JP2002031887A - Method for producing planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a planographic printing plate which ensures good residual color and residual film performances and printing durability and contamination resistances and suppresses the occurrence of scum and sludge in a developing solution during development. SOLUTION: In the method for producing a planographic printing plate, a planographic printing plate obtained by disposing a positive type photosensitive layer on an aluminum substrate with a surface which satisfies the relation of the expression 0.30<=A/(A+B)<=0.90 (where A is the peak area (counts.eV/sec) of fluorine (1S) obtained by measurement using X-ray photoelectron spectroscopy and B is the peak area (counts.eV/sec) of aluminum (2P) obtained by measurement using X-ray photoelectron spectroscopy) is developed with a developing solution not containing a silicate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to developability, corrosion resistance,
The present invention relates to a method for producing a lithographic printing plate having improved stain, printing durability, residual color and residual film performance.

[0002]

2. Description of the Related Art A conventional positive-type photosensitive lithographic printing plate comprises an ink-receiving photosensitive layer provided on a hydrophilic support. Image exposure is performed on the photosensitive layer of such a photosensitive lithographic printing plate, and then the exposed photosensitive layer is developed using a developing solution, whereby the exposed portion of the photosensitive layer is removed and the surface of the hydrophilic support is exposed. On the other hand, the photosensitive layer in the non-exposed area remains on the surface of the support to form an ink-accepting image area, whereby a lithographic printing plate is obtained. It is necessary to further hydrophilize the non-image area in order to prevent stains caused by ink on the non-image area in such a printing plate, but usually, a developing solution containing an alkali metal silicate is used at the time of development. As a result, only the non-image area is made hydrophilic to improve the stain performance. However, when a developer containing an alkali metal silicate is used, a solid due to SiO ₂ is likely to precipitate, or a gel due to SiO ₂ is generated when performing a neutralization treatment when processing a developing waste liquid. There was a problem such as doing. In addition, there has been a problem that the dye dissolved in the developing solution or the lipophilic component such as resin is re-adsorbed to the alkali metal silicate adhered by the development, thereby deteriorating the residual color and the residual film performance.

A developer capable of avoiding these disadvantages contains, as a development stabilizer, at least one compound selected from saccharides, oximes, phenols and fluorinated alcohols in an amount of 0.01 mol / L or more. ,
And a developer containing an alkali agent, that is, a silicate-free developer is conceivable, but when trying to develop a conventional positive-type photosensitive lithographic printing plate, the anodic oxide film on the aluminum support is dissolved by the developer, and It accumulates in the solution and becomes scum and sludge, deteriorating the washability of the automatic processor,
There were other disadvantages, such as clogging of the spray. Further, when a printing plate developed with such a developer is left at the time of printing, there is also a problem that ink is more difficult to be removed, that is, so-called stain is generated.

[0004] In order to solve these problems, various treatments have been proposed for the anodic oxide film of the support. Although steam treatment, which is said to have a dissolution preventing ability during development, can prevent the residual color and residual film phenomenon in the non-image area, the problem of standing stains cannot be solved. In addition, the silicate treatment of the anodized film can solve the problem of standing stains in the non-image area, but has the disadvantage of deteriorating the printing durability and the residual color performance. Not.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a lithographic printing plate having good residual color, residual film performance, printing durability and stain performance, and capable of suppressing scum and sludge in a developing solution during development. It is to provide a method for producing a plate.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and as a result, a lithographic printing method in which a positive photosensitive layer is provided on an aluminum support having a surface satisfying a relationship represented by the following formula: A lithographic printing plate manufacturing method characterized in that the plate is developed with a silicate-free developing solution. Positive photosensitive lithographic printing with excellent residual color, residual film performance, stain performance and printing durability. The present inventors have found that a plate can be obtained and that scum and sludge during development can be suppressed, and the present invention has been completed. That is, in the production method of the present invention, the aluminum support has a formula: 0.30 ≦ A / (A + B) ≦ 0.90 (where A is fluorine (1S) obtained by measurement using X-ray photoelectron spectroscopy. ) Represents the peak area (counts · eV / sec),
B is the peak area of aluminum (2P) obtained by measurement using X-ray photoelectron spectroscopy (represents counts · eV / sec)
It satisfies.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The method of the present invention will be described below in detail. The method for producing a photosensitive lithographic printing plate of the present invention is such that the surface of an aluminum support that has been optionally subjected to anodizing and surface roughening treatments is treated so as to have a constant fluorination rate. This is a method in which a positive photosensitive layer is provided, and after exposure, treatment is performed with a developer containing no silicate.
The method of the present invention is particularly characterized in that a lithographic printing plate manufactured using an aluminum support having a constant fluorination rate is developed with a silicate-free developer.

(Aluminum Support) The aluminum support used in the present invention has a surface of 0.30 ≦ A /
(A + B) ≦ 0.90 (where A represents the peak area (counts · eV / sec) of fluorine (1S) obtained by measurement using X-ray photoelectron spectroscopy, and B represents X-ray photoelectron spectroscopy. Law (Ele
The peak area (counts · eV / sec) of aluminum (2P) obtained by using ctron spectroscopy for chemical analysis (hereinafter, appropriately referred to as ESCA) must be satisfied.

Here, the ESCA will be described. When a sample surface is irradiated with X-rays of a constant energy (hν) in an ultra-high vacuum, electrons (photoelectrons) are emitted from the sample constituent atoms into the vacuum by a photoelectric effect. At this time, the kinetic energy (E _K ) of the emitted photoelectrons is represented by the formula (I), and by measuring E _K with an energy analyzer,
Photoelectron binding energy (E _B ) is required.

[0010]

E _K = hν−E _B −φ (I) (where φ represents a work function)

As the irradiation X-ray, M having a small energy width is used.
g-Kα (1253.6 eV) and Al-Kα (1486.
6 eV), and the penetration depth of such soft X-rays is about several μm from the sample surface. However, photoelectrons generated from a deep part of the sample have a very high probability of losing energy due to inelastic scattering with other atoms before reaching the sample surface. The analysis is performed by jumping out without colliding with the atoms while maintaining the relationship of the formula (I). For this reason, ESCA can measure several nm (several tens of degrees) of the outermost surface of the sample.

