an anodic oxidation treatment in order to increase the water retention and abrasion resistance of the surface. 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. In general, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. The concentration of these electrolytes 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. However, in general, the concentration of the electrolyte is 1 to 80% solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A / dm ^2. , Voltage 1-1
It is appropriate that the electrolysis time is in the range of 00 V and the electrolysis time is 10 seconds to 5 minutes. The amount of the anodized film is suitably 1.0 g / m ² or more, but more preferably in the range of 2.0 to 6.0 g / m ^2. When the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient, and the non-image area of the lithographic printing plate is easily damaged, and the ink adheres to the damaged area during printing. "Scratch dirt" is likely to occur. Incidentally, such an anodizing treatment is performed on the surface used for printing of the support of the photosensitive lithographic printing plate.
Generally, an anodic oxide film of ３3 g / m ² is formed.

As the hydrophilization treatment used after the above-mentioned treatment, a conventionally known hydrophilization treatment is used. Examples of such a hydrophilic treatment include U.S. Pat. Nos. 2,714,066 and 3,181,461.
There is an alkali metal silicate (for example, sodium silicate aqueous solution) method as disclosed in 3,280,734 and 3,902,734. In this method, the support is immersed or electrolytically treated in an aqueous solution of sodium silicate. Alternatively, potassium fluorozirconate disclosed in JP-B-36-22063 and U.S. Pat. Nos. 3,276,868 and 4,153,461.
No. 4,689,272, a method of treating with polyvinyl phosphonic acid or the like is used. Among these, a particularly preferred hydrophilic treatment in the present invention is a silicate treatment. The silicate treatment will be described below.

The anodic oxide film of the aluminum plate treated as described above was coated with an alkali metal silicate in an amount of 0.001-3.
0% by weight, preferably 0.005 to 10% by weight,
An aqueous solution having a pH of 10 to 13 at 25 ° C.
Immerse for 0.5 to 120 seconds at 5 to 80 ° C. If the pH of the aqueous alkali metal silicate solution is lower than 10, the solution gels and 1
If it is higher than 3.0, the oxide film will be dissolved. As the alkali metal silicate used in the present invention, sodium silicate, potassium silicate, lithium silicate and the like are used. Hydroxides used to raise the pH of the aqueous alkali metal silicate solution include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. In addition, an alkaline earth metal salt or a Group IVB metal salt may be added to the above-mentioned processing solution. As alkaline earth metal salts, calcium nitrate,
Nitrate such as strontium nitrate, magnesium nitrate, barium nitrate, sulfate, hydrochloride, phosphate, acetate,
And water-soluble salts such as oxalates and borates. IVB
Group IV metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride and the like. . Alkaline earth metal salt or
The Group IVB metal salts can be used alone or in combination of two or more. The preferred range of these metal salts is 0.0
1 to 10% by weight, more preferably 0.05 to 10% by weight.
5.0% by weight. Since the silicate treatment further improves the hydrophilicity on the aluminum plate surface, the ink hardly adheres to the non-image area during printing, and the stain performance is improved.

Further, a back coat is provided on the back surface of the support used in the photosensitive lithographic printing plate of the present invention, if necessary. Such a back coat is disclosed in JP-A-5-4.
Organic polymer compound described in JP-A No.
A coating layer comprising a metal oxide obtained by hydrolysis and polycondensation of an organic or inorganic metal compound described in JP-A-35174 is preferably used. Of these coating layers, Si
(OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC
Alkoxy compounds of silicon such as ₃ H ₇ ) ₄ and Si (OC ₄ H ₉ ) ₄ are easily available at a low cost, and a coating layer of a metal oxide provided therefrom is particularly preferable because of excellent development resistance.

