JP2000238455A - Manufacture of heat-sensitive lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the formation of aluminum and to further suppress the adherence of aluminum hydroxide to an aluminum support by providing a photosensitive layer on the support obtained by treating an anodized aluminum base plate with a water solution having a specific pH. SOLUTION: An aluminum plate is a plate-like material of an aluminum alloy or the like containing pure aluminum or aluminum as a main component and an infinitesimal amount of heteroatom. As the heteroatom, that of silicon, iron, manganese, copper, magnesium, chromium or the like is used. In an anodized aluminum support, formation of aluminum hydroxide is suppressed, adherence to the support is suppressed, and to eliminate a fault of an appearance, it is treated with acid water solution having a pH of 1.5 to 5 or preferably 2 to 4. If the pH is lower than the 1.5, an anodized film is dissolved, and hence a deterioration of stain in association with an increase in a pore size of the anodized film feasibly occurs. If the pH is higher than the 5, the formation of the oxide film cannot be prevented, and a fault of an appearance cannot be suppressed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a photosensitive lithographic printing plate.

[0002]

2. Description of the Related Art Generally, an aluminum support used for a lithographic printing plate is required to be excellent in hydrophilicity and water retention. For this purpose, fine irregularities are required by a mechanical, chemical or electrochemical method. It is well known that surface roughening (graining) is performed. In addition, it is known to anodize the surface to increase the mechanical strength of the grained surface and to increase the water retention. After the anodizing treatment, a water washing treatment is performed. At this time, aluminum ions contained in the anodizing solution and aluminum ions dissolved during the anodizing are retained on the aluminum support. The aluminum ions form aluminum hydroxide when washed with water and adhere to the aluminum support,
There was a drawback of causing an appearance failure. Conventionally, in order to solve this drawback, a method of strengthening water washing has been adopted, but there has been a problem that it is necessary to increase the amount of water washing, which is costly.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for washing a battery after anodic oxidation without increasing the amount of washing.
Suppresses the formation of aluminum hydroxide, and further suppresses the adhesion of aluminum hydroxide on the aluminum support,
An object of the present invention is to provide a method for producing an aluminum support for a photosensitive lithographic printing plate without causing an appearance failure.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, after anodizing treatment,
By treating with an aqueous solution of H1.5 to 5 and then rinsing, the generation of aluminum hydroxide during rinsing can be suppressed, and as a result, failure due to water and aluminum oxide can be prevented. And completed the present invention. That is, the present invention is a method for producing a photosensitive lithographic printing plate, comprising providing a photosensitive layer on an aluminum support obtained by treating an anodized aluminum substrate with an aqueous solution having a pH of 1.5 to 5. In another embodiment of the present invention, an anodized aluminum substrate is treated at pH 1.5.
After treating with an aqueous solution of an aluminum support, an alkali metal silicate treatment is performed so that the Si atom adhesion amount of the obtained aluminum support becomes 0.1 to 8 mg / m ² , A method for producing a photosensitive lithographic printing plate comprising providing a positive photosensitive layer.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive lithographic printing plate of the present invention will be described in detail below in the order of a support, an intermediate layer, a positive photosensitive layer, and a developing process.

First, the support used in the photosensitive lithographic printing plate of the present invention and its treatment will be described. (Aluminum Plate) The aluminum plate used in the present invention is a plate-like body such as pure aluminum or an aluminum alloy containing aluminum as a main component and containing a small amount of a different atom. The hetero atoms include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. As the alloy composition, a content of different atoms of 10% by weight or less is appropriate. Aluminum that is suitable for the present invention is pure aluminum, but it is preferable that completely pure aluminum contains as little foreign atoms as possible because it is difficult to produce due to refining technology. Further, any aluminum alloy having a different atomic content of the above-described level can be said to be a material that can be used in the present invention. The composition of the aluminum plate used in the present invention is not particularly limited, and conventionally known and publicly available materials can be appropriately used. Preferred materials are JIS A1050, JIS 1100, JIS 1200, JIS 3003, JIS 3103, and JIS A3
005 materials. The thickness of the aluminum plate used in the present invention is suitably about 0.1 mm to 0.6 mm. Prior to the surface roughening treatment of the aluminum plate, a degreasing treatment for removing a rolling oil on the surface, for example, a treatment with a surfactant or an alkaline aqueous solution is performed as necessary.

(Surface roughening treatment and anodic oxidation treatment) The surface of the above aluminum plate is generally roughened first. As a method of the surface roughening treatment, there are 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 alternating current or direct current in a hydrochloric acid or nitric acid electrolyte. Further, a method combining both of them, as disclosed in JP-A-54-63902, 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 that forms a porous oxide film can be used,
Generally, 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, but 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 within the range of 00 V and the electrolysis time of 10 seconds to 5 minutes.

The amount of the anodic oxide film is preferably 1.0 g / m ² or more, more preferably 2.0 to 6.0 g / m ^2.
Range. When the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient, and the non-image portion of the lithographic printing plate is easily damaged, and the ink adheres to the scratched portion during printing. "Scratch dirt" is likely to occur. In addition, such an anodizing treatment is applied to the surface used for printing of the support of the lithographic printing plate, and the back surface of the lines of electric force causes the back surface to have an anodic oxide film of 0.01 to 3 g / m ^2. It is generally formed.

(Aqueous Acid Treatment) In the present invention, the anodized aluminum support is used to suppress the formation of aluminum hydroxide, to prevent the aluminum support from adhering to the aluminum support, and to eliminate appearance defects. , PH 1.5-
5, preferably 2 to 4 treatments with acidic aqueous solution. If the pH is lower than 1.5, the anodic oxide film dissolves, and deterioration of the stain performance due to an increase in the pore size of the anodic oxide film is likely to occur. Also. If the pH is higher than 5, formation of an oxide film cannot be prevented, and appearance failure due to aluminum oxide cannot be suppressed. The temperature is suitably in the range of 10 ° C to 40 ° C, preferably 15 ° C to 30 ° C. When the temperature is higher than 40 ° C., the anodic oxide film is easily dissolved, and the contamination performance is easily deteriorated due to the increase in the pore diameter. If the temperature is lower than 10 ° C., the effect of suppressing the formation of aluminum hydroxide does not change, but the cost for cooling is undesirably high. The treatment is suitably performed for 0.5 to 120 seconds, preferably 3 to 20 seconds.

(Hydrophilic treatment) As the alkali metal silicate used in the hydrophilization treatment of the present invention, sodium silicate,
Potassium silicate, lithium silicate and the like are used. In this hydrophilization treatment, the content of the alkali metal silicate is 0.01 to 30% by weight, preferably 0.01 to 10% by weight, particularly preferably 0.05 to 3% by weight. By immersing the anodized aluminum support in an aqueous alkali metal silicate solution having a pH of 10 to 13 at 25 ° C. at 4 to 80 ° C. for 0.5 to 120 seconds, preferably for 2 to 30 seconds, Si
The treatment can be preferably carried out by appropriately selecting treatment conditions such as the concentration of the alkali metal silicate, the treatment temperature and the treatment time so that the attached amount of atoms becomes the above-mentioned specific amount. In performing the hydrophilization treatment, if the pH of the aqueous alkali metal silicate solution is lower than 10, the solution gels, and if the pH is higher than 13.0, the anodic oxide film is dissolved, and thus care must be taken. In the hydrophilization treatment of the present invention, if necessary, a hydroxide can be blended to adjust the pH of the aqueous solution of the alkali metal silicate to a high value. As the hydroxide, sodium hydroxide, potassium hydroxide, Lithium hydroxide and the like. If necessary, an alkaline earth metal salt or a Group IVB metal salt may be added to the aqueous alkali metal silicate solution. Examples of the alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate and barium nitrate, and sulfates, hydrochlorides, phosphates, acetates, oxalates, borates and the like of these alkaline earth metals. And water-soluble salts such as acid salts. Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetraiodide,
Zirconium chloride oxide, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride and the like can be mentioned. Alkaline earth metal salts or Group IVB metal salts can be used alone or in combination of two or more. The preferred use amount range of these metal salts is 0.01 to
10% by weight, and a more preferred range is 0.05 to
5.0% by weight.

When a positive photosensitive layer is used, the amount of metal silicate deposited on the surface of the aluminum support is 0.1 to 8 mg / m ² , preferably 0.5 to 6 as Si atom.
mg / m ² . If the attached amount is less than 0.1 mg / m ² as the amount of Si atoms, the fouling performance is inferior and the initial purpose cannot be achieved. Further, when a developer containing no alkali metal silicate is used in the developer, it is not possible to prevent whitening of a non-image portion during development and generation of scum and sludge during development. On the other hand, when the attached amount exceeds 8 mg / m ^{2 in} terms of the amount of Si atoms, the printing durability is poor and the initial purpose cannot be achieved.

In the present invention, the amount of the above-mentioned alkali metal silicate deposited on the surface of the aluminum support is measured by an X-ray fluorescence analyzer (XRF; X-ray Fluorescent).
It is measured as the amount of Si atoms (Simg / m ² ) by a calibration curve method using ceSpectrometer). The standard sample for preparing the calibration curve is a known amount of Si.
A solution obtained by uniformly dropping an aqueous solution of sodium silicate containing atoms in an area of 30 mmφ on an aluminum substrate and then drying the solution is used. Although there is no particular limitation on the model of the X-ray fluorescence spectrometer, in the examples described later, Rigaku Denki Kogyo Co., Ltd.
The amount of Si atoms was measured from the peak height of the Si-Kα spectrum under the following conditions using RIX3000 manufactured by Ricoh.

Apparatus: RIX3000 X-ray tube manufactured by Rigaku Corporation: Rh Measurement spectrum: Si-Kα Tube voltage: 50 kV Tube current: 50 mA Slit: COARSE Spectral crystal: RX4 Detector: F-PC Analysis area: 30 mmφ Peak position (2θ): 144.75 deg. Background (2θ): 140.70 deg. , 146.85 deg. Integration time: 80 seconds / sample

(Aqueous Aqueous Solution Treatment) In the present invention, the above-mentioned hydrophilized aluminum support can be treated with an acidic aqueous solution, if necessary. Examples of the acidic aqueous solution include aqueous solutions of sulfuric acid, nitric acid, hydrochloric acid, oxalic acid, phosphoric acid, and the like. In addition, this acidic aqueous solution treatment is performed by subjecting the aluminum support subjected to the hydrophilization treatment to an aqueous solution having an acid concentration of 0.001 to 10% by weight, preferably 0.01 to 1% by weight, at a temperature of 15 to 70%. ° C, preferably 25-
It is appropriate to perform the immersion at 50 ° C. for 0.5 to 120 seconds, preferably for 2 to 30 seconds. By this acidic aqueous solution treatment, adjustment can be made to reduce the amount of the alkali metal silicate attached to the aluminum support by the hydrophilization treatment.