In the present invention, the peak area of fluorine (1S) obtained when the surface of an aluminum support is measured by ESCA is defined as A (counts · eV / sec), and the peak area of aluminum (2P) similarly measured is defined as A (counts · eV / sec). B
When (counts · eV / sec), both have a relationship of 0.30 ≦ A / (A + B) ≦ 0.90, preferably satisfying 0.37 ≦ A / (A + B) ≦ 0.85. And more preferably the formula: 0.45 ≦ A / (A + B) ≦ 0.8
5, most preferably the formula 0.55 ≦ A / (A + B)
≤ 0.90). When A / (A + B) is less than 0.30, the content of the inorganic fluorine compound contained in the coating layer is too small, and the intended effect of improving acid resistance and alkali resistance becomes insufficient. On the other hand, if it exceeds 0.90, there is a problem that the adhesion between the substrate and the photosensitive layer is reduced, and the printing durability is deteriorated.

Such a support can be obtained by optionally subjecting the surface of the support to anodizing treatment and then treating it with a fluorine-containing compound or the like. A preferred example is a method of forming a coating layer containing an inorganic fluorine compound on a support. This coating layer may be formed directly on the aluminum substrate, but is preferably formed on the anodic oxide film after anodizing the aluminum support, from the viewpoint of durability and effect.

The coating layer can be formed by contacting an anodic oxide film of an aluminum support with an aqueous solution containing an inorganic fluorine compound. As the inorganic fluorine compound that can be used in the present invention, a metal fluoride is preferable. Specifically, for example, sodium fluoride, calcium fluoride,
Potassium fluoride, magnesium fluoride, potassium hexafluorozirconium, sodium hexafluorozirconium, sodium hexafluorotitanate, potassium hexafluorotitanate, hexafluorozirconium hydrogen acid, hexafluorotitanium hydrogen acid, hexafluorozirconium ammonium, hexafluorotitanium Ammonium acid, hexafluorosilicic acid, nickel fluoride, iron fluoride, phosphoric acid phosphoric acid, ammonium fluoride phosphate, and the like.
More than one species may be used in combination. Preferred inorganic fluorine compounds include sodium fluoride, potassium fluoride, ammonium fluoride and lithium fluoride.

The concentration of the inorganic fluorine compound in the above aqueous solution is suitably from 0.001 g / l to 100 g / l, preferably from 0.01 g / l to 50 g.
/ Liter, more preferably 0.1 g / liter to 2
0 g / liter. The aluminum support of the present invention has, for example, a pH at 25 ° C of 2 to 6, preferably a pH of 2 to 6.
Contacting an aluminum substrate with these aqueous solutions of 3 to 5 at a temperature of 20 ° C to less than 100 ° C, preferably 30 to 70 ° C for 0.5 seconds to 6 minutes, more preferably 1 second to 30 seconds. Can be obtained by As a method of contacting, an aqueous solution may be immersed in these aqueous solutions, or a method of spraying an aqueous solution by spraying on the surface on which the anodic oxide film is formed may be used. It may be carried out by any known method as long as the temperature and contact time of the aqueous solution can be controlled.

When forming a coating layer with an aqueous solution containing an inorganic fluorine compound, the surface of the support may be further treated with phosphoric acid to improve the hydrophilicity.
Examples of the phosphate that can be used for the treatment for improving the hydrophilicity of the support according to the present invention include phosphates of metals such as alkali metals and alkaline earth metals. Specifically, for example, zinc phosphate, aluminum phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, monoammonium phosphate, monopotassium phosphate, monosodium phosphate, dihydrogen phosphate Potassium, dipotassium hydrogen phosphate, calcium phosphate, ammonium sodium hydrogen phosphate, diammonium hydrogen phosphate, magnesium hydrogen phosphate, magnesium phosphate, ferrous phosphate, ferric phosphate, sodium dihydrogen phosphate, phosphorus Sodium phosphate, disodium hydrogen phosphate, lead phosphate, diammonium phosphate, calcium dihydrogen phosphate, lithium phosphate,
Examples include phosphotungstic acid, ammonium phosphotungstate, sodium phosphate tungstate, ammonium phosphomolybdate, and sodium phosphomolybdate. In addition, sodium phosphite, sodium tripolyphosphate and sodium pyrophosphate can be exemplified.
Preferred are sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate and the like. These may be used alone or in combination of two or more.

In the case of performing such a phosphoric acid treatment, a phosphoric acid mixture obtained by mixing the phosphoric acid with an aqueous solution containing an inorganic fluorine compound may be prepared and used for the treatment. Before and after the compound-containing coating layer forming step, treatment with a treatment liquid containing phosphoric acid may be performed. The concentration of phosphate in the aqueous solution is 10 g / liter to 1000 g.
/ Liter is suitable, and preferably 50 g / liter to 200 g / liter. In addition, the treatment method can be performed under the same conditions as those in which the treatment is first performed with an aqueous solution containing an inorganic fluorine compound.

When forming a coating layer with an aqueous solution containing an inorganic fluorine compound, a silicate treatment may be performed before and after to improve the hydrophilicity of the surface of the support. Examples of the silicate that can be used for the treatment for improving the hydrophilicity of the support according to the present invention include sodium silicate, potassium silicate, and lithium silicate.

When such a silicate treatment is performed, a mixed solution of these silicates mixed with an aqueous solution containing an inorganic fluorine compound may be prepared and used for the treatment. Before and after the coating layer forming step, the coating may be performed with a processing solution containing silicate. The concentration of the silicate in the aqueous solution is suitably from 0.1 g / L to 100 g / L, preferably from 1 g / L to 50 g / L.
Liters. In addition, the treatment method can be performed under the same conditions as those in which the treatment is first performed with an aqueous solution containing an inorganic fluorine compound.

When forming the coating layer with an aqueous solution containing an inorganic fluorine compound, the support may be further treated with a hydrophilic resin for the purpose of improving the hydrophilicity of the surface of the support. Examples of the hydrophilic resin that can be used for the treatment for improving the hydrophilicity of the support according to the present invention include polyvinyl phosphonic acid, polyvinyl alcohol, and CMC.

In the case of performing such a hydrophilic resin treatment, a mixed solution obtained by mixing these hydrophilic resins with an aqueous solution containing an inorganic fluorine compound may be prepared and used for the treatment. Before and after the compound-containing coating layer forming step, treatment with a treatment liquid containing a hydrophilic resin may be performed. The concentration of the hydrophilic resin in the above aqueous solution is suitably from 0.001 g / l to 100 g / l, preferably from 0.1 g / l to 100 g / l.
It is 1 g / liter to 50 g / liter. In addition, the treatment method can be performed under the same conditions as those in which the treatment is first performed with an aqueous solution containing an inorganic fluorine compound.