In the photosensitive lithographic printing plate of the present invention, (a) a unit interacting with the alumina layer and (a) are provided between the photosensitive layer and the aluminum support subjected to the anodic oxidation treatment and the hydrophilic treatment. B) It is preferable to have an intermediate layer containing a polymer compound containing a unit that interacts with the hydrophilic treatment layer. By having the intermediate layer containing the polymer compound, the adhesion was improved in the image area, and the printing durability and chemical resistance were significantly improved. Further, in the non-image area, the polymer compound has an affinity for the alkali developing solution, so that the polymer compound is removed from the surface of the support. Therefore, in the non-image area, the surface of the support subjected to the hydrophilization treatment by the development treatment was exposed, so that the stain performance was also good. In addition, since a developing solution containing silicate is not necessarily required as a developing solution, the developing solution containing silicate as a main component is solidified in a developing bath or a liquid feed pipe of an automatic developing machine, and a sensor is used. Problems such as erroneous operation and liquid clogging in the piping are eliminated, and complicated cleaning and replacement work are not required. Furthermore, surprisingly, the erasing performance, residual color and print-out performance were also very good.

The polymer compound contained in the intermediate layer will be described in detail. As described above, the polymer compound includes (a) a unit interacting with the alumina layer (referred to as unit (a)) and (b) a unit interacting with the hydrophilic treatment layer (referred to as unit (b)). Contains. here,
The “unit that interacts with the alumina layer” refers to a monomer (single monomer) having an Rf value of 0.5 or less, preferably 0.2 or less when developed by thin layer chromatography containing alumina as a main component with methanol. (Referred to as a compound (a)) and is a unit constituting a polymer compound produced by polymerization with the following monomer (b). The “unit that interacts with the hydrophilization treatment layer” refers to a monomer having an Rf value of 0.5 or less, preferably 0.2 or less when thin-layer chromatography containing silica as a main component is developed with methanol. It is a unit derived from a body (referred to as a monomer (b)) and constituting a polymer compound produced by polymerization with the monomer (a).

The polymer compound is preferably an addition polymer of a vinyl monomer exemplified by an acrylic resin, a methacrylic resin and polystyrene, or a polyaddition polymer or a polyaddition polymer exemplified by a urethane resin, polyester or polyamide. It is a condensation polymer. More preferably, it is an addition polymer of the vinyl monomer. Particularly preferred polymer compounds are those represented by the following general formula (1) or (2) as the monomer (a), and the following general formulas (3) and (4) as the monomer (b) ) Or (5) is obtained by copolymerization using the monomer represented by (5).

The monomer (A) can be appropriately selected from monomers having an acid group, monomers having an alkyleneoxy group, monomers having an onium group, and the like. First, the monomer (a) having an acid group will be described. Preferred as acid groups are those acid dissociation constant (pKa) of 7 or less, more preferably -COOH, -SO ₃ H, -OSO _{3
H, -PO 3 H 2, -OPO} 3 H 2, -CONHSO 2 -,
—SO ₂ NHSO ₂ —, more preferably —COOH
It is. Particularly preferred monomer (a) having an acid group is a monomer represented by the following general formula (1) or (2).

[0037]

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In the formula, A represents a divalent linking group. B represents an aromatic group or a substituted aromatic group. D and E each independently represent a divalent linking group. G represents a trivalent linking group. X and X 'each independently represent an acid group having a pKa of 7 or less, or an alkali metal salt or ammonium salt thereof. R ₁ represents a hydrogen atom, an alkyl group or a halogen atom. a, b, d, and e each independently represent 0 or 1. t is an integer of 1 to 3. In the formula, more preferably, A is -COO- or -CONH-, B is a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group, a halogen atom or an alkyl group, and D and E are independently represent an alkylene group or the formula C _n H _2n O, a divalent linking group represented by C _n H _2n S or _{C n H 2n + 1 n,} G has the formula C _n H _2n-1, C _n H
_2n-1 O, a divalent linking group represented by C _n H _2n-1 S or a trivalent linking group represented by C _n H _2n N (where n represents an integer of 1 to 12) ), X and X ′ are each independently a carboxylic acid, sulfonic acid, phosphonic acid, sulfuric acid monoester or phosphoric acid monoester, R ₁ is a hydrogen atom or an alkyl group, and a, b, d and e are Each is independently 0 or 1, but a and b are not simultaneously 0. Among the monomers (a) having an acid group, a compound represented by the general formula (1) is particularly preferable, wherein B represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group or a group having 1 to 3 carbon atoms. Is an alkyl group. D and E
Each independently represents an alkylene group having 1 to 2 carbon atoms or an alkylene group having 1 to 2 carbon atoms linked by an oxygen atom. R ₁ represents a hydrogen atom or a methyl group. X represents a carboxylic acid group. a is 0 and b is 1.