(Backcoat) In the present invention, a backcoat is provided on the back surface of the aluminum support, if necessary. Such a back coat is disclosed in
A coating layer composed of a metal oxide obtained by hydrolysis and polycondensation of an organic polymer compound described in -45885 and an organic or inorganic metal compound described in JP-A-6-35174 is preferably used. Among these coating layers, Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si
Alkoxy compounds of silicon, such as (OC ₃ H ₇ ) ₄ and Si (OC ₄ H ₉ ) ₄ , are inexpensive and easily available, and a metal oxide coating layer provided therefrom is particularly preferred because of its excellent development resistance.

(Intermediate layer) In the present invention, amino acids and salts thereof (Na salt, K salt) disclosed in Japanese Patent Application Laid-Open No. Alkali metal salts, ammonium salts, hydrochlorides, oxalates, acetates, phosphates, etc.), amines having a hydroxyl group and their salts (hydrochloride, oxalic acid) disclosed in JP-A-60-232998 Salts, phosphates, etc.), compounds having an amino group and a phosphonic acid group or salts thereof disclosed in JP-A-63-165183 can be used for the intermediate layer. Further, a compound having a phosphonic acid group disclosed in JP-A-4-282637 can also be used for the intermediate layer. Hereinafter, the case where the positive photosensitive layer is provided will be described in detail.

(Intermediate Layer of Polymer Compound Having Acid Group and Onium Group) As the polymer compound used for forming the intermediate layer,
A polymer compound having an acid group or a component having an onium group in addition to a component having an acid group is more preferably used. As the acid groups of the constituent components of the polymer compounds, acid dissociation constant (pKa) of preferably acid groups 7 or less, more preferably -COOH, -SO ₃ H, -
_{OSO 3 H, -PO 3 H 2} , -OPO 3 H 2, -CONHS
O ₂ and —SO ₂ NHSO ₂ —, particularly preferably —C
OOH. A suitable component having an acid group is a polymerizable compound represented by the following general formula (1) or general formula (2).

[0018]

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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. More preferably, among the components having an acid group, A is -COO- or -C
Represents ONH-, B represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group, a halogen atom or an alkyl group. Alkylene group or a molecular formula D and E are each independently represents C _n H _2n O, 2 divalent linking group represented by C _n H _2n S or C _n H _{2n + 1} N. G is the molecular formula represents _{C n H 2n-1, C} n H 2n-1 O, 3 -valent linking group represented by C _n H _2n-1 S or C _n H _2n N. However,
Here, n represents an integer of 1 to 12. X and X 'each independently represent a carboxylic acid, a sulfonic acid, a phosphonic acid, a sulfuric acid monoester or a phosphoric acid monoester. R ₁ represents a hydrogen atom or an alkyl group. a, b, d, and e each independently represent 0 or 1;
is not. Among the components having an acid group, particularly preferred is a compound represented by the general formula (1), wherein B represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. . D and E each independently represent 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 component having an acid group are shown below. However, the present invention is not limited to this specific example. Examples thereof include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, itaconic acid, maleic acid, and maleic anhydride, and further include the following.

[0021]

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[0022]

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[0023]

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The constituent having an acid group as described above includes 1
Types or two or more types may be combined.

(Intermediate Layer of Polymer Compound Having Onium Group) As the onium group as a constituent component of the polymer compound used for forming the intermediate layer, an atom of Group V or Group VI of the periodic table is preferable. And more preferably an onium group consisting of a nitrogen atom, a phosphorus atom or a sulfur atom, and particularly preferably an onium group consisting of a nitrogen atom. The polymer is preferably a polymer whose main chain structure is a vinyl polymer such as an acrylic resin, a methacrylic resin, or polystyrene, a urethane resin, a polyester, or a polyamide. Above all, a vinyl polymer having a main chain structure such as an acrylic resin, a methacrylic resin, or polystyrene is more preferable. A particularly preferred polymer compound is a polymer whose constituent component having an onium group is a polymerizable compound represented by the following general formula (3), (4) or (5).

[0026]

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In the formula, J represents a divalent linking group. K represents an aromatic group or a substituted aromatic group. M each independently represents a divalent linking group. Y ₁ represents an atom of Group V of the periodic table, and Y ₂ represents an atom of Group VI of the periodic table. And Z ^- represents a counter anion. R ₂ represents a hydrogen atom, an alkyl group or a halogen atom. R ₃ , R ₄ , R ₅ , and R ₇ each independently represent a hydrogen atom or, in some cases, an alkyl group, an aromatic group, or an aralkyl group to which a substituent may bind, and R ₆ represents an alkylidine group or a substituted alkylidine Represents R
₃ and R ₄ or R ₆ and R ₇ may be bonded to each other to form a ring. j, k, and m each independently represent 0 or 1. u represents an integer of 1 to 3. More preferably, among the components having an onium group, J is -COO- or-
K represents CONH-, K represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group, a halogen atom or an alkyl group. M represents a divalent linking group in the alkylene group or molecular formula represented by _{C n H 2n O, C n} H 2n S or C _n H _{2n + 1} N. Here, n is 1 to 1
Represents an integer of 2. Y ₁ represents a nitrogen atom or a phosphorus atom, and Y ₂ represents a sulfur atom. Z ^- is a halogen ion, P
F ₆ ^-, BF ₄ ^- or R ₈ SO ₃ ^- represents an (R ₈ MAY bonded substituent alkyl group having 1 to 10 carbon atoms, an aromatic group, an aralkyl group.). R ₂ represents a hydrogen atom or an alkyl group. _{R 3, R 4, R 5} , R 7 are each independently hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be bonded substituent optionally, an aromatic group, an aralkyl group, R ₆ Represents an alkylidene group having 1 to 10 carbon atoms or a substituted alkylidyne, wherein R ₃ and R ₄ or R ₆
And R ₇ may combine with each other to form a ring. j,
k and m each independently represent 0 or 1, but j and k
Are not simultaneously 0. Among the constituent components having an onium group, K is particularly preferably a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group or a carbon atom having 1 carbon atom.
To 3 alkyl groups. M 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. Z ^- is a chloride ion or R ₈ SO ₃ ^- represents a. R ₂ represents a hydrogen atom or a methyl group. j is 0
And k is 1.

Specific examples of the constituent having an onium group are shown below. However, the present invention is not limited to this specific example.

[0029]

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[0030]

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It is desirable that the polymer compound used for forming the intermediate layer contains at least 1 mol%, preferably at least 5 mol% of the above-mentioned constituent having an onium group. When the constituent having an onium group is contained in an amount of 1 mol% or more, the adhesion is further improved. Further, the constituent components having an onium group may be used alone or in combination of two or more. Further, as the polymer compound used for forming the intermediate layer, two or more kinds of compounds having different constituent components or composition ratios or different molecular weights may be used in combination.

In the polymer compound having an onium group in addition to the acid group, the component having the acid group is used in two components.
It is desirable that the composition contains 0 mol% or more, preferably 40 mol% or more, and contains 1 mol% or more, preferably 5 mol% or more of a component having an onium group. When the component having an acid group is contained in an amount of 20 mol% or more, dissolution and removal during alkali development are further promoted, and the adhesion is further improved by the synergistic effect of the acid group and the onium group. It is needless to say that two or more kinds of polymer compounds having different constituent components or composition ratios or molecular weights may be used in the polymer compound having an acid group together with the onium group. Hereinafter, typical examples of the polymer compound having an acid group together with the above-described onium group will be described. The composition ratio of the polymer structure represents a mole percentage.

[0033]

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[0034]

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[0035]

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[0036]

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(Method of Producing Polymer Compound for Forming Intermediate Layer) Any of the above-mentioned polymer compounds having an acid group or having an onium group together with an acid group, which are used for forming the intermediate layer, is generally prepared by a radical chain. It can be produced using a polymerization method (“Textbook of Polymer Science” 3rd ed,
(1984) FW Billmeyer, A Wiley-Interscience Publicati
on). The molecular weight of these high molecular compounds may be in a wide range, but when measured using a light scattering method, the weight average molecular weight (Mw) is preferably from 500 to 2,000,000. 000-600,000
More preferably, it is within the range. The amount of the unreacted monomer contained in the polymer compound may be wide, but is preferably 20% by weight or less.
More preferably, it is 0% by weight or less. Further, as a typical example of a polymer compound having an onium group together with an acid group, the above-mentioned copolymer of p-vinylbenzoic acid and vinylbenzyltrimethylammonium chloride (No. 1 in Table 1) is exemplified. An example of the synthesis is as follows. 146.9 g (0.99 mol) of p-vinyl benzoic acid [manufactured by Hokuko Chemical Industry Co., Ltd.], 44.2 g of vinylbenzyltrimethylammonium chloride
(0.21 mol) and 2-methoxyethanol 44
6 g was placed in a 1 L three-necked flask and heated to 75 ° C. while stirring under a nitrogen stream. Next, 2,76 g (12 mmol) of dimethyl 2,2-azobis (isobutyrate) was added, and stirring was continued. Two hours later, 2,76 g (12 mmol) of dimethyl 2,2-azobis (isobutyrate) was added. Two hours later, 2.76 g (12 mmol) of dimethyl 2,2-azobis (isobutyrate) was added. After stirring for 2 hours, the mixture was allowed to cool to room temperature. The reaction solution is stirred 1
Poured into 2 L of ethyl acetate. The precipitated solid is collected by filtration,
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 can be synthesized in a similar manner.

(Method for Forming Intermediate Layer) The intermediate layer was prepared by subjecting the above-mentioned polymer compound having an acid group or having an onium group together with an acid group (hereinafter simply referred to as “polymer compound”) to the above-mentioned hydrophilic treatment. It is applied by various methods on an aluminum support or an aluminum support which has been subjected to an aqueous acid treatment after the hydrophilization treatment (hereinafter simply referred to as "aluminum support"). One of the methods generally used for providing the intermediate layer is to dissolve a polymer compound in an organic solvent such as methanol, ethanol, methyl ethyl ketone or a mixed solvent thereof or a mixed solvent of these organic solvents and water. This is a method in which a solution is applied on an aluminum support and dried and provided. Another method is to use an organic solvent such as methanol, ethanol, methyl ethyl ketone, or a mixed solvent thereof, or a mixed solvent of these organic solvents and water. This is a method in which an aluminum support is immersed in a solution in which a molecular compound is dissolved to adsorb the polymer compound, followed by washing with water or the like and drying. In the former method, the 0.1.
Solutions having a concentration of from 005 to 10% by weight can be applied in various ways. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used.
In the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 5% by weight, the immersion temperature is 20 to 90 ° C, preferably 25 to 50 ° C, and the immersion time is Is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute.