Two or more of the above phosphoric acids, silicates and hydrophilic resins may be used in combination.

The aluminum support used in the method of the present invention is a dimensionally stable metal containing aluminum as a main component, and is made of aluminum or an aluminum alloy. In addition to a pure aluminum plate, it is selected from an alloy plate containing aluminum as a main component and containing a trace amount of a different element, or a plastic film or paper on which aluminum (alloy) is laminated or evaporated. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 may be used. In the following description, the above-mentioned substrates made of aluminum or an aluminum alloy are collectively used as an aluminum support. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc,
There are bismuth, nickel, titanium and the like, and the content of the foreign element in the alloy is 10% by mass or less. In the present invention, a pure aluminum plate is preferable, but completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. Thus, the composition of the aluminum plate applied to the present invention is not specified,
Conventionally known and publicly used materials such as JIS A10
50, JIS A1100, JIS A3103, JIS
A3005 can be used as appropriate. Also,
The thickness of the aluminum support used in the present invention is about 0.1 mm to about 0.6 mm. This thickness can be appropriately changed according to the size of the printing press, the size of the printing plate, and the purpose.

(Graining treatment) The aluminum support is preferably grained to a more preferable shape in addition to the anodic oxidation treatment. A graining treatment method is disclosed in
Mechanical graining, chemical etching, electrolytic grains, etc. as disclosed in US Pat. Furthermore, an electrochemical graining method of electrochemically graining in a hydrochloric acid or nitric acid electrolyte, a wire brush graining method in which the aluminum surface is scratched with a metal wire, and a ball in which the aluminum surface is grained with a polishing ball and an abrasive. A mechanical graining method such as a grain method, a brush grain method for graining the surface with a nylon brush and an abrasive can be used, and the above graining methods can be used alone or in combination.

Among them, a method of forming a grain surface usefully used in the present invention is an electrochemical method of chemically sanding in a hydrochloric acid or nitric acid electrolyte. in the range of amount ^{50C / dm 2 ~1000C / dm 2} . More specifically, in an electrolyte containing 0.1 to 50% hydrochloric acid or nitric acid, the temperature is 20 to 100 ° C., and the time is 1 second to
It is performed using DC or AC at a current density of 1 to 200 A / dm ² for 30 minutes. Electrochemical surface roughening is preferable in terms of improving the adhesion between the photosensitive layer and the substrate because it is easy to provide fine irregularities on the surface.

By this roughening, the average diameter is about 0.5 to 20.
Cutters or honeycomb-like pits of μm can be formed on the aluminum surface at an area ratio of 30 to 100%. The pits provided here have an effect of preventing the non-image portion of the printing plate from being stained and improving printing durability. In the electrochemical treatment, the quantity of electricity necessary to provide sufficient pits on the surface, that is, the product of the current and the time during which the current is passed is an important condition in electrochemical surface roughening. It is desirable from the viewpoint of energy saving that sufficient pits can be formed with a smaller amount of electricity. The surface roughness after the surface roughening treatment is Ra = 0.2.
~ 0.7 μm is preferred.

The aluminum support thus arbitrarily grained is preferably further chemically etched with an acid or an alkali. When an acid is used as an etching agent, it takes time to destroy a fine structure, which is disadvantageous in industrially applying the present invention. However, it can be improved by using an alkali as an etching agent. Examples of the alkali agent preferably used in the present invention include caustic soda, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, lithium hydroxide, and the like. The range is 1 to 50%, 20 to 20 respectively
It is preferable that the temperature is 100 ° C. and the amount of Al dissolved is 5 to 20 g / m ³ . After etching, pickling is performed to remove dirt (smut) remaining on the surface. As the acid used, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borofluoric acid and the like are used. In particular, as a method for removing the smut after the electrochemical surface-roughening treatment, it is preferable to contact with 15 to 65% by mass of sulfuric acid at a temperature of 50 to 90 ° C as described in JP-A-53-12739. And the alkali etching method described in JP-B-48-28123.

(Anodizing treatment) The aluminum support optionally treated as described above in the method of the present invention comprises:
It is preferable that the anodic oxidation treatment is performed before the fluorination treatment so as to have a certain fluorination rate. The anodizing treatment can be performed by a method conventionally performed in this field. Specifically, when a direct current or an alternating current is applied to aluminum in an aqueous solution or a non-aqueous solution by using sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid or the like alone or in combination of two or more thereof, aluminum is supported An anodized film can be formed on the body surface. At this time, at least the components normally contained in the Al alloy plate, the electrode, tap water, groundwater, and the like may naturally be contained in the electrolytic solution. Furthermore, the second and third components may be added. Here, the second and third components are, for example, Na, K, Mg, Li, Ca, Ti, Al, V, C
cations such as ions of metals such as r, Mn, Fe, Co, Ni, Cu and Zn, ammonium ions and the like, nitrate ions, carbonate ions, chloride ions, phosphate ions, fluorine ions, sulfite ions, titanate ions, Silicate ions,
Anions such as butyric acid ions are mentioned, and the concentration thereof is
O to about 10000 ppm may be contained. The conditions of the anodizing treatment vary depending on the electrolytic solution used, and thus cannot be determined unconditionally.
~ 80%, liquid temperature -5 ~ 70 ° C, current density 0.5 ~ 60A
/ Dm ² , a voltage of 1 to 100 V, and an electrolysis time of 10 to 200 seconds are appropriate. Among these anodizing treatments, the method of anodizing at a high current density in a sulfuric acid electrolyte described in British Patent No. 1,412,768 is particularly preferable. In the present invention, the anodic oxide film is 0.5 to
It is preferably 20 g / m ² , and if it is less than 0.5 g / m ² , the plate is easily damaged, and if it is more than 20 g / m ² , a large amount of electric power is required for production, which is economically disadvantageous. Preferably, it is 1.0 to 10 g / m ² . More preferably,
1.5 to 6 g / m ² .

(Intermediate Layer) In the present invention, a positive photosensitive layer can be provided directly on the aluminum support having a constant fluorination rate as described above. If necessary, an intermediate layer may be provided on the support. And a positive photosensitive layer may be provided on each intermediate layer.

As a method of providing the intermediate layer, for example, immersion treatment with a solution, spray treatment, coating treatment,
Examples include vapor deposition, sputtering, ion plating, thermal spraying, and plating, but are not particularly limited. As a specific processing method, for example, JP-A-60-14
No. 9491, at least one selected from the group consisting of at least one amino group, a carboxyl group and a salt group thereof, and a sulfo group and a salt group thereof.
JP-A-60-23
Japanese Patent Application Laid-Open No. Sho 62-1998 discloses a layer composed of a compound selected from a compound having at least one amino group and at least one hydroxyl group and a salt thereof,
No. 494, a phosphate-containing layer, and a polymer compound containing at least one sulfo group-containing monomer unit disclosed in JP-A-59-101651 as a repeating unit in a molecule. A method of providing a layer or the like by coating. Also, carboxymethylcellulose, dextrin, gum arabic,
Phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid which may have a substituent; Organic phosphonic acids, organic phosphoric acid esters such as optionally substituted phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, alkylphosphine There is also a method of providing a compound layer selected from acids and organic phosphinic acids such as glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochlorides of amines having a hydroxyl group such as hydrochloride of triethanolamine.

Further, a silane coupling agent having an unsaturated group may be applied, for example, N-3- (acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (3-acryloxy) Propyl) dimethylmethoxysilane, (3-acryloxypropyl) methyldimethoxysilane, (3-acryloxypropyl) trimethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, allyldimethoxysilane, allyltriethoxysilane, allyl Trimethoxysilane, 3-butenyltriethoxysilane, 2- (chloromethyl) allyltrimethoxysilane, methacrylamidopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane ,
(Methacryloxydimethyl) dimethylethoxysilane,
Methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropyldimethylethoxysilane, methacryloxypropyldimethylmethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyltriethoxysilane , Methacryloxypropylmethyltrimethoxysilane, methacryloxypropyltris (methoxyethoxy) silane, methoxydimethylvinylsilane, 1-
Methoxy-3- (trimethylsiloxy) butadiene, styrylethyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) -propyltrimethoxysilane hydrochloride, vinyldimethylethoxysilane, vinyldiphenylethoxysilane, vinylmethyl Diethoxysilane, vinylmethyldimethoxysilane, O- (vinyloxyethyl) -N- (triethoxysilylpropyl) urethane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri-t-butoxysilane, vinyltriisopropoxysilane, vinyl Examples include triphenoxysilane, vinyltris (2-methoxyethoxy) silane, and diallylaminopropylmethoxysilane.
Of these, acryloyl groups, methacryloyl groups, vinyl groups, coupling agents containing an allyl group are preferred,
In particular, a coupling agent containing a methacryloyl group or an acryloyl group having a high reactivity of an unsaturated group is particularly preferable. Also,
The intermediate layer of a polymer compound having an acid group and an onium group described in JP-A-11-109637 can be more preferably used.

(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 (2).

[0033]

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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 represents a hydrogen atom, an alkyl group or a halogen atom. a, b, d and e are each independently 0 or 1
Represents t is an integer of 1 to 3.

More preferably, A represents -COO- or -CONH-, B represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group, a halogen atom or an alkyl group. It is.
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 has a molecular formula of C _n H _2n-1 , C _n
3 represented by H _2n-1 O, C _n H _2n-1 S or C _n H _2n N
Represents a valent linking group. 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 represents a hydrogen atom or an alkyl group. a, b, d, and e each independently represent 0 or 1, but a and b are not simultaneously 0.

Among the components having an acid group, a compound represented by the general formula (1) is particularly preferable, wherein B represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. Group. 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 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 the following.

[0038]

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[0039]

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[0040]

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The constituent having an acid group as described above includes 1
Types or two or more types may be combined. Preferred as the onium group as a component of the polymer compound used for forming the intermediate layer is an onium group composed of an atom of Group V or Group VI of the periodic table, more preferably a nitrogen atom or a phosphorus atom. Alternatively, it is an onium group consisting of a sulfur atom, particularly preferably an onium group consisting of a nitrogen atom. The polymer is preferably a polymer whose main chain structure is a vinyl-based polymer such as an acrylic resin, a methacrylic resin, or polystyrene, a urethane resin, a polyester, or a polyamide. Among them, 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).

[0042]

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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 represents an atom belonging to Group V of the periodic table, and Y ′ represents an atom belonging to Group VI of the periodic table. And Z ^- represents a counter anion. R ′ represents a hydrogen atom, an alkyl group or a halogen atom. _{R '1, R' 2,} R '3, R' 5 are each independently a hydrogen atom or an alkyl group which may be bonded substituent optionally, an aromatic group, an aralkyl group, R _'4
Represents an alkylidyne group or substituted alkylidyne,
R _'1 and R' ₂ or R _'4 and R' ₅ 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 represents -COO- or -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 is an alkylene group or a molecular formula C _n H _2n O,
It represents a divalent linking group represented by C _n H _2n S or C _n H _{2n + 1} N. Here, n represents an integer of 1 to 12. Y
Represents a nitrogen atom or a phosphorus atom, and Y ′ represents a sulfur atom. Z ⁻ represents a halogen ion, PF ₆ ⁻ , BF ₄ ⁻ or R ′ ₆ SO ₃ ⁻ . R ′ ₆ represents a hydrogen atom or an alkyl group. R ′ ₁ , R ′ ₂ , R ′ ₃ , and R ′ ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms to which a substituent may be bonded, an aromatic group, or an aralkyl group. It represents, 'but ₄ represents an alkylidyne group or a substituted alkylidyne of 1 to 10 carbon atoms, R' R ₁ and R _'2 or R' ₄ and R _'5 may be bonded to each other to form a ring. j, k,
m independently represents 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 an alkyl group having 1 to 3 carbon atoms. 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 _'6 SO ₃ ^- represents a. R '
₆ represents a hydrogen atom or a methyl group. j is 0,
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.

[0047]

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[0048]

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It is desirable that the polymer compound used for forming the intermediate layer contains 1 mol% or more, preferably 5 mol% or more 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.

Further, in the polymer compound having an onium group together with 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 adhesion is further improved by a synergistic effect between the acid group and the onium group. In addition, it goes without saying that two or more kinds of polymer compounds having different constituent components or composition ratios or different 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 onium group will be described. The composition ratio of the polymer structure represents a mole percentage.

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Any of the high molecular compounds having an acid group or having an onium group together with an acid group, which are used for forming the intermediate layer as described above, can be generally produced by a radical chain polymerization method (" Textbook of Polymer Sc
ience "3rd ed, (1984) FW Billmeyer, A Wiley-Intersci
ence Publication). The molecular weight of these high molecular compounds may be wide, but when measured using a light scattering method, the weight average molecular weight (Mw) is 500 to 2.0.
00,000, and 2,000-6
More preferably, it is in the range of 00,000. Also,
The amount of unreacted monomer contained in this polymer compound may be wide, but is preferably 20% by weight or less, and more preferably 10% 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-vinylbenzoic acid [manufactured by Hokuko Chemical Industry Co., Ltd.]
Vinylbenzyltrimethylammonium chloride 44.
2 g (0.21 mol) and 446 g of 2-methoxyethanol were 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. After 2 hours, 2.76 g (12 mmol) of dimethyl 2,2-azobis (isobutyrate) was further 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. The obtained solid was measured for molecular weight by a light scattering method, and as a result, the weight average molecular weight (Mw) was 32,000. Other polymer compounds can be synthesized in a similar manner.

The intermediate layer having an acid group and an onium group is a polymer compound having the above-mentioned acid group or having an onium group together with the acid group (hereinafter simply referred to as “polymer compound”).
Is treated with the above-mentioned aqueous solution containing nitrous acid or nitrite, and further applied on an aluminum support optionally subjected to hydrophilic treatment by various methods. One of the generally employed methods 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, a solution of the polymer compound having a concentration of 0.005 to 10% by weight can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. 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 0.1 second to 20 minutes, preferably 2 seconds to 1 hour.
Minutes.

The solution of the above 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 may 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 when the amount is more than 100 mg / m ² .

In addition, a sol-gel coating treatment described in JP-A-5-50779, a coating treatment of phosphonic acids described in JP-A-5-246171, a JP-A-6-234
284, JP-A-6-191173 and JP-A-6-2305
63, a method of treating a material for a back coat by coating, a treatment of phosphonic acids described in JP-A-6-262873, a coating treatment described in JP-A-6-297875, and an anodizing treatment by a method described in JP-A-10-109480. And any of the immersion treatment methods described in Japanese Patent Application Nos. 10-252078 and 10-253411.

(Positive type photosensitive layer) The above-mentioned optional anodic oxidation treatment, surface roughening treatment and the like, optionally provided with an intermediate layer,
The following positive photosensitive layer is provided on a support having a constant fluorination rate.

The positive photosensitive layer is provided by dissolving the positive photosensitive composition in a solvent or the like as appropriate and coating it on the above support. As such a positive photosensitive composition,
Any material may be used as long as its solubility in a developer or swelling property changes before and after exposure. Hereinafter, a typical positive photosensitive composition will be described, but the present invention is not limited thereto.

(Positive Photosensitive Compound) Examples of the photosensitive compound in the positive photosensitive composition include an o-quinonediazide compound, and a typical example thereof is an o-naphthoquinonediazide compound. The o-naphthoquinonediazide compound is preferably an ester of 1,2-diazonaphthoquinonesulfonic acid chloride and pyrogallol-acetone resin described in JP-B-43-28403.

As other suitable o-quinonediazide compounds, there are described 1,2- and 2,2-diphenylzide compounds 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 US Pat. No. 3,454,4.
No. 00, No. 3,544,323, No. 3,573,91
No. 7, No. 3,674,495, No. 3,785,825
No. 1,227,602, UK Patent No. 1,251,3
No. 45, No. 1,267,005, No. 1,329,88
8, No. 1,330,932, German Patent No. 854,
No. 890 or the like, 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 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., No. 61-118744, No. 62-10645,
No. 62-10646, No. 62-153950, No. 6
Nos. 2-178562, 64-76047, U.S. Patent Nos. 3,102,809, 3,126,281, 3,130,047, 3,148,983, and Nos. 3,184,310, 3,188,210, and 4,639,406, and the like, each of which is described in each gazette or specification.

In synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2 to 1.2 equivalents of 1,2-diazonaphthoquinonesulfonic acid chloride with respect to the hydroxyl group of the polyhydroxy compound.
More preferably, the reaction is performed in an amount of from 0.3 to 1.0 equivalent.
As the 1,2-diazonaphthoquinonesulfonic acid chloride, 1,2-diazonaphthoquinone-5-sulfonic acid chloride is preferred, but 1,2-diazonaphthoquinone-4-chloride is preferred.
Sulfonyl chloride can also be used. The obtained 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. The proportion of the compound in the mixture (content of the completely esterified compound) is preferably 5 mol% or more, more preferably 20 to 99 mol%.

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 mass, and more preferably from 15 to 40% by mass.

(Binder) The o-quinonediazide compound alone may constitute the photosensitive layer, but is preferably used together with a resin soluble in alkaline water as a binder (binder). Such a resin soluble in alkaline water includes a novolak resin having this property, for example, 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 polymer 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 hydroxystyrenes having an aromatic hydroxyl group such as o-, m- or p-hydroxyphenyl acrylate or methacrylate, (2) acrylic acid, methacrylic acid , Maleic acid, maleic anhydride and its half esters, itaconic acid,
Unsaturated carboxylic acids such as 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 methacrylic esters such as o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, and 1- (3-aminosulfonylphenylnaphthyl) methacrylate;
(4) Phenylsulfonylacrylamide which may have a substituent such as tosylacrylamide, and phenylsulfonylmethacrylamide which may have a substituent such as tosylmethacrylamide.

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, acrylic acid Amyl, hexyl acrylate, cyclohexyl acrylate,
Octyl acrylate, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 4-hydroxybutyl acrylate, glycidyl acrylate, N-
(Substituted) acrylates such as dimethylaminoethyl acrylate, (7) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, methacrylic acid (Substituted) methacrylates such as phenyl, benzyl methacrylate, 2-chloroethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate,

(8) Acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-hexylacrylamide, 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) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether,
Vinyl ethers such as phenyl vinyl ether,

(10) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate; (11) styrenes such as styrene, α-methyl styrene, methyl styrene and chloromethyl styrene; 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-vinylpyrrolidone, N-vinylcarbazole; 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 mass or less, preferably 30 to 8%.
0 mass%, more preferably 50 to 70 mass%. This range is preferred from the viewpoint 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. It is preferable to use a condensate of phenol and formaldehyde or an o-naphthoquinonediazidosulfonic acid ester of these condensates (for example, those described in JP-A-61-243446) in order to improve the oil sensitivity of an image.

(Development Accelerator) It is preferable to add cyclic acid anhydrides, phenols and organic acids to the photosensitive composition in order to increase sensitivity and improve developability.
Examples of cyclic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy-Δ4-tetrahydrophthalic anhydride described in U.S. Pat. No. 4,115,128. And tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like. 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, etc. Further, as organic acids, JP-A-60-88942 and JP-A-Hei 2
Sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids,
There are phosphoric esters and carboxylic acids, and specifically, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, phosphoric acid Diphenyl, 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-mentioned cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is preferably from 0.05 to 15% by mass, more preferably from 0.1 to 5% by mass.

(Development Stabilizer) Further, in the photosensitive composition, JP-A-62-151740 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 or 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 from 0.05 to 15% by mass, more preferably from 0.1 to 5% by mass.

(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 mass of the entire photosensitive composition.

Further, compounds capable of generating a photo-decomposed product which changes the color tone by interacting with the dye described in JP-A-5-313359, for example, JP-A-50-36209 (US Pat. No. 3,969,118) -)-Naphthoquinonediazide-4-sulfonic acid halogenide described in
No. 36223 (U.S. Pat. No. 4,160,671) describes trihalomethyl-2-pyrone and trihalomethyltricidin, and JP-A-55-62444 (U.S. Pat.
801), various o-naphthoquinonediazide compounds described in JP-A-55-77742 (U.S. Pat.
No. 982), for example, a 2-trihalomethyl-5-aryl-1,3,4-oxadiazole compound. These compounds can be used alone or as a mixture. Of these compounds, those having absorption at 400 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 besides the dyes described in JP 13359 can be used. 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 (or more, manufactured by Orient Chemical Co., Ltd.), Victoria Pure Blue BOH, Victoria Pure Blue NAPS, Ethyl Violet 6H
NAPS (both from 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 not less than 70% of the absorbance at 436 nm can be added.

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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, n1 represents 0 or 1.

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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. n2 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 nonmetallic 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 one 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. .

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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 mass. 0.5g / m ² ~4.0g / m ² is preferred as the coating amount. If the amount is less than 0.5 g / m ² , the printing durability will deteriorate.
When the amount is more than 4.0 g / m ² , the printing durability is improved, but the sensitivity is lowered. 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 as described in JP-A-62-170950 may be added to the photosensitive composition. it can. The preferable addition amount is 0.01 to 1% by mass of the whole photosensitive composition, and more preferably 0.05.
~ 0.5% by mass. 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.

(Exposure) In the present invention, a lithographic printing plate provided with a photosensitive layer is subjected to development processing after image exposure. The light source of the actinic rays used for image exposure is a carbon arc lamp, a mercury lamp, a metal halide lamp, a xenon lamp,
There are a tungsten lamp, a chemical lamp, and the like. Examples of the radiation include an electron beam, an X-ray, an ion beam, and a far-infrared ray. In addition, g-line, i-line, Deep-UV light, and high-density energy beam (laser beam) 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.

(Developing Process) Next, the developing process in the method of the present invention will be described. The developer used in the method of the present invention does not contain silicate. Preferred as such a developing solution is an alkaline aqueous solution substantially free of an organic solvent,
An aqueous solution such as H, KOH, LiOH, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium carbonate, sodium bicarbonate, potassium carbonate, aqueous ammonia, etc. is suitable. is there. 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 addition,
In this specification, a developer means a development initiator (a developer in a narrow sense) and a development replenisher unless otherwise specified.

(Non-Reducing Sugar and Base) The developer 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 in 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. As sugar alcohols, D, L-arabit, ribit, xylit, D,
L-sorbit, D, L-mannit, D, L-idit, D, L-tallit, zuricit, allozurcit and the like. 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. 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 proportion in the developer is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass. 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. In addition, when a reducing sugar is used in combination with a base, there is a problem that the color changes to brown with time, the pH gradually decreases, and the developing property is lowered.

As the base to be combined with the non-reducing sugar, conventionally known alkaline agents other than silicates can be used. For example, sodium hydroxide, potassium, lithium, trisodium phosphate, potassium, ammonium,
Inorganic alkaline agents such as disodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium hydrogencarbonate, potassium, ammonium, sodium borate, potassium, and ammonium are exemplified. In addition, 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. Among these, sodium hydroxide and potassium hydroxide are preferred. The reason is that by adjusting these amounts with respect to the non-reducing sugar, the pH can be adjusted in a wide pH range. Further, trisodium phosphate, potassium phosphate, sodium carbonate, potassium phosphate and the like are also preferable since they themselves have a buffering action. These alkaline agents are added so that the pH of the developing solution is in the range of 9.0 to 13.5, and the amount of addition is determined depending on the desired pH, the type and the amount of non-reducing sugar, and more preferably p.
The H range is 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 10.0.
13.2 is preferred. Such weak acids include P
IONISATION CONSTANTS OF ORGAN published by ergamon Press
It is selected from those described in IC ACIDS IN AQUEOUS SOLUTION and the like, for example, 2,2,3,3-tetrafluoropropanol-1 (pKa 12.74), trifluoroethanol (12.37), trichloroethanol (12.37) Alcohols such as 12.24), pyridine-2-
Aldehydes such as aldehyde (12.68), pyridine-4-aldehyde (12.5) and 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), 3,4-dihydroxybenzoic acid (11.94), 1,2,4-trihydroxybenzene (11.82), hydroquinone (11.56), pyrogallol (11.56) 11.34), o-cresol (10.33), resorcinol (11.2)
7) compounds having a phenolic hydroxyl group such as p-cresol (10.27) and 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 (11.3)
Oximes such as 5), adenosine (12.56),
Nucleic acid-related substances such as inosine (12.5), guanine (12.3), cytosine (12.2), hypoxanthine (12.1), xanthine (11.9), and diethylamino Methylphosphonic acid (id. 12.32), 1-
Amino-3,3,3-trifluorobenzoic acid (12.2.
9), isopropylidene diphosphonic acid (12.1)
0) 1,1-ethylidene diphosphonic acid (11.5)
4) 1-hydroxy 1,1-ethylidene diphosphonic acid (11.52), benzimidazole (12.8)
6), thiobenzamide (12.8), picoline thioamide (12.55), barbituric acid (12.5) and the like.

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) Various surfactants and organic solvents can be added to the developing solution as needed for the purpose of accelerating developability, dispersing development scum, and enhancing 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, polyoxyethylenated 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 salts, polyoxyethylene alkyl ether phosphate salts, polyoxyethylene alkyl phenyl ether phosphate salts, partially saponified styrene / maleic anhydride copolymers, partially 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.

More preferred surfactants are fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Examples of the fluorine-based surfactant include an anionic type such as perfluoroalkyl carboxylate, perfluoroalkyl sulfonate and perfluoroalkyl phosphate, an amphoteric type such as 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 Non-ionic types such as group-containing oligomers, urethanes containing perfluoroalkyl groups and lipophilic groups are included. The above-mentioned 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 mass, more preferably 0.01 to 5% by mass.

(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
The water-soluble ethylene oxide addition compound obtained by adding 4 mol or more of ethylene oxide to the acid or alcohol described in JP-A No. 7 and the water-soluble polyalkylene compound are exemplified.

(Organic Solvent) The developer contains substantially no organic solvent, but an organic solvent is added if necessary. Such an organic solvent has a solubility in water of about 1
Those having 0% by mass or less are suitable, and preferably 5% by mass.
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-
Methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanolamine, N-phenyldiethanolamine and the like can be mentioned. To be substantially free of an organic solvent in the developer means that the content of the organic solvent is 5% by mass 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 is to prevent stains on 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 methol, methoxyquinone, resorcin, and 2-methylresorcin, and amine compounds such as phenylenediamine and phenylhydrazine. Further 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 the developer in use in the range of 0.05 to 5% by mass.

(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, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid,
There are 1-naphthoic acid and 2-naphthoic acid, and hydroxynaphthoic acid is particularly effective. The above aliphatic and aromatic carboxylic acids are preferably used as a sodium salt, a potassium salt or an ammonium salt in order to enhance 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 mass, the effect is not sufficient, and if the content is more than 10% by mass, the effect cannot be further improved. Dissolution may be hindered when an additive is used in combination. Therefore, the preferred amount of addition is 0.1 to 10% by mass, more preferably 0.5 to 4% by mass, based on the developer used.
% By mass.

(Others) The developer may further contain a preservative, a coloring agent, a thickener, an antifoaming agent, a water softener and the like, if necessary. Examples of water softeners include polyphosphoric acid and its sodium, potassium, and ammonium salts, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid and the like. 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 mass, more preferably 0.01 to 0.1% by mass.
The range is 5% by mass. If the added amount is less than this range, the intended purpose is not sufficiently achieved, and if the added amount is larger than this range, an adverse effect on an image portion such as color omission appears. 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.

(Development and Post-processing) A lithographic printing plate developed with a developer having such a composition is washed with water, a rinsing solution containing a surfactant, etc., and a finisher or protective material mainly containing gum arabic or a starch derivative. Post-treatment with gum solution. In the post-treatment of the photosensitive lithographic printing plate in the method of the present invention, these treatments 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 a device for transporting a photosensitive lithographic printing plate;
Each of the processing liquid tanks and the spray device is used to perform development and post-processing by spraying each processing liquid pumped up by a pump from a spray nozzle while horizontally transporting the exposed photosensitive lithographic printing plate. Recently, a photosensitive lithographic printing plate is immersed and transported by a submerged guide roll in a processing solution tank filled with the processing solution to carry out development processing, or a certain amount of small amount of washing water is supplied 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, processing can be performed while replenishing each processing solution with a replenisher in accordance with the processing amount, 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.

[0107]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. (Examples 1 to 16) <Method for Producing Support> (a) A molten aluminum composed of the components shown in Table 1 below was prepared, subjected to molten metal treatment and filtered, and then was formed to a thickness of 500 mm and a width of 120.
0mm ingot is made by DC casting method and the surface is 10m on average
After shaving off with an m-plane, it was kept at 550 ° C for about 5 hours, and when the temperature dropped to 400 ° C, a 2.7 mm thick rolled plate was formed by hot rolling, and a continuous annealing machine was used. After heat treatment at 500 ° C, cold rolling was performed to a thickness of
Finished to 24 mm. After this aluminum plate was made 1030 mm in width, it was continuously treated.

[0108]

[Table 1]

(B) The surface of the aluminum plate was treated with a nylon brush and an aqueous suspension of 400 mesh pumicestone.
After graining, it was thoroughly washed with water. Spray etching was performed at a caustic soda concentration of 26% by mass, an aluminum ion concentration of 6.5% by mass and a temperature of 70 ° C. to dissolve the aluminum plate at 7 g / m ² . Thereafter, washing with water was performed by spraying. (C) Desmut treatment was performed by spraying with a 1% by weight aqueous solution of nitric acid at a temperature of 30 ° C. (containing 0.5% by weight of aluminum ions), and then washing with water by spraying. As the nitric acid aqueous solution used for the desmutting, a waste liquid from a step of performing electrochemical surface roughening using an alternating current in a nitric acid aqueous solution was used.

(D) Electrochemical surface roughening treatment was performed continuously using an AC voltage of 60 Hz. At this time, the electrolytic solution was a 1% by mass aqueous nitric acid solution (containing 0.5% by mass of aluminum ions and 0.007% by mass of ammonium ions) at a temperature of 50 ° C. The AC power supply waveform is the waveform shown in FIG. 2 and the time TP until the current value reaches a peak from zero is 2 m.
Electrochemical surface roughening treatment was performed using a carbon electrode as a counter electrode using a trapezoidal rectangular wave alternating current with a sec and duty ratio of 1: 1. Ferrite was used for the auxiliary anode. Two electrolyzers were used. The current density is 30 A at the peak value of the current.
/ Dm ² , and the amount of electricity was 230 C / dm ² in total of the amount of electricity when the aluminum plate was an anode. 5% of the current flowing from the power supply was diverted to the auxiliary anode. Thereafter, water washing by spraying was performed.

(E) The aluminum plate was treated with caustic soda concentration 2
When the etching treatment by spraying is performed at 70 ° C. at 6% by mass and the aluminum ion concentration is 6.5% by mass, and the aluminum plate is dissolved at 1 g / m ² , and the surface is electrochemically roughened using the preceding alternating current. The smut component mainly composed of aluminum hydroxide formed was removed, and the edge portion of the generated pit was dissolved to smooth the edge portion. Then, it was washed with water by spraying. (F) Desmut treatment by spraying was performed with an aqueous solution of 25% by mass of sulfuric acid (containing 0.5% by mass of aluminum ions) at a temperature of 60 ° C., followed by washing with water by spraying.