Specific examples of the monomer (a) having an acid group are shown below. However, the present invention is not limited to this specific example. (Specific Examples of Monomer (A) Having Acid Group) Acrylic acid (Rf: 0.09), methacrylic acid (Rf: 0.0
9), maleic acid (Rf: 0.00),

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[0041]

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Specific examples of another type of the monomer (a) include the following monomers.

[0043]

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The monomer (b) is appropriately selected from a compound having an onium group, a monomer having an alkyleneoxy group, and the like. The monomer (b) having an onium group is typically represented by the following general formulas (3), (4), and (5).

[0045]

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In the above formulas (3) to (5), J is a divalent linkage
Represents a group. K represents an aromatic group or a substituted aromatic group.
M each independently represents a divalent linking group. Y₁Is the period
Y represents an atom belonging to Group V of the_TwoIs an atom from Group VI of the periodic table
Represents Z^-Represents a counter anion. R_TwoIs a hydrogen atom, al
Represents a kill group or a halogen atom. R_Three, R_Four, R_Five, R ₇
Are each independently a hydrogen atom or, in some cases,
Alkyl group, aromatic group, aralkyl
R₆Is an alkylidyne group or substituted alkyl
Represents lysine, but R_ThreeAnd R_FourOr R₆And R₇Are each
They may combine to form a ring. j, k and m are German
Stands for 0 or 1. u represents an integer of 1 to 3.

More preferred monomer (b) having an onium group is a compound represented by the general formulas (3) to (5) wherein J is -CO
O- or -CONH-, K is a phenylene group or a substituted phenylene group, the substituent is a hydroxyl group, a halogen atom or an alkyl group, and M is an alkylene group or a formula C
_n H _2n O, 2 represented by C _n H _2n S or C _n H _{2n + 1} N
A divalent linking group (where n is an integer of 1 to 12), Y ₁ is a nitrogen atom or a phosphorus atom, Y ₂ is a sulfur atom, Z ⁻ is a halogen ion, PF ₆ ⁻ , BF ₄
^- or R ₈ SO ₃ ^- a and, R ₂ is a hydrogen atom or an alkyl _{group, R 3, R 4, R} 5, R 7 are each independently
Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms to which a substituent may be bonded, an aromatic group, or an aralkyl group, and R ₆ is an alkylidine group having 1 to 10 carbon atoms or a substituted alkylidine; R ₃ and R ₄ or R ₆ and R ₇ may be bonded to each other to form a ring, and j, k, m
Are each independently 0 or 1 (provided that j and k are
Do not become 0 at the same time).

In particular, the above monomer having an onium group (b)
Is a group in which K is a phenylene group or a substituted phenylene group, the substituent is a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and M has 1 to 1 carbon atoms linked by an alkylene group having 1 to 2 carbon atoms or an oxygen atom. a second alkylene group, Z ^- is chloride ion or R ₈ SO ₃ ^- is, R ₂ is a hydrogen atom or a methyl group, j is 0, and those k is 1.

Specific examples of the above monomer (b) having an onium group are shown below. However, it is not limited to this specific example. (Specific examples of monomer (b) having an onium group)

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As another type of the monomer (b), 4-
Those containing crown ether and 6-crown ether can be mentioned.

The polymer compound of the present invention contained in the intermediate layer contains unit (a) in an amount of 5 mol% or more, preferably 10 mol%.
As described above, it is particularly preferable that the content is 15 to 95 mol%, and the unit (b) is 1 mol% or more, preferably 5 mol% or more, and particularly preferably 5 to 85 mol%. When the unit (A) is contained in an amount of 20 mol% or more, the removability during alkali development is further promoted. Is done. The unit (a) is one type or two.
More than one kind may be combined, and the unit (b) may be one kind or two or more kinds. Further, the intermediate layer may contain two or more kinds of units (a) and (b), and high molecular compounds having different composition ratios or molecular weights of these units.

Next, typical examples of the polymer compound used for the intermediate layer are shown below. The composition ratio of the polymer structure represents a mole percentage.