The solution of the above-mentioned polymer compound may be a basic substance such as ammonia, triethylamine or potassium hydroxide, an inorganic acid such as hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid, or an organic sulfone such as nitrobenzenesulfonic acid or naphthalenesulfonic acid. Acids, organic phosphonic acids such as phenylphosphonic acid, benzoic acid, coumaric acid, various organic acidic substances such as organic carboxylic acids such as malic acid, naphthalene sulfonyl chloride, the pH is adjusted with an organic acid chloride such as benzenesulfonyl chloride, etc. It can be used in the range of pH = 0 to 12, more preferably pH = 0 to 5. Further, a yellow dye can be added for improving the tone reproducibility of the photosensitive lithographic printing plate. The coating amount after drying of the polymer compound, 2 to 100 mg / m ² are suitable, preferably from 5 to 50 mg / m ^2. The coating amount is 2m
If it is less than g / m ² , a sufficient effect cannot be obtained. The same is true even if the amount is more than 100 mg / m ² .

<3> Positive-type photosensitive layer In the present invention, an aluminum support obtained by treating the anodized aluminum substrate with an aqueous solution having a pH of 1.5 to 5;
After treating with an aqueous solution of pH 5 to 5, an aluminum support treated with an alkali metal silicate and an anodized aluminum substrate were treated with an aqueous solution having a pH of 1.5 to 5 and then treated with an alkali metal silicate and further treated with an acidic aqueous solution. The positive photosensitive composition used to provide a positive photosensitive layer on an aluminum support, or the above aluminum support provided with an intermediate layer, may have solubility in a developing solution before or after exposure, or swelling. Any substance can be used as long as its properties change. Hereinafter, a typical positive photosensitive composition will be described, but the present invention is not limited thereto.

(Photosensitive compound) Examples of the photosensitive compound of the photosensitive composition include an o-quinonediazide compound.
A typical example is an o-naphthoquinonediazide compound. As the o-naphthoquinonediazide compound,
1, 2 described in JP-B-43-28403.
Those which are esters of diazonaphthoquinone sulfonic acid chloride with pyrogallol-acetone resin;

Other suitable o-quinonediazide compounds include those described in US Pat. Nos. 3,046,120 and 3,188,210.
There are esters of diazonaphthoquinone sulfonic acid chloride with phenol formaldehyde resin.

Other useful o-naphthoquinonediazide compounds include those reported and known in numerous patents. For example, JP-A-47-5303
No. 48-63802, No. 48-63803, No. 48-96575, No. 49-38701, No. 48-
13354, JP-B-37-18015, 41-1
No. 1222, No. 45-9610, No. 49-17481
JP-A-5-11444, JP-A-5-19477
JP-A-5-19478, JP-A-5-107755
No. 2,797,213 and No. 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, etc. or those described in the specification.

As other o-quinonediazide compounds, o-naphthoquinonediazide compounds obtained by reacting a polyhydroxy compound having a molecular weight of 1,000 or less with 1,2-diazonaphthoquinonesulfonic acid chloride can also be used. For example, JP-A-51-1394
No. 02, No. 58-150948, No. 58-20343
No. 4, No. 59-165053, No. 60-112445
No. 60-134235, No. 60-16343
No. 61-118744, No. 62-10645,
No. 62-10646, No. 62-153950, No. 6
2-178562, 64-76047, U.S. Pat. Nos. 3,102,809 and 3,126,281,
No. 3,130,047, No. 3,148,983
No. 3,184,310, No. 3,188,21
No. 0, No. 4,639,406 and the like, and those described in each gazette or specification.

When synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2-1.2 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-diazonaphthoquinone sulfonic 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. The resulting o-naphthoquinonediazide compound is a mixture of various 1,2-diazonaphthoquinonesulfonic acid ester groups having different positions and introduced amounts, but all of the hydroxyl groups are converted to 1,2-diazonaphthoquinonesulfonic acid ester. Of the compound in the mixture (content of the completely esterified compound) is 5 mol%
Or more, more preferably 20 to 9
9 mol%.

Further, as a photosensitive compound which acts positively without using an o-naphthoquinonediazide compound, for example, a polymer compound containing an o-nitrile carbinol ester group described in JP-B No. 52-2696 or pyridinium Group-containing compounds (for example, JP-A-4-365049) and diazonium group-containing compounds (for example, JP-A-5-2496).
No. 64, JP-A-6-83047, JP-A-6-3244
No. 95, JP-A-7-72621) can also be used. Further, a compound capable of generating an acid by photolysis (JP-A-4-121748, JP-A-4-365043)
No.), a C—O—C group or C—O dissociated by an acid
A combination system with a compound having a -Si group can also be used. For example, a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (Japanese Patent Application Laid-Open No. 48-89003), a combination of an orthoester or an amide acetal compound (Japanese Patent Application Laid-open No.
Combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-1).
No. 33429) and combinations with enol ether compounds (JP-A-55-12959, JP-A-4-1974).
No. 8, JP-A-6-230574), a combination with an N-acylimino carbon compound (JP-A-55-12623).
No. 6, etc.), a combination with a polymer having an orthoester group in the main chain (JP-A-56-17345, etc.), and a combination with a polymer having a silyl ester group (JP-A-6-17345).
No. 0-10247) and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-37549).
No. 112446, JP-A-63-236028, JP-A-63-236029, JP-A-63-276046, and the like. The amount of these positive-acting photosensitive compounds (including the above combinations) in the photosensitive composition is suitably from 10 to 50% by weight, more preferably from 15 to 40% by weight.

(Binder) The o-quinonediazide compound alone can constitute the photosensitive layer, but is preferably used together with a resin soluble in alkaline water as a binder. Such resins soluble in alkaline water include novolak resins having this property, such as phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin,
Phenol / cresol (m-, p-, o- or m-
/ P- / o-mixture) and cresol formaldehyde resins such as mixed formaldehyde resins. These alkaline soluble high molecular compounds preferably have a weight average molecular weight of 500 to 100,000. In addition, resol type phenol resins are also preferably used, and phenol / cresol (m-, p-,
o- or m- / p- / o-mixture). A mixed formaldehyde resin is preferred.
Phenolic resins described in Japanese Patent No. 217034 are preferred.

Also, a phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, an acrylic resin containing a phenolic hydroxyl group as disclosed in JP-A-51-34711, and JP-A-2-866. Patent Publication No. 7-28244, a vinyl resin or urethane resin having a sulfonamide group described in
JP-A-7-36184, JP-A-7-36185
JP-A-7-248628, JP-A-7-26139
No. 4, JP-A-7-333839, etc., various alkali-soluble polymer compounds such as vinyl resins having a structural unit can be contained. In particular, in the case of a vinyl resin, a film-forming resin having as a polymerization component at least one selected from the following alkali-soluble group-containing monomers (1) to (4) is preferable.

(1) N- (4-hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) methacrylamide, o-, m- or p-hydroxystyrene, o- or m-bromo-p-hydroxystyrene, o- or m-chloro-p-hydroxystyrene,
acrylamides, methacrylamides, acrylates, methacrylates, and vidroxystyrenes having an aromatic hydroxyl group such as o-, m- or p-hydroxyphenyl acrylate or methacrylate; (2) acrylic acid, methacrylic acid , Maleic acid, unsaturated carboxylic acids such as maleic anhydride and its half esters, itaconic acid, itaconic anhydride and its half esters,

(3) N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N- [1- (3-aminosulfonyl) Naphthyl] acrylamide, acrylamides such as N- (2-aminosulfonylethyl) acrylamide, N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonyl) Phenyl)
Methacrylamides such as methacrylamide, N- [1- (3-aminosulfonyl) naphthyl] methacrylamide, N- (2-aminosulfonylethyl) methacrylamide, and o-aminosulfonylphenyl acrylate and m-aminosulfonylphenyl Acrylate, p
-Aminosulfonylphenyl acrylate, 1- (3-
Unsaturated sulfonamides such as acrylates such as aminosulfonylphenylnaphthyl) acrylate;
unsaturated sulfonamides such as methacrylates such as o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate and 1- (3-aminosulfonylphenylnaphthyl) methacrylate; (4) tosylacrylamide And phenylsulfonyl methacrylamide which may have a substituent such as tosyl methacrylamide.

Further, in addition to these alkali-soluble group-containing monomers, a film-forming resin obtained by copolymerizing the following monomers (5) to (14) is preferably used. (5) Acrylic esters and methacrylic esters having an aliphatic hydroxyl group, for example, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (6) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate , Amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 4-hydroxybutyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, etc. (Substituted) acrylate, (7) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, silicone methacrylate Hexyl, octyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-chloroethyl, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N- dimethyl (substituted) methacrylic acid esters such as aminoethyl methacrylate,

(8) Acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide, N-hexyl acrylamide, N
-Hexyl methacrylamide, N-cyclohexyl acrylamide, N-cyclohexyl methacrylamide, N
-Hydroxyethylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N
Acrylamides such as -phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide, N-ethyl-N-phenylacrylamide and N-ethyl-N-phenylmethacrylamide Or methacrylamide, (9) vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether;

(10) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate; (11) styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and (12) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone; (13) olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene; (14) N-vinyl pyrrolidone, N-vinyl carbazole; 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like.

These alkali-soluble polymer compounds are
Those having a weight average molecular weight of 500 to 500,000 are preferred. Such alkali-soluble polymer compounds may be used alone or in combination of two or more. The proportion of the polymer compound in the photosensitive composition is suitably 80% by weight or less, and preferably 30 to 8% by weight.
0% by weight, more preferably 50-70% by weight. This range is preferred from the viewpoints of developability and printing durability.

Further, as described in US Pat. No. 4,123,279, a compound having an alkyl group having 3 to 8 carbon atoms as a substituent, such as a t-butylphenol formaldehyde resin and an octylphenol formaldehyde resin. Condensates of phenol and formaldehyde or o-naphthoquinonediazidosulfonic acid esters of these condensates (for example, JP-A-61-243446).
It is preferable to use the above-mentioned compounds in combination in order to improve the oil sensitivity of the image.

(Development Accelerator) It is preferable to add a cyclic acid anhydride, a phenol and an organic acid to the photosensitive composition in order to increase sensitivity and improve developability.
As cyclic acid anhydrides, US Pat. No. 4,115,128
Pat has been and phthalic anhydride described, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic acid anhydride, chlorosulfonic maleic anhydride , Α-phenyl maleic anhydride, succinic anhydride,
Pyromellitic anhydride and the like can be used. As phenols, bisphenol A, p-nitrophenol, p
-Ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ',
4 "-trihydroxy-triphenylmethane, 4,
4 ', 3 ", 4"-tetrahydroxy-3,5,3',
5'-tetramethyltriphenylmethane and the like. Further, as organic acids, JP-A-60-8894
2, sulfonic acids, sulfinic acids, alkyl sulfates, and the like described in JP-A-2-96755 and the like.
Examples include phosphonic acids, phosphoric esters and carboxylic acids, and specifically, 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-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and the like. The proportion of the above cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is from 0.05 to
It is preferably 15% by weight, more preferably 0.1 to 5% by weight.