(G) Sulfuric acid concentration of 17 using anodizing equipment
At 0 g / l (containing 0.5% by mass of aluminum ions), at a temperature of 40 ° C. and 30 A / dm ² , the anodic oxidation amount was 2.5 g / l.
After performing anodizing treatment so as to obtain m ² , washing with water was performed by spraying. The substrate so far was designated as A. Next, after treatment with an aqueous solution containing a fluoride shown in Table 2, the substrate was washed with water to prepare each substrate.

The fluorination rate of the obtained substrate surface was measured using the following apparatus under the following conditions. Device name: PHI-5400MC (manufactured by ULVAC-PHI) X-ray _{source: MgK α (400W) Pass energy} : 71.55eV Analysis area: take-off angle of 1.1mmφ photoelectron: 45 °

Next, the polymer compound shown below was applied on the substrate treated as described above according to the following formulation.
C. and dried for 15 seconds. Coating amount after drying is 6.5 mg /
m ₂ . Next, a photosensitive layer was provided by applying the following photosensitive solution A. The coated amount of the photosensitive layer after drying is 1.3 g / m ^2.
Met. In order to further shorten the vacuum adhesion time, a photosensitive lithographic printing plate was prepared by forming a mat layer by the method described in JP-B-61-28986.

[Prescription] Polymer compound (molecular weight Mw = 28,000): 0.1 g Methanol: 100 g Pure water: 1 g

[0116]

Embedded image

[Photosensitive solution A] Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709). 8 g Binder Novolak I (see the following structural formula) 1.5 g Novolak II (see the following structural formula) 0.2 g Resin other than novolak III (see the following structural formula) 0.4 g p-n-octylphenol-formaldehyde resin (US Pat. No. 4,123) , 279) 0.02 g naphthoquinone-1,2-diazide-4-sulfonic acid chloride 0.01 g tetrahydrophthalic anhydride 0.02 g benzoic acid 0.02 g pyrogallol 0.05 g 4- [P-N, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) -S- Liazine (hereinafter abbreviated as triazine A) 0.07 g Victoria Pure Blue BOH (a dye produced by replacing the counter anion with 1-naphthalenesulfonic acid manufactured by Hodogaya Chemical Co., Ltd.) 0.045 g F176PF (fluorinated surfactant, large 0.01 g of methyl ethyl ketone 15 g 1-methoxy-2-propanol 10 g

[0118]

Embedded image

The photosensitive lithographic printing plate thus prepared was
The image was exposed for 1 minute with a 3 kW metal halide lamp from a distance of m and developed at 30 ° C. for 12 seconds using the following developer A or B with a PS processor 900VR manufactured by Fuji Photo Film Co., Ltd.

Developer A (pH = 13): D-sorbitol 5.1 parts by weight Sodium hydroxide 1.1 parts by weight Triethanolamine / ethylene oxide adduct (30 mol) 0.03 parts by weight Water 93.8 parts by weight Part Developer B: [SiO ₂ ] / [Na ₂ O] molar ratio 1.2, SiO ₂ 1.4 mass% sodium silicate aqueous solution 100 parts by weight Ethylenediamine / ethylene oxide adduct (30 mol) 0.03 parts by weight

The lithographic printing plate obtained by the development treatment as described above was measured for printing durability, stain resistance, residual color, residual film performance, scum and sludge. The results are shown in Table 2. In addition, the evaluation method of the said performance is as follows.

Printing durability: Evaluation was carried out using a printing machine Sprint manufactured by Komori Printing Machine Co., Ltd., based on the number of prints until normal printing was stopped. The greater the number of prints, the better the printing durability.

Stainability: After printing 1,000 sheets with a SOR-M printer manufactured by Heidelberg, the printing is stopped and left for 30 minutes. Then, it was attached to the printing machine again and 100 sheets were printed. At that time, the number of ink-discharged portions in the non-image area was evaluated. The smaller the number, the better the stain performance.

Sludge: After processing 1 m ² of the plate with 1 liter of the developing solution, the degree of dissolution of the oxide film in the alkali developing solution at this time was determined based on the state of the residue remaining in the developing solution.・ ・ ・: No scum and sludge are generated. ・ ・ ・: Scum and sludge are generated, but not as large as x. ×: Large amounts of scum and sludge are generated

Residual film: 2 in the non-image area of the lithographic printing plate after development
The difference (ΔD) between the reflection optical density at 80 nm light and the 280 nm reflection optical density of the support surface before coating the photosensitive layer was measured. The smaller the ΔD, the better the residual film performance.

Residual color: 6 in the non-image area of the lithographic printing plate after development
The difference (ΔD) between the reflection optical density at a light of 00 nm and the reflection optical density at a light of 600 nm on the support surface before coating the photosensitive layer was measured. The smaller the ΔD, the better the residual color performance.

As is clear from the following table, a lithographic printing plate obtained by developing a photosensitive lithographic printing plate having a fluorination ratio of the support in the range of 0.3 to 0.9 with a developing solution containing no silicate (working example). All of Examples 1 to 7) were excellent in stain, printing durability, residual color, and residual film performance, and neither scum nor sludge was generated in the developer.
On the other hand, the substrates shown in Comparative Examples (1 to 4) were all soiled,
Printing durability, residual color, residual film, and scum and sludge were not compatible, and were not satisfactory.

[0128]

[Table 2]

[0129]

According to the method for producing a lithographic printing plate of the present invention,
A positive photosensitive lithographic printing plate having good residual color, residual film performance, stain performance and printing durability can be obtained, and scum and sludge during development can be suppressed.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 2H025 AA00 AA04 AA12 AB03 AC01 AD03 BE02 CB29 CB52 DA18 FA03 FA17 2H096 AA07 CA03 CA20 EA02 GA08 GA09 GA10 GA13 LA16 2H114 AA04 AA14 AA23 BA01 BA10 DA06 FA04 EA02 GA04 GA09

Claims (2)

[Claims] 1. A lithographic printing plate comprising: a lithographic printing plate having a positive photosensitive layer provided on an aluminum support having a surface satisfying the following formula: Manufacturing method of printing plate: 0.30 ≦ A / (A + B) ≦ 0.90 (where A is the peak area of fluorine (1S) obtained by measurement using X-ray photoelectron spectroscopy (counts · eV) / sec), and B is aluminum (2P) obtained by measurement using X-ray photoelectron spectroscopy.
Represents the peak area (counts · eV / sec). 2. A silicate-free developer contains (a) at least one saccharide selected from non-reducing sugars and (b) at least one base (excluding silicate) and has a pH of 9.0. The method for producing a lithographic printing plate according to claim 1, wherein the developer is a developer in the range of from 1 to 13.5.