[0054]

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[0055]

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[0056]

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[0057]

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The polymer compound can be generally produced by using a radical chain polymerization method (“Textbook
f Polymer Science "3rd ed, (1984) FW Billmeyer, A Wi
ley-Interscience Publication). Although the molecular weight of the polymer compound may be in a wide range, when measured by a light scattering method, the weight average molecular weight (Mw) is 500 to 2.0.
00,000 and preferably 2,000 to
More preferably, it is in the range of 600,000. Further, the amount of unreacted monomer contained in the polymer compound may be wide, but is preferably 20% by weight or less, and more preferably 10% by weight or less.

Next, a synthesis example of the polymer compound contained in the intermediate layer will be described. [Synthesis Example] Synthesis of copolymer (No. 1) of p-vinylbenzoic acid and vinylbenzyltrimethylammonium chloride p-vinylbenzoic acid [manufactured by Hokuko Chemical Industry Co., Ltd.] 146.
9 g (0.99 mol), 44.2 g (0.21 mol) of vinylbenzyltrimethylammonium chloride and 446 g of 2-methoxyethanol were placed in a 1-liter three-neck flask, and heated to 75 ° C. while stirring under a nitrogen stream.
Kept. Next, 2,76 g (12 mmol) of dimethyl 2,2-azobis (isobutyrate) was added, and stirring was continued. 2
After an hour, 2,2-azobis (isobutyric acid) dimethyl 2,7
An additional 6 g (12 mmol) was added. After another two hours,
2.76 g of dimethyl 2,2-azobis (isobutyrate) (1
2 mmol) was added. After stirring for 2 hours, the mixture was allowed to cool to room temperature. The reaction solution was poured into 12 liters of ethyl acetate with stirring. The precipitated solid was collected by filtration and dried. The yield was 189.5 g. As a result of measuring the molecular weight of the obtained solid by a light scattering method, the weight average molecular weight (Mw) was 32,000. Other polymer compounds are synthesized in a similar manner.

The intermediate layer containing the above-mentioned polymer compound is provided on the aluminum plate which has been subjected to the above-mentioned hydrophilic treatment, by applying the intermediate layer by various methods.

This intermediate layer can be provided by the following method. A method in which a solution obtained by dissolving the above-mentioned polymer compound in an organic solvent such as methanol, ethanol, methyl ethyl ketone or the like or a mixed solvent thereof or a mixed solvent of these organic solvents and water is applied on an aluminum plate, dried, and provided. Ethanol, a solution in which the above-described polymer compound is dissolved in an organic solvent such as methyl ethyl ketone or a mixed solvent of these organic solvents and water, or a solution obtained by dissolving the above-described polymer compound in a mixed solvent thereof is adsorbed on the aluminum plate to adsorb the polymer compound. This is a method of providing an organic intermediate layer by washing and drying with water or the like. In the former method, a solution of the polymer compound having a concentration of 0.005 to 10% by weight can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. Also, in the latter method, the concentration of the solution is 0.1.
01 to 20% by weight, preferably 0.05 to 5% by weight, and the immersion temperature is 20 to 90 ° C, preferably 25 to 50 ° C.
The immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute. The above solution is a basic substance such as ammonia, triethylamine and potassium hydroxide, inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid, organic sulfonic acids such as nitrobenzenesulfonic acid and naphthalenesulfonic acid, and phenylsulfonic acid and the like. Various organic acidic substances such as organic phosphonic acids, benzoic acid, coumaric acid, organic carboxylic acids such as malic acid,
The pH can be adjusted with an organic acid chloride such as naphthalene sulfonyl chloride and benzenesulfonyl chloride, and the pH can be used in the range of 0 to 12, more preferably 0 to 5. Further, a yellow dye can be added for improving the tone reproducibility of the photosensitive lithographic printing plate. The coating amount of the polymer compound of the present invention after drying is from 2 to
100 mg / m ² is appropriate, preferably 5 to 50 m
g / m ² . If the coating amount is less than 2 mg / m ² , a sufficient effect cannot be obtained. In addition, 100 mg / m ²
The same applies to more.