(Development Stabilizer) Further, in the photosensitive composition, JP-A-62-251740 and JP-A-4-68355 may be used in order to widen the stability of processing under development conditions (so-called development tolerance). Nonionic surfactants as described in JP-A-59-121044,
An amphoteric surfactant as described in JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate,
Sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene sorbitan monooleate, polyoxyethylene nonyl phenyl ether and the like can be mentioned. Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine,
Alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) ) And alkyl imidazolines (eg, Levon 15, trade name, manufactured by Sanyo Chemical Co., Ltd.). The proportion of the nonionic surfactant and the amphoteric surfactant in the photosensitive composition is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

(Print-out agent, dye, etc.) In the photosensitive composition, a print-out agent for obtaining a visible image immediately after exposure,
Dyes and other fillers as image colorants can be added. As the dye, JP-A-5-31335
No. 9, a cation having a basic dye skeleton,
A basic dye comprising a salt with an organic anion having 10 or more carbon atoms and having a sulfonic acid group as a sole exchange group and having 1 to 3 hydroxyl groups can be given. The amount of addition is 0.2 to 5% by weight of the total photosensitive composition.

Further, compounds capable of interacting with the dyes described in JP-A-5-313359 to generate photodegradable products that change color tone, such as those described in JP-A-50-36209 (US Pat. No. 3,969,118) -Naphthoquinonediazide-4-sulfonic acid halogenide described in
No. 3-36223 (U.S. Pat. No. 4,160,671) discloses trihalomethyl-2-pyrone and trihalomethyltricidin, and JP-A-55-62444 (U.S. Pat.
38,801), various o-naphthoquinonediazide compounds described in JP-A-55-77742 (U.S. Pat.
279, 982).
An aryl 1,3,4-oxadiazole compound or the like can be added. These compounds can be used alone or as a mixture. 400 of these compounds
A compound having an absorption at nm may be used as the yellow dye.

As a colorant for an image, the above-mentioned Japanese Patent Application Laid-Open No.
Other dyes can be used in addition to the dyes described in JP-A-13359. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes.
Specifically, Oil Green BG, Oil Blue BO
S, Oil Blue # 603 (orientated by Orient Chemical Co., Ltd.), Victoria Pure Blue BOH, Victoria Pure Blue NAPS, Ethyl Violet 6H
NAPS (above, manufactured by Hodogaya Chemical Industry Co., Ltd.), Rhodamine B (C145170B), Malachite Green (C1
42000), methylene blue (C152015) and the like.

In the photosensitive composition, 417n represented by the following general formula [I], [II] or [III] is used.
A yellow dye having an absorbance at m of 70% or more of the absorbance at 436 nm can be added.

[0062]

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In the formula [I], R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or an alkenyl group. R ₁ and R ₂ may form a ring. R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom,
It represents an alkyl group having 1 to 10 carbon atoms. G ₁ and G ₂ each independently represent an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or a fluoroalkylsulfonyl group. G ₁ and G ₂ may form a ring. Further R
₁ , at _{least one} of R ₂ , R ₃ , R ₄ , R ₅ , G ₁ , G ₂
It has two or more sulfonic acid groups, carboxyl groups, sulfonamide groups, imide groups, N-sulfonylamido groups, phenolic hydroxyl groups, sulfonimide groups, or metal salts, inorganic or organic ammonium salts thereof. Y is O, S, NR
(R is a hydrogen atom or an alkyl group or an aryl _{group), Se, -C (CH 3} ) 2 -, - CH = CH- than a divalent atomic group selected, n ₁ represents 0 or 1.

[0064]

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In the formula [II], R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocyclic group, a substituted heterocyclic group, an allyl group or a substituted allyl group. And R ₆ and R ₇ may form a ring together with the carbon atom to which they are attached. n ₂ represents 0, 1 or 2. G ₃ and G ₄
Are each independently a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an aryloxycarbonyl group, a substituted aryloxycarbonyl group,
Represents an acyl group, a substituted acyl group, an arylcarbonyl group, a substituted arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or a fluoroalkylsulfonyl group. However, G ₃ and G ₄ are not simultaneously hydrogen atoms. In addition, G ₃ and G
₄ may form a ring consisting of a non-metallic atom together with the carbon atom to which it is attached. Further, R ₆ , R ₇ , G ₃ , G ₄
One or more of which has at least one sulfonic acid group, carboxyl group, sulfonamide group, imide group, N-sulfonylamide group, phenolic hydroxyl group, sulfonimide group, or a metal salt thereof, or an inorganic or organic ammonium salt. .

[0066]

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In the formula [III], R ₈ , R ₉ , R ₁₀ , R ₁₁ , R
₁₂ and R ₁₃ may be the same or different, and each may be a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, a hydroxyl group, an acyl group,
Represents a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a nitro group, a carboxyl group, a chloro group, or a bromo group.

(Formation of Positive-Type Photosensitive Layer, etc.) The positive-type photosensitive layer is obtained by dissolving the components of each of the above-mentioned photosensitive compositions in a solvent that dissolves them, and coating the mixture on a support. 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-propanol Propyl acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide,
Dimethylacetamide, dimethylformamide, water, N
-Methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, isopropanol, diethylene glycol dimethyl ether and the like, and these solvents can be used alone or in combination. The concentration (solid content) of the photosensitive composition component in the solution is suitably from 2 to 50% by weight. 0.5g / m ² ~4.0g / m ² is preferred as the coating amount. When the amount is less than 0.5 g / m ² , the printing durability deteriorates. When the amount is more than 4.0 g / m ² , the printing durability is improved.
The sensitivity decreases. A method for forming a photosensitive layer, such as coating a photosensitive composition solution on a support, can be based on various conventionally known methods.

A surfactant for improving the coating method, for example, a fluorine-based surfactant described in JP-A-62-170950 may be added to the photosensitive composition. it can. A preferable addition amount is 0.01 to 1% by weight of the total photosensitive composition, and more preferably 0.01% by weight.
5 to 0.5% by weight. With the lithographic printing plate obtained as described above, a printed matter faithful to the original picture film can be obtained, but the print blurring and the roughness of the printed matter are poor. As a method for improving the burning blur, there is a method of making the surface of the photosensitive layer provided in this way uneven. For example, as described in Japanese Patent Application Laid-Open No. 61-258255, there is a method in which particles of several μm are added to a photosensitive composition solution, and the particles are coated. Roughness is not improved at all.

However, for example, Japanese Patent Application Laid-Open No. Sho 50-12580
No. 5, JP-B-57-6582, JP-B-61-28986
And Japanese Patent Application Laid-Open No. 62-62337, a method of forming a component having irregularities on the surface of a photosensitive layer can improve bokeh blur and improve the roughness of printed matter. Furthermore, as described in JP-B-55-30619, when a light absorbing agent having absorption in the photosensitive wavelength region of the photosensitive material is contained in the mat layer, the burning blur and the roughness are further improved. In addition, an original film having a line number of 300 lines or more per inch and an original film obtained by FM screening, which is more easily burned out than an original film having a line number of 175 lines per inch and which easily gives a sense of roughness of a printed material, is used. Thus, a good printed matter can be obtained. As described above, the following minute patterns are desirably provided on the surface of the photosensitive layer of the photosensitive printing plate. That is, the height of the coated portion is preferably in the range of 1 to 40 μm, particularly 2 to 20 μm, and the size (width) is 10 to 10000 μm, particularly 2
The range of 0 to 200 μm is preferred. The amount is 1 to 100
0 / mm ² , preferably in the range of 5 to 500 / mm ² .

<3> Development Processing Next, the development processing of the positive photosensitive lithographic printing plate of the present invention will be described. (Exposure) The positive photosensitive lithographic printing plate of the present invention is developed after being subjected to image exposure. The light source of the actinic ray used for image exposure includes a carbon arc lamp, a mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, a chemical lamp, and the like. As radiation, electron beam, X-ray,
There are ion beams, far infrared rays, and the like. G line, i
Lines, Deep-UV light, high density energy beams (laser beams) are also used. Examples of the laser beam include a helium-neon laser, an argon laser, a krypton laser, a helium-cadmium laser, a KrF excimer laser, a semiconductor laser, and a YAG laser.

(Developer) A preferable developer for the positive photosensitive lithographic printing plate of the present invention is an alkaline aqueous solution containing substantially no organic solvent. Specifically, sodium silicate, potassium silicate, NaOH, KOH, LiO
H, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium carbonate, sodium bicarbonate,
Aqueous solutions such as potassium carbonate, aqueous ammonia and the like are suitable. More preferably, the developer contains (a) at least one saccharide selected from non-reducing sugars and (b) at least one base, and has a pH in the range of 9.0 to 13.5. Hereinafter, the developer will be described in detail. In the present specification, unless otherwise specified, the developing solution means a developing solution (a developing solution in a narrow sense) and a developing replenisher.

(Non-Reducing Sugar and Base) The developing solution comprises at least one compound selected from non-reducing sugars and at least one base, and the pH of the solution is 9.0 to 13.5. It is characterized by being within the range. Such non-reducing sugars are saccharides having no free aldehyde group or ketone group and exhibiting no reducing property, trehalose-type oligosaccharides in which reducing groups are bonded to each other, glycosides in which a reducing group of a saccharide is bonded to a non-saccharide. It is classified as a sugar alcohol reduced by hydrogenation of a body and a saccharide, and both are suitably used. Trehalose-type oligosaccharides include saccharose and trehalose,
Glycosides include alkyl glycosides, phenol glycosides,
And mustard oil glycosides. Examples of sugar alcohols include D, L-arabit, ribit, xylit,
D, L-sorbit, D, L-mannit, D, L-idit, D, L-talit, zuricit and allozurcit. Further, maltitol obtained by hydrogenation of disaccharide and reductant (reduced starch syrup) obtained by hydrogenation of oligosaccharide are preferably used. Among these, non-reducing sugars which are particularly preferred are sugar alcohols and saccharose, and D-sorbitol, saccharose and reduced starch syrup are particularly preferred because they have a buffering action in an appropriate pH range and are inexpensive. These non-reducing sugars can be used alone or in combination of two or more kinds, and their ratio in the developing solution is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight. Below this range, a sufficient buffering effect cannot be obtained, and at concentrations above this range, it is difficult to achieve high concentration, and there is a problem of cost increase. When a reducing sugar is used in combination with a base,
There is a problem in that the color changes to brown with the passage of time, and the pH gradually decreases, thereby deteriorating the developability.

As the base to be combined with the non-reducing sugar, a conventionally known alkali agent can be used. For example,
Sodium hydroxide, potassium, lithium, trisodium phosphate, potassium, ammonium, disodium phosphate, potassium, ammonium, sodium carbonate,
Inorganic alkali agents such as potassium, ammonium, sodium bicarbonate, potassium, ammonium, sodium borate, potassium, and ammonium are exemplified. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropynolamine, diisopropanolamine And organic alkali agents such as ethyleneimine, ethylenediamine and pyridine. These alkali agents are used alone or in combination of two or more. Preferred among these are sodium hydroxide and potassium hydroxide. The reason is that by adjusting these amounts to non-reducing sugars, pH
This is because adjustment becomes possible. Trisodium phosphate, potassium phosphate, sodium carbonate, potassium phosphate, etc. are also preferable because they have a buffering action by themselves. These alkaline agents are added so that the pH of the developer is in the range of 9.0 to 13.5, and the amount of addition is determined by the desired pH and the type and amount of non-reducing sugar. The range is from 10.0 to 13.2.

Further, an alkaline buffer consisting of a weak acid other than saccharides and a strong base can be used in combination with the developer. As a weak acid used as such a buffer, pKa is 10.0 to
13.2 is preferred. Such weak acids include
IONISATION CONSTANTS OF ORGA published by Pergamon Press
Selected from those described in NIC ACIDS IN AQUEOUS SOLUTION and the like, for example, 2,2,3,3-tetrafluoropropanol-1 (pKa 12.74), trifluoroethanol (12.37), and trichloroethanol (12 Alcohols such as 12.24), pyridine-2-
Aldehydes such as aldehyde (12.68), pyridine-4-aldehyde (12.05), salicylic acid (13.0), 3-hydroxy-2-naphthoic acid (12.84) and catechol (12.84) 12.6), gallic acid (12.4), sulfosalicylic acid (11.7),
3,4-dihydroxysulfonic acid (12.2 above), 3,
4-dihydroxybenzoic acid (11.94), 1,2,2
4-trihydroxybenzene (11.82), hydroquinone (11.56), pyrogallol (11.3)
4), o-cresol (10.33), resorcinol (11.27), p-cresol (10.2)
7) compounds having a phenolic hydroxyl group such as m-cresol (10.09);

2-butanone oxime (12.45);
Acetoxime (12.42), 1,2-cycloheptanedione dioxime (12.3), 2-hydroxybenzaldehyde oxime (12.10), dimethylglyoxime (11.9), ethanediamide dioxime (11.37) and acetophenone oxime (11.37).
Oximes such as 35) and adenosine (12.5
6), inosine (12.5) and guanine (12.
3), cytosine (12.2), hypoxanthine (1)
2.1), nucleic acid-related substances such as xanthine (11.9), and diethylaminomethylphosphonic acid (12.
32), 1-amino-3,3,3-trifluorobenzoic acid (12.29), isopropylidene diphosphonic acid (12.10), 1,1-ethylidene diphosphonic acid (11.54) , 1,1-ethylidene diphosphonic acid 1
-Hydroxy (11.52), benzimidazole (12.86), thiobenzamide (12.8),
Weak acids such as picoline thioamide (12.55) and barbituric acid (12.5).

Preferred among these weak acids are sulfosalicylic acid and salicylic acid. As the base to be combined with these weak acids, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide are preferably used.
These alkali agents are used alone or in combination of two or more. The above-mentioned various alkaline agents are used by adjusting the pH within a preferred range depending on the concentration and combination.

(Surfactant) To the developer, various surfactants and organic solvents can be added as necessary for the purpose of accelerating the developing property, dispersing the developing residue and increasing the ink affinity of the printing plate image area. Preferred surfactants include anionic,
Cationic, nonionic and amphoteric surfactants are included. Preferred examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, and sorbitan. Fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol monofatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, poly Glycerin fatty acid partial esters, polyoxyethylated castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acids Ethanol amides, N, N
Non-ionic surfactants such as -bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, and trialkylamine oxides;

Fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts,
Dialkyl sulfosuccinates, linear alkylbenzene sulfonates, branched alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl- N-oleyltaurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated tallow oil, sulfate esters of fatty acid alkyl esters, alkyl sulfate salts, polyoxyethylene alkyl ether sulfate salts, Fatty acid monoglyceride sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, polyoxyethylene styryl phenyl ether sulfate salts, Alkyl phosphate phosphate salts, polyoxyethylene alkyl ether phosphate salts, polyoxyethylene alkyl phenyl ether phosphate salts, partially saponified styrene / maleic anhydride copolymers, partial olefin / maleic anhydride copolymers Anionic surfactants such as saponified products and naphthalene sulfonate formalin condensates; quaternary ammonium salts such as alkylamine salts and tetrabutylammonium bromide; cationic interfaces such as polyoxyethylene alkylamine salts and polyethylene polyamine derivatives. Activators, amphoteric surfactants such as carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfates, and imidazolines. Among the surfactants mentioned above, the term "polyoxyethylene" can be read as a polyoxyalkylene such as polyoxymethylene, polyoxypropylene, or polyoxybutylene, and these surfactants are also included.

Further preferred surfactants are fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Examples of such a fluorine-based surfactant include an anionic type such as a perfluoroalkyl carboxylate, a perfluoroalkyl sulfonate and a perfluoroalkyl phosphate, an amphoteric type such as a perfluoroalkyl betaine, and a perfluoroalkyltrimethylammonium salt. Cationic and perfluoroalkylamine oxides, perfluoroalkylethylene oxide adducts, oligomers containing perfluoroalkyl groups and hydrophilic groups, oligomers containing perfluoroalkyl groups and lipophilic groups, perfluoroalkyl groups, hydrophilic groups and lipophilic Nonionic types such as group-containing oligomers, urethanes containing perfluoroalkyl groups and lipophilic groups are included. The above surfactants can be used alone or in combination of two or more, and are added to the developer in an amount of 0.001 to 10% by weight, more preferably 0.01 to 5% by weight.

(Development Stabilizer) Various development stabilizers are used in the developer. Preferred examples thereof include polyethylene glycol adducts of sugar alcohols described in JP-A-6-282079, tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium such as diphenyliodonium chloride. Salts are mentioned as preferred examples. Moreover,
Anionic or amphoteric surfactants described in JP-A-50-51324 and JP-A-55-95946.
Water soluble cationic polymer described in
There is a water-soluble amphoteric polymer electrolyte described in JP-A-142528. Further, an organic boron compound to which an alkylene glycol has been added described in JP-A-59-84241, a polyoxyethylene / polyoxypropylene block polymerization type water-soluble surfactant described in JP-A-60-111246, Polyoxyethylene / polyoxypropylene-substituted alkylenediamine compounds described in JP-A-60-129750, polyethylene glycol having a weight average molecular weight of 300 or more described in JP-A-61-215554, and cations described in JP-A-63-175858 Fluorinated surfactant having a functional group, JP-A-2-3915
No. 7 include water-soluble ethylene oxide adducts obtained by adding 4 mol or more of ethylene oxide to the acid or alcohol, and water-soluble polyalkylene compounds.

(Organic Solvent) Although the developer contains substantially no organic solvent, an organic solvent is added if necessary. Such an organic solvent has a solubility in water of about 1
Those having 0% by weight or less are suitable, preferably 5% by weight.
Selected from: For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 4-phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2-phenoxyethanol, Benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-
Examples include methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanolamine and N-phenyldiethanolamine. To be substantially free of an organic solvent in the developer means that the content of the organic solvent is 5% by weight or less based on the total weight of the used solution. The amount used is closely related to the amount used of the surfactant, and it is preferable to increase the amount of the surfactant as the amount of the organic solvent increases. This is because when the amount of the surfactant is small and the amount of the organic solvent is large, the organic solvent is not completely dissolved, and therefore, it is impossible to expect good developing property.

(Reducing Agent) A reducing agent can be further added to the developer. This prevents contamination of the printing plate, and is particularly effective when developing a negative photosensitive lithographic printing plate containing a photosensitive diazonium salt compound. Preferred organic reducing agents include thiosalicylic acid, hydroquinone,
Examples include phenol compounds such as metol, methoxyquinone, resorcin, and 2-methylresorcin, and amine compounds such as phenylenediamine and phenylhydrazine. More preferred inorganic reducing agents include sodium salts, potassium salts, and ammonium salts of inorganic acids such as sulfurous acid, bisulfite, phosphorous acid, hydrogen phosphite, diphosphite, thiosulfate and dithionite. Salts and the like can be mentioned. Among these reducing agents, sulfites are particularly excellent in the stain prevention effect. These reducing agents are preferably contained in a range of 0.05 to 5% by weight with respect to the developing solution at the time of use.

(Organic carboxylic acid) An organic carboxylic acid can be further added to the developer. Preferred organic carboxylic acids are aliphatic and aromatic carboxylic acids having 6 to 20 carbon atoms. Specific examples of the aliphatic carboxylic acid include caproic acid, enantiic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. . Further, unsaturated fatty acids having a double bond in the carbon chain or branched fatty acids may be used. As the aromatic carboxylic acid, a benzene ring, a naphthalene ring,
Compounds in which a carboxyl group is substituted on the anthracene ring or the like, specifically, o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic acid, o-aminobenzoic acid, p- Aminobenzoic acid, 2,
4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, There are 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-naphthoic acid and the like, and hydroxynaphthoic acid is particularly effective. The above aliphatic and aromatic carboxylic acids are preferably used as sodium salts, potassium salts or ammonium salts in order to increase the water solubility. The content of the organic carboxylic acid in the developer is not particularly limited, but if the content is less than 0.1% by weight, the effect is not sufficient.
If it is 10% by weight or more, not only the effect cannot be further improved, but also dissolution may be hindered when another additive is used in combination. Therefore, the preferred amount of addition is 0.1 to 10% by weight, more preferably 0.1 to 10% by weight, based on the developer used.
5 to 4% by weight.

(Others) The developer may further contain a preservative, a colorant, a thickener, an antifoaming agent, a water softener and the like, if necessary. Examples of the water softener include polyphosphoric acid and its sodium salt, potassium salt and ammonium salt, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid. Aminopolycarboxylic acids such as acetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts;
Aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and 1-
Hydroxyethane-1,1-diphosphonic acid and its sodium, potassium and ammonium salts can be mentioned.

The optimum value of such a water softener varies depending on the chelating power, the hardness of the hard water used and the amount of the hard water. 01 to 5% by weight, more preferably 0.01 to 5% by weight
It is in the range of 0.5% by weight. If the added amount is less than this range, the intended purpose is not sufficiently achieved, and if the added amount is more than this range, adverse effects on the image area such as color omission appear. The remaining component of the developer is water. It is advantageous from the viewpoint of transportation that the developing solution is a concentrated solution having a smaller water content than at the time of use and is diluted with water at the time of use. In this case, the concentration is suitably such that the components do not separate or precipitate.

As the developer for the photosensitive lithographic printing plate of the present invention, the developer described in JP-A-6-282079 can also be used. This is because an alkali metal silicate having a molar ratio of SiO ₂ / M ₂ O (M represents an alkali metal) of 0.5 to 2.0, and a sugar alcohol having 4 or more hydroxyl groups are added with 5 mol or more of ethylene oxide. Developer containing a water-soluble ethylene oxide addition compound obtained by the above method. Sugar alcohol is a polyhydric alcohol corresponding to one obtained by reducing an aldehyde group and a ketone group of a sugar to form primary and secondary alcohol groups, respectively. Specific examples of sugar alcohols include D, L-trait, erythritol, D, L-arabit, rebit, xylit, D, L-sorbit,
D, L-mannit, D, L-idit, D, L-talit, dursit, allozursit and the like, and also di-, tri-, tetra-, penta- and hexaglycerin condensed with a sugar alcohol. The water-soluble ethylene oxide adduct is obtained by adding 5 mol or more of ethylene oxide to 1 mol of the sugar alcohol. Further, propylene oxide may be block-copolymerized with the ethylene oxide-added compound, if necessary, as long as the solubility is acceptable. These ethylene oxide addition compounds may be used alone or in combination of two or more. The amount of these water-soluble ethylene oxide addition compounds to be added is 0.001 to 1.0 with respect to the developer (solution used).
5% by weight is suitable, more preferably 0.001-2%
% By weight. The above-mentioned various surfactants and organic solvents can be further added to this developer, if necessary, for the purpose of promoting the developability, dispersing the development residue, and increasing the ink affinity of the printing plate image area.

(Development and post-processing) The photosensitive lithographic printing plate developed with a developer having such a composition is washed with water, a rinsing solution containing a surfactant and the like, and a finisher mainly containing gum arabic and starch derivatives. And a post-treatment with a protective gum solution. In the post-processing of the photosensitive lithographic printing plate of the present invention, these processings can be used in various combinations. In recent years, in the plate making / printing industry, automatic developing machines for photosensitive lithographic printing plates have been widely used in order to rationalize and standardize plate making operations. This automatic developing machine generally comprises a developing section and a post-processing section, and comprises a device for transporting a photosensitive lithographic printing plate, and each processing solution tank and a spray device, and horizontally transports an exposed photosensitive lithographic printing plate. The developing and post-processing are performed by spraying each processing solution pumped up by a pump from a spray nozzle. Recently, a method of immersing and transporting a photosensitive lithographic printing plate in a processing solution tank filled with a processing solution by a submerged guide roll or the like to perform development processing, or supplying a fixed amount of small amount of washing water to the plate after development A method is also known in which the waste water is reused as diluting water for the undiluted developer solution. In such automatic processing, the processing can be performed while replenishing each processing liquid with a replenisher according to the processing amount, the operating time, and the like. Further, a so-called disposable processing method in which processing is performed with a substantially unused processing liquid can also be applied. The lithographic printing plate obtained by such a process is set on an offset printing machine and used for printing a large number of sheets.

Next, the photosensitive composition of the present invention when used as a negative photosensitive layer of a photopolymerizable printing plate will be described. When the photosensitive composition of the present invention is a photopolymerizable photosensitive composition, the main components thereof include, in addition to the fluorine-based polymer, a compound containing an addition-polymerizable ethylenic double bond, And a compound such as a thermal polymerization inhibitor, if necessary.

The compound containing an addition-polymerizable double bond is
It can be arbitrarily selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. For example, those having a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. Examples of monomers and copolymers thereof include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, and unsaturated esters. Examples include amides of carboxylic acids and aliphatic polyamine compounds.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3.
-Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol pentaacrylate
G, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer and the like.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, sorbitol tri Methacrylate, sorbitol tetramethacrylate , Bis [p- (3--methacryloxy-2-hydroxypropoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
There are 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like.

The crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. The maleic acid ester includes ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like. Furthermore, a mixture of the above-mentioned ester monomers can also be mentioned.

Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like. Another example is JP-B-48-417.
08 polyisocyanate compound having two or more isocyanate groups in one molecule described in
A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule to which a hydroxyl group-containing vinyl monomer represented by the following general formula (A) is added is exemplified. CH ₂ ＣC (R ₅ ) COOCH ₂ CH (R ₆ ) OH (A) (where R ₅ and R ₆ represent H or CH ₃ )

Further, urethane acrylates as described in JP-A-51-37193,
64183, JP-B-49-43191, JP-B-52
And polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in JP-A-30490. In addition, Journal of the Adhesion Society of Japan vol. 20, No. 7, 300-30
Those introduced as photocurable monomers and oligomers on page 8 (1984) can also be used. In addition, the amount of these used is 5-70 with respect to all components.
% By weight (hereinafter abbreviated as%), preferably 10 to 50%
%.

As the photopolymerization initiator contained in the photopolymerizable photosensitive composition used in the present invention, various photopolymerization initiators known in patents and literatures, or 2 A combination system of two or more photopolymerization initiators (photopolymerization initiation system) can be appropriately selected and used. For example, when light near 400 nm is used as a light source, benzyl, benzoin ether, Michler's ketone, anthraquinone, thioxanthone, acridine, phenazine, benzophenone, and the like are widely used.

Also, visible light of 400 nm or more, Ar laser, second harmonic of semiconductor laser, SHG-YAG
Even when a laser is used as a light source, various photopolymerization initiation systems have been proposed, for example, US Pat. No. 2,850,44.
Certain photoreducing dyes described in No. 5, such as rosbengal, eosin, erythrosine, and the like, or a system based on a combination of a dye and a photopolymerization initiator, for example, a complex initiation system of a dye and an amine (Japanese Patent Publication No. Sho 44) -20189), a combination system of hexaarylbiimidazole, a radical generator and a dye (JP-B-45-37377), and a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (JP-B-47-2528; 54-1 Kaisho
55292), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183), a system of a cyclic triazine and a merocyanine dye (JP-A-54-151024).
No.), a system of 3-ketocoumarin and an activator (JP-A-52-1)
No. 12681, JP-A-58-15503), a system of biimidazole, a styrene derivative and a thiol (JP-A-59-15503).
140203), a system of an organic peroxide and a dye (JP-A-5
9-1504, JP-A-59-140203, JP-A-59-189340, JP-A-62-174203,
JP-B-62-1641, U.S. Pat. No. 4,766,055
No.), a system of a dye and an active halogen compound (JP-A-63-2
58903, JP-A-2-63054, etc.),

Dye and borate compound system
No. 143044, JP-A-62-150242, JP-A-64-13140, JP-A-64-13141, JP-A-64-13142, JP-A-64-13143, JP-A-64-13144 JP-A-64-17048,
JP-A-1-229003, JP-A-1-298348
And a system comprising a dye having a rhodanine ring and a radical generator (Japanese Patent Laid-Open No. 2-1796).
No. 43, JP-A-2-244050), titanocene and 3
-Ketocoumarin dye system (JP-A-63-221110)
), A system combining a titanocene and a xanthene dye and an addition-polymerizable ethylenically unsaturated compound containing an amino group or a urethane group (JP-A-4-221958,
JP-A-4-219756), a system of titanocene and a specific merocyanine dye (JP-A-6-295061), and a system of titanocene and a dye having a benzopyran ring (JP-A-8-295).
No. 334897). The amount of these photopolymerization initiators used is 100 ethylenically unsaturated compounds.
It can be used in an amount of 0.05 to 100 parts by weight, preferably 0.1 to 70 parts by weight, more preferably 0.2 to 50 parts by weight, based on parts by weight.

Further, in the photopolymerizable photosensitive composition of the present invention, in addition to the above basic components, unnecessary thermal polymerization of an ethylenically unsaturated compound which can be polymerized during the production or storage of the photosensitive composition. It is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent the polymerization. Suitable thermal polymerization inhibitors include haloid quinone, p-methoxyphenol, di-t
-Butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-
Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol),
N-nitrosophenylhydroxylamine cerium salt, N-nitrosophenylhydroxylamine aluminum salt and the like can be mentioned. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% to about 5% based on the weight of the whole composition.
Further, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. . The addition amount of the higher fatty acid derivative is preferably about 0.5% to about 10% of the whole composition.

A lithographic printing plate having a photosensitive layer using a photopolymerizable composition as the photosensitive composition of the present invention is provided on the photopolymerizable photosensitive layer with an oxygen barrier to prevent polymerization inhibition by oxygen. A protective layer may be provided. Examples of the water-soluble vinyl polymer contained in the oxygen-blocking protective layer include polyvinyl alcohol, and its partial esters, ethers, and acetal, or a substantial amount of unsubstituted vinyl alcohol units that have the necessary water solubility. And copolymers thereof. Polyvinyl alcohol is hydrolyzed by 71 to 100% and has a polymerization degree of 30.
Those having a range of 0 to 2400 are exemplified.

Specifically, PVA-10 manufactured by Kuraray Co., Ltd.
5, PVA-110, PVA-117, PVA-117
H, PVA-120, PVA-124, PVA-124
H, PVA-CS, PVA-CST, PVA-HC, P
VA-203, PVA-204, PVA-205, PV
A-210, PVA-217, PVA-220, PVA
-224, PVA-217EE, PVA-217E, P
VA-220E, PVA-224E, PVA-405,
PVA-420, PVA-613, L-8 and the like. Examples of the copolymer include polyvinyl acetate chloroacetate or propionate, polyvinyl formal and polyvinyl acetal which have been hydrolyzed 88 to 100%, and copolymers thereof. Other useful polymers include polyvinylpyrrolidone, gelatin and gum arabic, which may be used alone or in combination.

The solvent used for coating the oxygen barrier protective layer of the present invention is preferably pure water, but alcohols such as methanol and ethanol, and ketones such as acetone and methyl ethyl ketone may be mixed with pure water. . The concentration of the solid content in the coating solution is suitably from 1 to 20% by weight. Known additives such as a surfactant for improving coating properties and a water-soluble plasticizer for improving physical properties of a film may be added to the oxygen-barrier protective layer of the present invention. Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin, and sorbitol. Further, a water-soluble (meth) acrylic polymer or the like may be added. The coating amount of the oxygen-barrier protective layer is suitably in the range of about 0.1 / m ² to about 15 / m ² by weight after drying. More preferably, it is 1.0 / m ² to about 5.0 / m ² .

Examples of the printing-out agent for obtaining a visible image immediately after exposure include a combination of a photosensitive compound which releases an acid upon exposure and an organic dye which forms a salt with an acid and changes the color tone. it can.

The photosensitive compound which releases an acid upon exposure includes, for example, o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-36209; No. 223, trihalomethyl-2-pyrone and trihalomethyl-s-triazine; various o-naphthoquinonediazide compounds described in JP-A-55-62,444; 77, 742, 2-trihalomethyl-5-aryl-1,3,4-oxadiazole compounds; diazonium salts and the like. These compounds can be used alone or as a mixture, and the amount added is based on the total weight of the composition.
A range from 0.3 to 15% by weight is preferred.

In the photosensitive composition of the present invention, at least one or more organic dyes which change the color tone by interacting with the photolysis product of a compound which generates an acidic substance upon photolysis are used. Such organic dyes include diphenylmethane, triarylmethane,
Thiazine-based, oxazine-based, phenazine-based, xanthene-based, anthraquinone-based, iminonaphthoquinone-based, and azomethine-based dyes can be used. Specifically, it is as follows.

Brilliant green, eosin, ethyl violet, erythrosin B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein, methyl violet 2B, quinaldine red, Rose bengal, thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenylthiocarbazone, 2,7-
Dichlorofluorescein, paramethyl red, congo red, benzopurpurine 4B, α-naphthyl red,
Nile blue 2B, Nile blue A, phenacetaline,
Methyl violet, malachite green, parafuchsin, oil blue # 603 [Orient Chemical Industry Co., Ltd.
Oil Pink # 312 [Orient Chemical Industry Co., Ltd.], Oil Red 5B [Orient Chemical Industry Co., Ltd.], Oil Scarlet # 308 [Orient Chemical Industry Co., Ltd.], Oil Red OG [Orient Chemical Co., Ltd.] Industrial Co., Ltd.), Oil Red RR (Orient Chemical Co., Ltd.), Oil Green # 502 (Orient Chemical Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Co., Ltd.), Victoria Pure Blue BOH (made by Hodogaya Chemical Industry Co., Ltd.),

Patent Pure-Blue (manufactured by Sumitomo Sangoku Chemical Co., Ltd.), Sudan Blue II (manufactured by BASF), m
-Cresol purple, cresol red, rhodamine B, rhodamine 6G, first acid violet R, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2 -Carbostearylamino-4-p-dihydroxyethyl-amino-phenyliminonaphthoquinone, p-methoxybenzoyl-p'-diethylamino-
o'-methylphenyliminoacetanilide, cyano-
p-diethylaminophenyliminoacetanilide, 1
-Phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, 1-β-naphthyl-4-
p-diethylaminophenylimino-5-pyrazolone and the like.

A particularly preferred organic dye is a triarylmethane dye. Triarylmethane dyes are disclosed in JP-A-62-293471 and JP-A-5-3133.
Those having a sulfonic acid compound as a counter anion as disclosed in JP-A-59-5959 are particularly useful. These dyes can be used alone or as a mixture, and the addition amount is preferably 0.3 to 15% by weight based on the total weight of the photosensitive composition. Also can be used with other dyes and pigments as needed,
70% by weight based on the total weight of dyes and pigments
Or less, more preferably 50% by weight or less.

Others In the composition of the present invention, various resins having a hydrophobic group, for example, octylphenol / formaldehyde resin, t-butylphenol / formaldehyde resin, t
-Butylphenol-benzaldehyde resin, rosin-modified novolak resin, and o of these modified novolak resins
-Naphthoquinonediazide sulfonic acid ester and the like; depending on various purposes, such as a plasticizer for improving the flexibility of the coating film, such as dibutyl phthalate, dioctyl phthalate, butyl glycolate, tricresyl phosphate, and dioctyl adipate. Various additives can be added. The amount of these additives is preferably in the range of 0.01 to 30% by weight based on the total weight of the composition.

Further, a known resin for further improving the abrasion resistance of the film can be added to these compositions. These resins include, for example, a polyvinyl acetal resin, a polyurethane resin, an epoxy resin, a vinyl chloride resin, a nylon, a polyester resin, an acrylic resin, and the like, and can be used alone or in combination. The addition amount is preferably in the range of 2 to 40% by weight based on the total weight of the composition.

Further, in the photosensitive composition of the present invention, in order to widen the latitude of development, Japanese Patent Application Laid-Open No.
Non-ionic surfactants described in JP-A-251740 and JP-A-4-68355;
An amphoteric surfactant as described in JP-A-9-121044 and JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearate, polyoxyethylene sorbitan monooleate, polyoxyethylene nonyl phenyl ether, and the like. Specific examples of the activator include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, Amogen K (trade name, manufactured by Dai-ichi Kogyo Seiyaku 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 composition is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

Improvement of coated surface quality: In the photosensitive composition of the present invention, a surfactant for improving coated surface quality, for example, fluorine as described in JP-A-62-170950. A system surfactant can be added.
The preferable addition amount is 0.001 to 1.
0% by weight, and more preferably 0.005 to 0.5% by weight.

The photosensitive composition of the present invention contains a yellow dye, preferably having an absorbance at 417 nm of 436 nm.
More than 70% of yellow dyes can be added. The present invention relates to a positive type using the above quinonediazide or a compound having an alkali-soluble group protected by an acid-decomposable group.
In addition to PS plates and negative PS plates using a photopolymerization system, the following types of lithographic printing plate materials can be similarly used. (1) Negative lithographic printing plate material using diazo resin (2) Negative lithographic printing plate material using photocrosslinkable resin (3) Alkali-soluble binder, acid generator, acid (heat) crosslinkable compound Negative type laser direct drawing type lithographic printing material including

Hereinafter, the materials used in each example will be described in detail. The diazo resin used in (1) includes, for example, a diazo resin represented by a salt of a condensate of a diazodiarylamine and an active carbonyl compound, and is preferably photosensitive, water-insoluble, and soluble in an organic solvent. Particularly preferred diazo resins include, for example, 4-diazodiphenylamine,
-Diazo-3-methyldiphenylamine, 4-diazo-
4'-methyldiphenylamine, 4-diazo-3'-methyldiphenylamine, 4-diazo-4'-methoxydiphenylamine, 4-diazo-3-methyl-4'-ethoxydiphenylamine, 4-diazo-3-methoxydiphenylamine and the like Formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, 4,4 '
An organic acid salt or an inorganic acid salt of a condensate with bis-methoxymethyldiphenyl ether or the like.

Examples of the organic acid at this time include methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid,
Xylenesulfonic acid, mesitylenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, propylnaphthalenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 2-hydroxy-4-methoxy Benzophenone-5-sulfonic acid and the like can be mentioned, and inorganic acids include hexafluorophosphoric acid, tetrafluoroboric acid, thiocyanic acid and the like. Further, JP-A-54-30,
No. 121, a diazo resin whose main chain is a polyester group; a reaction between a polymer having a carboxylic anhydride residue described in JP-A-61-273538 and a diazo compound having a hydroxyl group. A diazo resin obtained by reacting a polyisocyanate compound with a diazo compound having a hydroxyl group can also be used.

The use amount of these diazo resins is preferably in the range of 0 to 40% by weight based on the solid content of the composition. If necessary, two or more diazo resins may be used in combination. In preparing the negative photosensitive composition, an organic polymer binder is usually used in combination. As such an organic polymer binder, for example, acrylic resin, polyamide resin,
Examples include polyester resin, epoxy resin, polyacetal resin, polystyrene resin, and novolak resin. Further, in order to improve performance, known additives, for example,
Thermal polymerization inhibitors, dyes, pigments, plasticizers, stability improvers and the like can be added.

Suitable dyes include, for example, crystal violet, maracay green, Victoria blue,
Basic oil-soluble dyes such as methylene blue, ethyl violet, and rhodamine B are included. Examples of commercially available products include “Victoria Pure Blue BOH” (manufactured by Hodogaya Chemical Industry Co., Ltd.) and “Oil Blue # 603”.
(Manufactured by Orient Chemical Industry Co., Ltd.). Examples of the pigment include phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone red, and the like.

Examples of the plasticizer include diethyl phthalate, dibutyl phthalate, dioctyl phthalate, tributyl phosphate, trioctyl phosphate, tricresyl phosphate, tri (2-chloroethyl) phosphate, tributyl citrate and the like. Further, as known stability improvers, for example, phosphoric acid, phosphorous acid, oxalic acid, tartaric acid, malic acid, citric acid, dipicolinic acid, polyacrylic acid, benzenesulfonic acid, toluenesulfonic acid and the like can be used in combination. The amount of these various additives varies depending on the purpose, but generally, the amount of the solid content of the photosensitive composition is 0 to 0.
A range of 30% by weight is preferred.

As the photocrosslinkable resin used in (2), a photocrosslinkable resin having an affinity for an aqueous alkaline developer is preferable. For example, a cinnamic acid group described in JP-B No. 54-15711 can be used. A copolymer having a carboxyl group; a phenylenediacrylic acid residue described in JP-A-60-165646 and a polyester resin having a carboxyl group; and a phenylenediacrylic acid residue described in JP-A-60-203630. Polyester resin having a phenolic hydroxyl group; polyester resin having a phenylenediacrylic acid residue and a sodium iminodisulfonyl group described in JP-B-57-42858;
Polymers having an azide group and a carboxyl group in the side chain described in JP-A-7-295212, and polymers having a maleimide group in the side chain described in JP-A-7-295212 can be used.

An alkali-soluble binder used in (3),
As the acid generator, the same materials as those described above for the positive PS plate using quinonediazide or a compound having an alkali-soluble group protected by an acid-decomposable group can be used. The acid (thermal) crosslinkable compound refers to a compound that crosslinks in the presence of an acid, and includes, for example, aromatic compounds and heterocyclic compounds that are polysubstituted with a hydroxymethyl group, an acetoxymethyl group, or an alkoxymethyl group. Among them, preferred examples include compounds obtained by condensing phenols and aldehydes under basic conditions. Preferred among the above compounds are, for example, compounds obtained by condensing phenol and formaldehyde under basic conditions as described above, similarly, compounds obtained from m-cresol and formaldehyde, and compounds obtained from bisphenol A and formaldehyde. Compound,
Compounds obtained from 4,4'-bisphenol and formaldehyde, and other compounds disclosed as resol resins in GB 2,082,339 are exemplified.

These acid crosslinking compounds have a weight average molecular weight of 500 to 100,000 and a number average molecular weight of 200 to 100.
50,000 are preferred. Other preferred examples include aromatic compounds substituted with an alkoxymethyl or oxiranylmethyl group disclosed in EP-A-0,212,482, EP-A-0,133,216, and D-A.
EA No. 3,634,671, DE No. 3,711,2
No. 64, monomer and oligomer melamine-formaldehyde condensates and urea-formaldehyde condensates, alkoxy-substituted compounds disclosed in EP-A-0,212,482. Still other preferred examples are, for example, melamine-formaldehyde derivatives having at least two free N-hydroxymethyl, N-alkoxymethyl or N-acyloxymethyl groups.
Of these, N-alkoxymethyl derivatives are particularly preferred.

Also, low molecular weight or oligomeric silanols can be used as silicon-containing crosslinkers. Examples of these are dimethyl- and diphenyl-silanediols and oligomers which have already been precondensed and contain these units, for example those disclosed in EP-A 0,377,155. Among aromatic compounds and heterocyclic compounds poly-substituted with an alkoxymethyl group, a compound having an alkoxymethyl group at a position adjacent to a hydroxyl group, and the alkoxy group of the alkoxymethyl group having 18 or less carbon atoms is preferable. Examples can be given. The acid-crosslinkable compound used in the present invention accounts for 5 to 80% by weight, preferably 10 to 75% by weight, particularly preferably 20 to 70% by weight, based on the total solid content of the lithographic printing plate material.
Is used in the amount added. If the addition amount of the acid-crosslinkable compound is less than 5% by weight, the durability of the photosensitive layer of the resulting lithographic printing plate material deteriorates, and if it exceeds 80% by weight, storage stability is not preferred. (Development and Finishing) Development is generally performed by an automatic developing machine 800H manufactured by Fuji Photo Film Co., Ltd. using a solution obtained by diluting an alkaline aqueous solution developer DN-3C manufactured by Fuji Photo Film Co., Ltd. 1: 1 with water. Immediately after the development, a solution obtained by diluting a finishing solution FN-2 manufactured by Fuji Photo Film Co., Ltd. with water at a ratio of 1: 1 is applied and dried.

[0124]

The present invention will be further described below with reference to examples.
You. However, the present invention is limited by these examples.
Not something. Example 1 The percentages in this example are
All percentages are by weight unless otherwise specified. 0.24mm thick
The surface of JIS A1050 aluminum plate
Rashi and sand using 400 mesh pumice ton suspension
After sharpening, it was washed well with water. 10% sodium hydroxide
Immersed in aluminum at 70 ° C. for 60 seconds and etched.
20% HNO after washing with water_ThreeAnd washed with water. this
And V_ASine wave alternating current under the condition of = 12.7V
230 coulomb / dm in 1% nitric acid aqueous solution ^TwoSunshine
Electrolytic surface-roughening treatment was performed with an extreme amount of electricity. Its surface roughness
When measured, it was 0.55 μm (Ra display).
30% H_TwoSO_Four55 ° C immersed in aqueous solution
Desmut for 2 minutes and rinse with water to create substrate (A)
did. The substrate [A] is placed in a 10% sulfuric acid aqueous solution at 50 ° C.
And current density 30A / dm^Two2.2 g of anodized film
/ M^TwoAfter anodizing to a considerable extent, adjust the pH with sulfuric acid.
The aqueous solution adjusted to 2 was sprayed at 15 ° C. for 10 seconds.
Thereafter, the substrate was washed with water to produce a substrate [B].

Example 2 The above substrate [A] was heated at 50 ° C.
After anodizing in a 0% sulfuric acid aqueous solution such that the current density is 30 A / dm ² and the amount of the anodic oxide film is equivalent to 2.2 g / m ² , the aqueous solution adjusted to pH 3 with sulfuric acid is sprayed at 10 ° C. for 20 seconds. The substrate was treated and washed with water to produce a substrate [C]. Example 3 After anodizing the substrate [A] in a 10% aqueous sulfuric acid solution at 50 ° C. so that the current density was 30 A / dm ² and the amount of anodized film was 2.2 g / m ^2. An aqueous solution adjusted to pH 4 with sulfuric acid was sprayed at 30 ° C. for 10 seconds, and washed with water to produce a substrate [D]. [Examples 4 to 6] The above substrate [C] was treated with a 0.1% aqueous solution of sodium silicate No. 3 and washed with water to form a substrate [E1].
[E2] and [E3] were produced. The amount of sodium silicate deposited on the substrate [C] was 0.3 mg / m 2 as the atomic weight of Si.
^2, 1.5mg / m ^2, was 7.8mg / m ^2.

In the above embodiment, the adhesion amount of sodium silicate on the substrates [E1], [E2] and [E3] after the treatment with the aqueous sodium silicate solution was calibrated using a fluorescent X-ray analyzer as described above. It was measured as the amount of Si atoms (mg / m ² ) by the linear method. That is, the amount of Si atoms was measured from the peak height of the Si-Kα spectrum under the following conditions using RIX3000 manufactured by Rigaku Corporation as a model of the X-ray fluorescence analyzer. Apparatus: RIX3000 manufactured by Rigaku Denki Kogyo Co., Ltd. X-ray tube: Rh Measurement spectrum: Si-Kα Tube voltage: 50 kV Tube current: 50 mA Slit: COARSE Spectral crystal: RX4 Detector: F-PC Analysis area: 30 mmφ Peak position ( 2θ): 144.75 deg. Background (2θ): 140.70 deg. , 146.85 deg. Integration time: 80 seconds / sample The amount of Si atoms shown in Examples 4 to 6 is an amount corrected by subtracting the amount of Si atoms contained in aluminum.

[Comparative Example 1] The substrate [A] of Example 1 was replaced with 50
Current density 30A / dm in 10% sulfuric acid aqueous solution at ℃ ^Two, Yang
2.2 g / m of extremely oxidized film^TwoAnodic acid to be considerable
After that, an aqueous solution adjusted to pH 11 with sulfuric acid is added to 60
After spraying for 2 minutes at ℃, rinse with water
Produced. [Comparative Example 2] The substrate [A] of Example 1 was subjected to 10% sulfuric acid treatment at 50 ° C.
Current density 30A / dm in acid aqueous solution ^Two, Anodized film amount
Is 2.2 g / m^TwoAfter anodizing to be considerable,
No. 3 after treating with water of pH 7 at 15 ° C for 10 seconds, washing with water
Treated with a 2.5% aqueous solution of sodium silicate at 30 ° C for 10 seconds
Then, a substrate [G] was produced. Silicic acid of this substrate [G]
The amount of attached atoms is 4 mg / m as the atomic weight of Si.^TwoSo
Was.

The following solution [A] having an onium group together with an acid group described in JP-A-10-301269 was applied to the surface of each of the substrates [B] to [G] and dried at 100 ° C. for 10 seconds. did. The coating amount after drying was 6.5 m in each case.
g / m ² . [Intermediate layer solution A] The following polymer compound (A) 0.14 g methanol 100 g water 1 g

[0129]

Embedded image

Next, the following photosensitive solution [A] was applied on each of the substrates treated as described above to form a photosensitive layer. The coating amount of the photosensitive layer after drying was 1.8 g / m ² . Furthermore, in order to shorten the vacuum adhesion time, Japanese Patent Publication No. 61-28986
The photosensitive lithographic printing plate was prepared by forming a mat layer according to the method described in Japanese Patent Application Laid-Open Publication No. H11-163,036. [Photosensitive solution A] Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (described in Example 1 of U.S. Pat. No. 3,635,709). 8 g Binder Novolak (I) (below) 1.5 g Novolak (II) (below) 0.2 g Resin (III) other than novolak (below) 0.4 g

[0131]

Embedded image

P-Normal octylphenol-formaldehyde resin (described in US Pat. No. 4,123,279) 0.02 g naphthoquinonediazide-1,2-diazide-4-sulfonic acid chloride 0.01 g tetrahydro Phthalic anhydride 0.02 g Benzoic acid 0.02 g Pyrogallol 0.05 g Triazine A 0.07 g Victoria Pure-Blue BOH (a dye manufactured by Hodogaya Chemical Co., Ltd. in which the counter anion is changed to 1-naphthalenesulfonic acid) 0.045 g F176PF (fluorinated surfactant) (manufactured by Dainippon Ink and Chemicals, Inc.) 0.01 g methyl ethyl ketone 15.0 g 1-methoxy-2-propanol 10.0 g

The photosensitive lithographic printing plate thus produced was image-exposed from a distance of 1 m with a 3 kW metal halide lamp for 1 minute, and was exposed to light using a PS processor 900VR manufactured by Fuji Photo Film Co., Ltd. using the following developer. Developed for seconds. Developing solution: [SiO ₂ ] / [Na ₂ O] molar ratio 1.2 SiO ₂ 1.4% by weight of sodium silicate aqueous solution 100 parts by weight Ethylenediamine / ethylene oxide adduct (30 mol) 0.03 parts by weight Development as described above The method for evaluating the stain property of the lithographic printing plate obtained by the treatment is described below. Stain properties: SO manufactured by Heidelberg
Stop printing after printing 1000 sheets with the R-M printer,
Leave for a minute. After that, it is attached to the printing machine again and 100
Printed. The manner in which the ink was removed from the non-image area at that time was observed and evaluated as follows. ○ ・ ・ ・ Fast ink dispensing method (not easy to stain) △ ・ ・ ・ Ink dispensing method is slow but not as slow as × × ・ ・ ・ Ink dispensing method is slow (easy to stain) Aluminum hydroxide Appearance failure due to adhesion The degree of adhesion of aluminum hydroxide to the aluminum support was visually evaluated on the substrates [A] to [G] prepared in Examples and Comparative Examples.・ ・ ・: No appearance failure due to adhesion of aluminum hydroxide was observed. Δ: Slight appearance failure due to adhesion of aluminum hydroxide was observed. X: Appearance failure due to adhesion of aluminum hydroxide is observed. The above results are shown in Table 1.

[0134]

[Table 1]

[0135]

According to the present invention, it is possible to produce a photosensitive lithographic printing plate which is free from ink stains in the non-image area, and which does not cause appearance failure due to adhesion of aluminum hydroxide.

Claims (3)

[Claims] 1. An anodized aluminum substrate is treated with p
A method for producing a photosensitive lithographic printing plate, comprising providing a photosensitive layer on an aluminum support treated with an aqueous solution of H 1.5 to 5. 2. An anodized aluminum substrate is treated with p
A method for producing a photosensitive lithographic printing plate, comprising treating with an aqueous solution of H5 to H5, followed by alkali metal silicate treatment, and providing a photosensitive layer on the obtained aluminum support. 3. An anodized aluminum substrate is treated with p
After treating with an aqueous solution of H1.5 to 5, an alkali metal silicate treatment was performed so that the Si atom adhesion amount of the obtained aluminum support was 0.1 to 8 mg / m ² , A method for producing a photosensitive lithographic printing plate, comprising providing a positive photosensitive layer on a body.