The developer for the photosensitive lithographic printing plate of the present invention is preferably an alkaline aqueous solution substantially free of an organic solvent, and specifically, sodium silicate, potassium silicate,
Sodium hydroxide, potassium hydroxide, lithium hydroxide,
An aqueous solution such as sodium phosphate tribasic, sodium phosphate dibasic, ammonium phosphate tribasic, ammonium phosphate dibasic, sodium metasilicate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, aqueous ammonia, etc. Suitably, they are added in a concentration of 0.1 to 10% by weight, preferably 0.5 to 5% by weight. Among these, potassium silicate, lithium silicate,
A developer containing an alkali silicate such as sodium silicate is preferable because it hardly causes stain at the time of printing. The composition of the alkali silicate is [SiO ₂ ] / [M] = 0.5 to 0.5 in a molar ratio.
2.5 (where [SiO ₂ ] and [M] are Si
The molar concentration of O _{2 and} the molar concentration of total alkali metal are shown. )
, And the and the developer containing SiO ₂ 0.8 to 8 wt% 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 preferred content of these compounds in the developer is 0.002 to 4% by weight, preferably 0.1 to 4% by weight.
0.01 to 1% by weight.

In the developer, JP-A-50-5132 was used.
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, 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 of the total alkali metal because less insoluble matter is generated in the developer, more preferably 90 mol% or more, and most preferably 100 mol% or more.
It is the case of mol%. Further, the developing solution used in the present invention may contain some organic solvents such as alcohols and
Chelating agents described in JP-A-0952, JP-B-1
An antifoaming agent such as a metal salt and an organic silane compound as described in JP-A-30139 can 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
-8002, 55-115045 and 59-58
Needless to say, the plate-making process may be performed by the method described in each publication of No. 431. That is, after the development processing, washing with water and then desensitization processing, or desensitization processing as it is,
Alternatively, treatment with an aqueous solution containing an acid or treatment with an aqueous solution containing an acid may be followed by 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 after automatic development. 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. The above-described plate making process is preferably performed by an automatic developing machine as described in JP-A-2-7054 and JP-A-2-32357. Further, when 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-2-13293. It is preferable to use such an erasing liquid. Further, as the desensitized gum which is optionally applied in the final step of the plate making process, JP-B-62-16834 and JP-B-62-25
No. 118, 63-52600, JP-A-62-759
No. 5, No. 62-11693, and No. 62-83194 are preferable. Furthermore, when the photosensitive lithographic printing plate of the present invention is image-exposed, developed, rinsed or rinsed, optionally erased, washed with water and burned, before burning, the lithographic printing plate is prepared before burning.
Nos. 2518, 55-28062, and JP-A-62-131.
It is preferable to treat with a surface-regulating liquid as described in JP-A Nos. 859 and 61-159655.

[0065]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, "%" indicates "% by weight" unless otherwise specified.

(Preparation of Support) The surface of an aluminum plate having a thickness of 0.30 mm was grained with a nylon brush and an aqueous suspension of 400 mesh bamistone, and then washed thoroughly with water. 60% at 70 ° C in 10% sodium hydroxide
After immersion for 2 seconds and etching, 20% H
It was neutralized and washed with NO ₃ and washed with water. This was subjected to electrolytic surface roughening treatment in a 1% nitric acid aqueous solution at an anode electricity of 260 coulombs / dm ² using a sine wave alternating current under the condition of V _A = 12.7 V. When the surface roughness was measured, it was found to be 0.
It was 55 μ (Ra indication). 30% H
_After immersion in a ₂ SO ₄ aqueous solution and desmutting at 55 ° C. for 2 minutes, anodic oxidation in a 20% H ₂ SO ₄ aqueous solution at a current density of 2 A / dm ^{2 so} as to have a thickness of 1.6 g / m ² ,
A substrate was prepared.

The substrate was prepared by adding 2.5% by weight of sodium silicate
The substrate was treated with an aqueous solution at 30 ° C. for 10 seconds and washed with water to form a support. The undercoat liquid described below was applied to the surface of the support thus treated, and dried at 80 ° C. for 15 seconds. The coating amount after drying was 10 mg / m ² .

[Undercoat liquid] Polymer compound 2 0.3 g Methanol 100 g Water 1 g

Examples 1 to 3 and Comparative Examples 1 to 3 The following photosensitive solution was applied on the support thus treated by rod coating at 25 ml / m ² and dried at 100 ° C. for 1 minute. Thus, a positive photosensitive lithographic printing plate was obtained. The coated amount after drying was about 1.0 g / m ² . (Photosensitive liquid)

Esterified product of 0.8 g of 1,2-diazonaphthoquinone-5-sulfonyl chloride with pyrogallol-acetone resin (as described in Example 1 of US Pat. No. 3,635,709) Cresol-formaldehyde novolak resin 1.8 g (meta-para ratio 6: 4, weight average molecular weight 8000) Phenol-formaldehyde resin 0.2 g (weight average molecular weight 10,000) P-octylphenol-formaldehyde resin (US Pat. No. 4,123) No. 279) 0.02 g) Tetrahydroxyphthalic anhydride 0.2 g Compound (I) 0.06 g Benzoic acid 0.01 g Fluorine-containing polymer consisting of the following components 0.01 g 30 parts by weight of a fluorine-containing monomer having a structure, methyl methacrylate 20 parts by weight, hydroxyethyl methacrylate 10 parts by weight, isobutyl methacrylate 15 parts by weight) naphthoquinone-1,2-diazide-4 Table 1 -sulfonic acid chloride (baking agent A) Bis (ethoxycarbonylmethyl) Table-1 Aminophenyl] -2,6-bis (trichloromethyl) -S-triazine (baking agent B) Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) Counter anion in Table-1 (Colored dye C) Dye of the following structural formula (II) (yellow dye D) Table 1 Methyl ethyl ketone 30 g 1-methoxy-2-propanol 10 g

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[0072]

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[0073]

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Based on the method described in Example 1 of JP-B-61-28986, the (methyl methacrylate / ethyl acrylate / sodium acrylate = 68/20/12) A mat layer was provided by dissolving 0.1 g of tartrazine in 100 g of the aqueous copolymer solution and electrostatically spraying.

Using the thus obtained photosensitive lithographic printing plate as a light source, a 2KW metal halide lamp (Idolfin 2000 manufactured by Iwasaki Electric Co., Ltd.) was used, and after exposure to 8.0 mW / cm ² , exposure was performed so that the FOGRA PMSK value was 10 μm. The time was adjusted. After exposure, the planographic image quality of the photosensitive lithographic printing plate was visually evaluated, and then SiO ₂ / Na ₂ O was used as a developer.
5.26% aqueous solution (pH = 12.7) of sodium silicate having a molar ratio of 1.74 and FP-2W (1: 1) manufactured by Fuji Photo Film Co., Ltd. as a finisher liquid. Automatic Developing Machine Stavlon 9
Processed through 00D. The image of the printing plate thus obtained was checked for ease of viewing and the presence or absence of an image at the edge of the film. The clear sensitivity was determined from the number of steps where the image of the step guide P manufactured by Fuji Photo Film Co., Ltd. completely disappeared in the above exposure processing. Table 1 shows the results.

[0076]

[Table 1]

As shown in Table 1, it was found that Examples 1 to 3 satisfied all the performances.

[0078]

According to the present invention, a positive-type photosensitive material having a high sensitivity, in which an unnecessary image at an edge portion of a film is hardly formed on a plate, a visible image after exposure and a plate inspection after development are good. A lithographic printing plate can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA00 AB03 AC01 AD03 BE00 BE01 CB29 CB52 CC15 DA18 DA40 FA03 FA17 2H096 AA00 AA07 AA08 BA10 BA20 CA03 CA05 CA20 EA02 GA08 2H114 AA04 AA14 AA23 AA28 DA04 DA04 DA52 DA56 DA59 DA60 DA61 EA02 EA05 EA08 FA18 GA09

Claims (2)

[Claims] 1. A photosensitive layer containing a photoacid generator, o-naphthoquinonediazide, and a compound whose absorption is changed by an acid, wherein the photosensitive layer contains no photo-acid generator and o-naphthoquinonediazide.
A photosensitive lithographic printing plate wherein the absorbance at 00 nm increases by 0.03 or more before and after exposure. 2. A polymer compound comprising (a) a unit interacting with an alumina layer and (b) a unit interacting with a hydrophilic treatment layer, on an aluminum support subjected to anodizing treatment and hydrophilic treatment. The photosensitive lithographic printing plate according to claim 1, wherein the photosensitive layer is provided on an intermediate layer containing: