JP2000112135A - Photosensitive planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive planographic printing plate having exposure latitude and development latitude while maintaining stain resistance in a nonpicture area, and to provide a photosensitive planographic printing plate being compatible with stain performance and exposure latitude and development latitude even when the plate is developed with a developer containing no silicate. SOLUTION: This printing plate is produced by forming an intermediate layer on an aluminum supporting body subjected to anodic-oxidation treatment and hydrophilic imparting treatment, and then forming a photosensitive layer on the intermediate layer. The intermediate layer contains a polymer compd. having a structural component having acid groups and a structural component having onium groups. The photosensitive layer contains a polymer compd. having fluoroaliphatic groups and >=25 deg.C glass transition point.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a lithographic printing plate,
In particular, it relates to a positive photosensitive lithographic printing plate.

[0002]

2. Description of the Related Art Conventionally, a positive-working photosensitive lithographic printing plate, which has been widely used, generally has only an exposed portion of a photosensitive layer dissolved and removed with an alkali developing solution to expose a support layer and to remove water. And a non-image portion that easily repels the oil-based ink. On the other hand, the unexposed portion remains on the plate as it is insoluble in the alkali developing solution, and becomes an image portion that repels water and easily receives oily ink. However, when exposed to fluorescent light or sunlight in the working room, or oversupplemented with an alkali developing replenisher, the unexposed portion of the photosensitive layer, which is supposed to be an image portion, can be easily dissolved by the alkali developing solution. is there.
When such a phenomenon occurs, there is a problem that the film thickness of the image portion after the alkali development is reduced, resulting in unevenness of the ink density on the printed matter or reduction of the image area. On the other hand, when the solubility of the photosensitive layer in an alkali developing solution is reduced in order to increase the resistance to minute light exposure (hereinafter referred to as exposure latitude) and the resistance to slight increase in alkali strength (hereinafter referred to as development latitude). In addition, there has been a problem that the photosensitive layer remains in a portion to be a non-image portion to cause stain.

Therefore, we have proposed a method for sufficiently dissolving and removing the photosensitive layer and the intermediate layer in the non-image area even if the solubility in an alkali developing solution is slightly reduced, as disclosed in Japanese Patent Application Laid-Open No. 10-6 / 1998.
An intermediate layer containing a polymer compound described in Japanese Patent Application No. 9092 (Japanese Patent Application No. 8-225335) was developed. In this way, while maintaining the adhesion of the image portion, the non-image portion can sufficiently remove the photosensitive layer and the intermediate layer with an alkali developing solution.
The surface of the hydrophilic support was easily exposed, and stains were hardly generated. However, in order to enhance the alkali developer resistance of the image portion, simply reducing the solubility of the alkali developer is not sufficient.
Clear sensitivity at the same exposure amount is reduced, and the exposure work becomes more burdensome than before. Therefore, improvement has been desired.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photosensitive lithographic printing plate having an exposure latitude and a development latitude while maintaining the stainability of a non-image portion. It is a further object of the present invention to provide a photosensitive lithographic printing plate that achieves both stain performance and exposure latitude and development latitude even when developed using a silicate-free developer.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have solved the above object by the following photosensitive lithographic printing plate. That is, the present invention provides an intermediate layer containing a polymer compound having a component having an acid group and a component having an onium group on an aluminum support subjected to a hydrophilization treatment after anodization treatment. Further, it is a photosensitive lithographic printing plate provided with a photosensitive layer containing a polymer compound having a fluoroaliphatic group and having a glass transition point of 25 ° C. or higher.

Heretofore, in order to sufficiently dissolve and remove the photosensitive layer and the intermediate layer in the non-image area even if the solubility in an alkali developing solution is somewhat reduced, it is necessary to use a component having an acid group and an onium group. An intermediate layer containing a high molecular compound having a component has been developed to improve the soiling performance. However, this alone could not sufficiently improve the exposure latitude and the development latitude.

On the other hand, it is surprising that a polymer compound having a component having an acid group and a component having an onium group is provided on an aluminum support which has been subjected to a hydrophilization treatment after an anodization treatment. When a photosensitive layer containing a polymer compound which has a fluoroaliphatic group in which a hydrogen atom is substituted by a fluorine atom and which is a solid at room temperature is further provided thereon, the stain performance is improved. It was found that both the exposure latitude and the development latitude were greatly improved while maintaining the same. This is because the polymer compound having a fluoroaliphatic group, which is solid at room temperature, suppresses initial penetration of the developing solution, and in a portion to be a non-image portion, a component having an acid group and a component having an onium group It is presumed that this is because the photosensitive layer and the intermediate layer are easily removed by rapidly dissolving the polymer compound having the formula (1) in the developer. Further, the developing solution containing silicate as a main component, which is generally used in the above developing process, makes it difficult to stain the non-image area during printing, but on the other hand, solidifies in the developing bath of the automatic developing machine, and the sensor Cause malfunction of
There are also problems such as liquid clogging, and a complicated washing operation is required. However, it has also been found that the photosensitive lithographic printing plate of the present invention does not require a hydrophilizing treatment of the non-image area with a developing solution containing silicate as a main component.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Compounds used in the present invention
Will be described in detail. First, the height contained in the middle layer
The molecular compound will be described. Alcohol used in the present invention
The child compound has a monomer having an acid group as a polymerization component.
Of high molecular compounds and monomers containing onium groups
A high molecular compound having the same is contained. The present invention
These polymer compounds preferably have a main chain structure of
Like krill resin, methacrylic resin, or polystyrene
Vinyl polymer, urethane resin, or polystyrene
A polymer that is a tell or polyamide. Better
More preferably, the main chain structure of these polymer compounds is acrylic.
Resins such as resin, methacrylic resin or polystyrene.
It is a polymer that is a phenyl-based polymer. The acid group of the present invention
Polymer having a monomer as a polymerization component
The acid group is preferably an acid dissociation index (pKa).
7 or less, more preferably -COOH, -S
O_ThreeH, -OSO_ThreeH, -PO_ThreeH_Two, -OPO
_ThreeH _Two, -CONHSO_Two, -SO_TwoNHSO_Two-
And particularly preferably -COOH. It also has an acid group.
The monomer represented by the following general formula (1) or general formula (2)
And a polymerizable compound represented by the formula:

[0009]

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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. a, b, d, and e each independently represent 0 or 1. t is an integer of 1 to 3. More preferably, A is -COO- or -CON among the components having an acid group.
H represents H, B represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group, a halogen atom or an alkyl group. Alkylene group or a molecular formula D and E are each independently represents C _n H _2n O, 2 divalent linking group represented by C _n H _2n S or C _n H _{2n + 1} N. G has a molecular formula of C _n H _2n-1 , C _n H _2n-1 O, C _n H _2n-1 S or C _n
It represents a trivalent linking group represented by H _2n N. However, here
n represents an integer of 1 to 12. X and X ′ each independently represent a carboxylic acid, a sulfonic acid, a phosphonic acid, a sulfuric acid monoester or a phosphoric acid monoester. R1 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 monomers having an acid group, particularly preferred is a compound represented by the general formula (1), wherein B represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. is there. D and E each independently represent an alkylene group having 1 to 2 carbon atoms or an alkylene group having 1 to 2 carbon atoms linked by an oxygen atom. R ₁ represents a hydrogen atom or a methyl group. X represents a carboxylic acid. a is 0 and b is 1.

Specific examples of the monomer having an acid group are shown below. However, the present invention is not limited to this specific example. (Specific examples of monomers having an acid group) acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, itaconic acid, maleic acid, maleic anhydride

[0012]

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[0013]

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[0014]

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In the polymer compound having a monomer having an onium group as a polymerization component, the onium group is preferably an onium group consisting of an atom of Group V or Group VI of the periodic table, and more preferably. Is an onium group consisting of a nitrogen atom, a phosphorus atom or a sulfur atom, particularly preferably an onium group consisting of a nitrogen atom. The monomer having an onium group is represented by the following general formula (3):
The polymerizable compound represented by the general formula (4) or (5) is exemplified.

[0016]

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In the formula, J represents a divalent linking group. K represents an aromatic group or a substituted aromatic group. M each independently represents a divalent linking group. Y ₁ represents an atom belonging to Group V of the periodic table, and Y ₂ represents an atom belonging to Group VI of the periodic table. And Z ^- represents a counter anion. R ₂ represents a hydrogen atom, an alkyl group or a halogen atom. _{R 3, R 4, R 5} , R 7 are each independently a hydrogen atom or an alkyl group which may be bonded substituent optionally, an aromatic group, an aralkyl group, R ₆
Represents an alkylidyne group or substituted alkylidyne,
R ₃ and R ₄ or R ₆ and R ₇ may be bonded to each other to form a ring. j, k, and m are each independently 0 or 1
Represents 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 represents a divalent linking group in the alkylene group or molecular formula represented by _{C n H 2n O, C n} H 2n S or C _n H _{2n + 1} N. Here, n is 1 to
Represents an integer of 12. Y ₁ represents a nitrogen atom or a phosphorus atom, and Y ₂ represents a sulfur atom. Z ^- is a halogen ion, P
Represents F ₆ ⁻ , BF ₄ ⁻ or R ₈ SO ₃ ⁻ . R ₂ represents a hydrogen atom or an alkyl group. _{R 3, R 4, R 5} , R 7 are each independently hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be bonded substituent optionally, an aromatic group, an aralkyl group, R ₆ Represents an alkylidine group having 1 to 10 carbon atoms or a substituted alkylidine, and R ₃ and R ₄ or R ₆ and R ₇ may be bonded to each other to form a ring. j, k, and m each independently represent 0 or 1, but j and k are not 0 at the same time. R ₈ represents an alkyl group having 1 to 10 carbon atoms to which a substituent may be bonded, an aromatic group, or an aralkyl group. Among the constituents having an onium group, K is particularly preferably a phenylene group or a substituted phenylene group, wherein the substituent is a hydrogen atom or a carbon atom having 1 carbon atom.
To 3 alkyl groups. M represents an alkylene group having 1 to 2 carbon atoms or an alkylene group having 1 to 2 carbon atoms linked by an oxygen atom. Z ^- is a chloride ion or R ₈ SO ₃ ^- represents a. R ₂ represents a hydrogen atom or a methyl group. j is 0
And k is 1. R ₈ represents an alkyl group having 1 to 3 carbon atoms.

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

[0019]

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[0020]

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[0021]

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The monomer having an acid group may be used alone or in combination of two or more. The monomer having an onium group may be used alone or in combination of two or more. Further, the polymer according to the present invention,
Monomers with different composition ratios or molecular weights
You may mix and use more than one type. At this time, the polymer having a monomer having an acid group as a polymerization component contains the monomer having an acid group in an amount of 1 mol% or more, preferably 5 mol% or more,
It is desirable that the polymer having the onium group-containing monomer as a polymerization component contains the onium group-containing monomer in an amount of 1 mol% or more, preferably 5 mol% or more.

Further, these polymers are represented by the following (1) to
At least one selected from the polymerizable monomers shown in (14) may be contained as a copolymer component. (1) N- (4-hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) methacrylamide, o-, m- or p-hydroxystyrene, o-
Or acrylamides having an aromatic hydroxyl group such as m-bromo-p-hydroxystyrene, o- or m-chloro-p-hydroxystyrene, o-, m- or p-hydroxyphenyl acrylate or methacrylate;
Methacrylamides, acrylates, methacrylates and hydroxy styrenes, (2)
Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride and its half esters, itaconic acid, itaconic anhydride and its half esters,

(3) N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N- [1- (3-aminosulfonyl) Naphthyl] acrylamide, acrylamides such as N- (2-aminosulfonylethyl) acrylamide, N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonyl) Phenyl)
Methacrylamides such as methacrylamide, N- [1- (3-aminosulfonyl) naphthyl] methacrylamide, N- (2-aminosulfonylethyl) methacrylamide, and o-aminosulfonylphenyl acrylate and m-aminosulfonylphenyl Acrylate, p
-Aminosulfonylphenyl acrylate, 1- (3-
Unsaturated sulfonamides such as acrylates such as aminosulfonylphenylnaphthyl) acrylate;
unsaturated sulfonamides such as methacrylic esters such as o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, 1- (3-aminosulfonylphenylnaphthyl) methacrylate;

(4) phenylsulfonylacrylamide which may have a substituent such as tosylacrylamide;
And phenylsulfonyl methacrylamide which may have a substituent such as tosyl methacrylamide. Further, in addition to these alkali-soluble group-containing monomers, a film-forming resin obtained by copolymerizing the following monomers (5) to (14) is preferably used. (5) Acrylic esters and methacrylic esters having an aliphatic hydroxyl group, for example, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (6) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate , Amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, phenyl acrylate, benzyl acrylate, acrylic acid-2-
(Substituted) acrylates such as chloroethyl, 4-hydroxybutyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, (7) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, (Substituted) methacrylic acid such as hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate ester,

(8) Acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide, N-hexyl acrylamide, N
-Hexyl methacrylamide, N-cyclohexyl acrylamide, N-cyclohexyl methacrylamide, N
-Hydroxyethylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N
Acrylamides such as -phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide, N-ethyl-N-phenylacrylamide and N-ethyl-N-phenylmethacrylamide Or methacrylamide, (9) 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-methylstyrene, methylstyrene and chloromethylstyrene; (12) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone; (13) olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene; (14) N-vinyl pyrrolidone, N-vinyl carbazole; 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like.

The polymer used here contains at least 20%, preferably at least 40%, of a component having an acid group and at least 1%, preferably at least 5% of a component having an onium group. It is desirable. When the component having an acid group is contained in an amount of 20% or more, the dissolution and removal during alkali development is further promoted. Be improved. Further, the constituent component having an acid group may be used alone or in combination of two or more, and the constituent component having an onium group may be used alone or in a combination of two or more types. Further, the polymer according to the present invention is a polymer having different components or composition ratios or different molecular weights.
You may mix and use more than one type. Next, typical examples of the polymer compound used for the intermediate layer of the present invention are shown below. The composition ratio of the polymer structure represents a mole percentage.
In addition, the high molecular compound is shown by linking the structural units constituting it, but includes block copolymers, random copolymers, graft copolymers, etc., and copolymers of a specific bonding mode It is not limited to.

[0029]

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[0030]

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[0031]

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[0032]

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The polymer according to the present invention can be generally produced by a radical chain polymerization method (“Textbo
ok of Polymer Science "3rd ed, (1984) FW Billmeyer,
A Wiley-Interscience Publication). The molecular weight of the polymer according to the present invention is a number average molecular weight (Mn) calculated from the integrated intensity ratio between the terminal group and the side chain functional group in NMR measurement.
Is from 300 to 5,000, preferably from 500 to
4,800, more preferably 800-4,
The range is 500. If it is less than 300, the adhesion to the substrate will be weak, and the printing durability will be degraded. It cannot be removed, and furthermore, the erasability deteriorates, which is not suitable. Also,
The amount of unreacted monomer contained in the polymer may be wide, but is preferably 20 wt% or less,
Further, the content is more preferably 10% by weight or less.

A polymer having a molecular weight within the above range can be obtained by adjusting the amounts of the polymerization initiator and the chain transfer agent when the corresponding monomers are copolymerized. Note that a chain transfer agent refers to a substance that moves an active site of a reaction by a chain transfer reaction in a polymerization reaction, and the likelihood of occurrence of the transfer reaction is represented by a chain transfer constant Cs. Chain transfer constant Cs of the chain transfer agent used in the present invention
× 10 ⁴ (60 ° C.) is preferably 0.01 or more, more preferably 0.1 or more, and particularly preferably 1 or more. As the polymerization initiator, peroxides, azo compounds, and redox initiators generally used in radical polymerization can be used as they are. Of these, azo compounds are particularly preferred.

Specific examples of the chain transfer agent include halogen compounds such as carbon tetrachloride and carbon tetrabromide, alcohols such as isopropyl alcohol, isobutyl alcohol, and the like.
Olefins such as methyl-1-butene, 2,4-diphenyl-4-methyl-1-pentene, ethanethiol, butanethiol, dodecanethiol, mercaptoethanol, mercaptopropanol, methyl mercaptopropionate, ethyl mercaptopropionate, mercapto Propionic acid, thioglycolic acid, ethyl disulfide,
Examples thereof include, but are not limited to, sulfur-containing compounds such as sec-butyl disulfide, 2-hydroxyethyl disulfide, thiosalicylic acid, thiophenol, thiocresol, benzyl mercaptan, and phenethyl mercaptan. More preferably, ethanethiol, butanethiol, dodecanethiol, mercaptoethanol, mercaptopropanol, methyl mercaptopropionate, ethyl mercaptopropionate, mercaptopropionic acid, thioglycolic acid, ethyl disulfide, sec-butyl disulfide, 2-hydroxyethyl disulfide , Thiosalicylic acid, thiophenol,
Thiocresol, benzyl mercaptan, phenethyl mercaptan, particularly preferably ethanethiol,
Butanethiol, dodecanethiol, mercaptoethanol, mercaptopropanol, methyl mercaptopropionate, ethyl mercaptopropionate, mercaptopropionic acid, thioglycolic acid, ethyl disulfide, sec-butyl disulfide, and 2-hydroxyethyl disulfide.

The intermediate layer in the photosensitive lithographic printing plate of the present invention may contain a compound represented by the following general formula (6) in addition to the above polymer.

[0037]

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(Wherein, R ₁ represents an arylene group having 6 to 14 carbon atoms, and m and n each independently represent an integer of 1 to 3.) For the compound represented by the above general formula (6), Will be described. The carbon number of the arylene group represented by R ₁ is 6 to
14 is preferable, and 6 to 10 are more preferable. Specific examples of the arylene group represented by R ₁ include a phenylene group, a naphthyl group, an anthryl group, and a phenathril group. The arylene group represented by R ₁ has 1 to 1 carbon atoms.
10 alkyl groups, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, carboxylic acid ester groups, alkoxy groups, phenoxy groups, sulfonic acid ester groups, phosphonic acid Ester group,
It may be substituted with a sulfonylamide group, a nitro group, a nitrile group, an amino group, a hydroxy group, a halogen atom, an ethylene oxide group, a propylene oxide group, a triethylammonium chloride group, or the like.

Specific examples of the compound represented by the general formula (6) include, for example, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, salicylic acid, 1-hydroxy-2-
Examples include naphthoic acid, 2-hydroxy-1-naphthoic acid, 2-hydroshiki 3-naphthoic acid, 2,4-dihydroxybenzoic acid, and 10-hydroxy-9-anthracene carboxylic acid. However, the present invention is not limited to the above specific examples, and the compound represented by the general formula (6)
They may be used alone or in combination of two or more.

The intermediate layer containing the polymer according to the present invention and the compound represented by the general formula (6), which is optionally added, is formed on an aluminum support which has been subjected to a hydrophilization treatment described later. It is provided by being applied by a method.

This intermediate layer can be provided by the following method. To the organic solvent such as methanol, ethanol, methyl ethyl ketone or the like or a mixed solvent thereof or a mixed solvent of these organic solvents and water, the polymer according to the present invention and the compound represented by the general formula (6) which is added as necessary. A coating method in which a dissolved solution is applied on an aluminum support and dried. Alternatively, the polymer according to the present invention and an organic solvent such as methanol, ethanol, and methyl ethyl ketone, or a mixed solvent thereof, or a mixed solvent of these organic solvents and water are represented by the following general formula (6). A coating method in which an aluminum support is immersed in a solution in which a compound is dissolved, and then washed with water or air and the like and dried to form an intermediate layer can be used.

In the former method, the total of the above compounds is 0.0
A solution having a concentration of 05 to 10% by weight can be applied in various ways. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. In the latter method, the concentration of the solution is 0.005 to 20% by weight, preferably 0.01% to 10% by weight, and the immersion temperature is 0 ° C to 70 ° C, preferably 5 to 60 ° C. The time is 0.1 seconds to 5 minutes, preferably 0.5 seconds to 120 seconds.

The above solution 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; an organic sulfonic acid such as nitrobenzenesulfonic acid or naphthalenesulfonic acid; The pH is adjusted with various organic acidic substances such as organic phosphonic acids such as acids, benzoic acid, coumaric acid, and organic carboxylic acids such as malic acid, and organic chlorides such as naphthalene sulfonyl chloride and benzenesulfonyl chloride. More preferably, pH = 0 to 6
Can also be used. Further, in order to improve the tone reproducibility of the photosensitive lithographic printing plate, a substance absorbing ultraviolet light, visible light, infrared light or the like can be added.

After drying the compound constituting the intermediate layer of the present invention
Coating amount is 1 to 100 mg / m ^Two Is appropriate and good
Preferably 2 to 70 mg / m^Two It is. The above coating amount is 1mg / m^Two 
If it is less than this, a sufficient effect cannot be obtained. Also 100mg
/ m^Two The same applies to more than that.

Next, the polymer compound in the photosensitive layer, which is used in a specific combination when the polymer compound is used for the intermediate layer, will be described. The photosensitive layer of the present invention contains a polymer compound having a fluoroaliphatic group in which a hydrogen atom is substituted by a fluorine atom and having a glass transition point of 25 ° C. or higher. Here, the fluoroaliphatic group in which a hydrogen atom is substituted by a fluorine atom is a saturated or generally monovalent or divalent aliphatic group. This is a linear,
Including branched or cyclic. Fluoroaliphatic groups, in order to exert a sufficient effect for the purpose of the present invention,
It has from 3 to 20, preferably from 2 to 12, carbon atoms and has at least 40%, preferably at least 50%, by weight of fluorine bonded to carbon atoms. Suitable fluoro-aliphatic _{groups, C n F 2n + 1 -} (n is 1 or more, preferably an integer of 3 or more) substantially completely or fully fluorinated perfluoro aliphatic group such as (hereinafter, Abbreviated as Rf group)
It is.

As the addition polymerizable monomer part in the addition polymerizable monomer having an Rf group, a vinyl monomer having a radically polymerizable unsaturated group is preferably used. Of these vinyl monomers, particularly preferred are acrylate, methacrylate, acrylamide, methacrylamide, styrene and vinyl.
Specific examples of acrylates and methacrylates to which a fluoroaliphatic group is bonded include, for example, Rf-R'-OOC-
C (R ″) ＝ CH ₂ (where R ′ is, for example, a single bond, alkylene, sulfonamidoalkylene, or carbonamidoalkylene, and R ″ is a hydrogen atom, a methyl group,
A halogen atom or a perfluoroaliphatic group).

Specific examples of these are disclosed in, for example, US Pat. Nos. 2,803,615, 2,642,416 and 282.
No. 6564, No. 3102103, No. 328290
No. 5, No. 3,304,278, JP-A-6-2562.
No. 89, JP-A-62-1116, JP-A-62-487
No. 72, JP-A-63-77574, JP-A-62-36
657 and the Chemical Society of Japan 1985 (No.
10) Those described on pages 1884-1888. In addition to these fluoroaliphatic group-bonded monomers, Reports Res. Lab. Asahi Glass C
o., Ltd., vol. 34, 1984, pp. 27-34, a macromer to which a fluoroaliphatic group is bonded can be used. Further, as the fluoroaliphatic group-bonding monomer, a mixture having different lengths of perfluoroalkyl groups as shown in the following structural formula can be used.

[0048]

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The glass transition point (hereinafter referred to as T
g) is 25 ° C. or higher and is usually solid at room temperature. The measurement of Tg was carried out by using SSC5 manufactured by Seiko Denshi Kogyo KK
000 thermal analysis system at a heating rate of 10 ° C./min. The fluoroaliphatic group-containing polymer compound used in the present invention has a Tg higher than 25 ° C.
It is preferably higher than 5 ° C, more preferably the Tg is higher than 65 ° C.

In the present invention, the content of the high molecular compound having a fluoroaliphatic group and having a glass transition point of 25 ° C. or higher is determined based on the solid content of the photosensitive layer in the photosensitive composition (photosensitive layer). 0.01% to 10%, preferably 0.05%
-8%, more preferably 0.08-6%.

Next, among the photosensitive lithographic printing plates of the present invention, the positive photosensitive lithographic printing plate will be described in detail in the order of (1) support, (2) photosensitive composition, and (3) developing treatment. In the present invention, the photosensitive lithographic printing plate may be a PS plate.

<1> Support The support used in the positive photosensitive lithographic printing plate of the present invention and the processing thereof will be described below. (Aluminum Plate) The aluminum plate used in the present invention is a plate-like body such as pure aluminum or an aluminum alloy containing aluminum as a main component and containing a small amount of a different atom. The hetero atoms include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The alloy composition has a different atomic content of 10% by weight or less. Aluminum that is suitable for the present invention is pure aluminum, but it is preferable that completely pure aluminum contains as little foreign atoms as possible because it is difficult to produce due to refining technology. Further, any aluminum alloy having a different atomic content of the above-described level can be said to be a material that can be used in the present invention. As described above, the composition of the aluminum plate used in the present invention is not particularly limited, and conventionally known and publicly available materials can be appropriately used. Preferred materials include JIS A 10
50, 1100, 1200, 3003, 310
3, the same 3005 materials are included. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm. Prior to the surface roughening treatment of the aluminum plate, a degreasing treatment for removing a rolling oil on the surface, for example, a treatment with a surfactant or an alkaline aqueous solution is performed as necessary.

(Roughening Treatment and Anodizing Treatment) As methods for roughening the surface of the aluminum plate, there are a method of mechanically roughening, a method of electrochemically dissolving and roughening the surface, and a method of chemically roughening. There is a method of selectively dissolving the surface. As the mechanical method, a known method called a ball polishing method, a brush polishing method, a blast polishing method, a buff polishing method, or the like can be used. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used.

The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment, if necessary, and then subjected to an anodic oxidation treatment to increase the water retention and abrasion resistance of the surface. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, any electrolyte that forms a porous oxide film can be used, and generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte.

The anodizing treatment conditions vary depending on the electrolyte used and cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A. / Dm ² , voltage 1-100V, electrolysis time 10
It is suitable if it is in the range of seconds to 5 minutes. The amount of the anodized film is suitably 1.0 g / m ² or more, but more preferably in the range of 2.0 to 6.0 g / m ^2. When the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient,
The non-image portion of the lithographic printing plate is easily scratched, and so-called "scratch stain" in which ink adheres to the scratched portion during printing is likely to occur. Although such anodizing treatment is performed on a surface used for printing of the support of the lithographic printing plate, the back around the electric lines of force, the anodized film 0.01 to 3 g / m ² on the back surface It is generally formed.

(Hydrophilization treatment) As the hydrophilization treatment used after the above-mentioned treatment, a conventionally known hydrophilization treatment may be used.
A hydrophilization treatment is used. Examples of such a hydrophilic treatment include U.S. Pat. Nos. 2,714,066 and 3,181.
No. 461, No. 3,280,734, No. 3,902,7
No. 34 discloses an alkali metal silicate (for example, an aqueous solution of sodium silicate). In this method, the support is immersed or electrolytically treated in an aqueous solution of sodium silicate. Alternatively, Japanese Patent Publication No. 36-22
No. 063, potassium fluoride zirconate and U.S. Pat. Nos. 3,276,868 and 4,153.
For example, a method of treating with polyvinyl phosphonic acid as disclosed in No. 461, No. 4,689,272 is used. Among these, a particularly preferred hydrophilic treatment in the present invention is a silicate treatment. The silicate treatment will be described below.

(Silate treatment) The anodic oxide film of the aluminum plate treated as described above was treated with an alkali metal silicate of 0.001 to 30% by weight, preferably 0.05 to 10% by weight, at 25 ° C. Is immersed in an aqueous solution having a pH of 9 to 13 at, for example, 5 to 80 ° C. for 0.5 to 120 seconds. If the pH of the alkali metal silicate aqueous solution is lower than 9, the solution will gel, and if it is higher than 13.0, the oxide film will be dissolved.
As the alkali metal silicate used in the present invention, sodium silicate, potassium silicate, lithium silicate and the like are used. Hydroxides used for increasing the pH of the aqueous alkali metal silicate solution include sodium hydroxide, potassium hydroxide, and lithium hydroxide. Incidentally, an alkaline earth metal salt or a Group IVB metal salt may be added to the above-mentioned treatment solution. Examples of the alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate, and water-soluble salts such as sulfate, hydrochloride, phosphate, acetate, oxalate, and borate. No. As a Group IVB metal salt, titanium tetrachloride, titanium trichloride, potassium titanium fluoride, titanium potassium oxalate,
Titanium sulfate, titanium tetraiodide, zirconium chloride,
Zirconium dioxide, zirconium oxychloride, zirconium tetrachloride and the like can be mentioned. Alkaline earth metal salts or Group IVB metal salts can be used alone or in combination of two or more. The preferred range of these metal salts is 0.10 to 10% by weight, and the more preferred range is 0.05 to 5.0% by weight. By the silicate treatment, the hydrophilicity on the aluminum plate surface is further improved, so that during printing, the ink hardly adheres to the non-image area,
The dirt performance is improved.

(Backcoat) On the back surface of the support, a backcoat is provided if necessary. Examples of such a back coat include a coating comprising a metal oxide obtained by hydrolyzing and polycondensing an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in JP-A-6-35174. Layers are preferably used. Among these coating layers, Si (OCH ₃ ) ₄ , Si
(OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC
An alkoxy compound of silicon such as ₄ H ₉ ) ₄ is inexpensive and easily available, and a metal oxide coating layer provided therefrom is particularly preferable because of its excellent development resistance.

<2> Photosensitive Composition Next, other photosensitive compositions used in the photosensitive lithographic printing plate of the present invention will be described in detail. As the photosensitive composition used as required in the present invention, any one can be used as long as its solubility in a developer or swelling property before and after exposure changes. Hereinafter, typical photosensitive compositions will be described, but the present invention is not limited thereto.

The photosensitive compound of the photosensitive composition includes o
-Quinonediazide compound, and a typical example thereof is an o-naphthoquinonediazide compound. Examples of o-naphthoquinonediazide compounds include JP-B-43-28.
Preferred is an ester of 1,2-diazonaphthoquinonesulfonic acid chloride and pyrogallol-acetone resin described in JP-A-403-403.

Other suitable o-quinonediazide compounds include US Pat.
There are esters of 1,2-diazonaphthoquinone sulfonic acid chloride and phenol formaldehyde resin described in 188,210.

Other useful o-naphthoquinonediazide compounds include those reported and known in numerous patents. For example, JP-A-47-5303
No. 48-63802, No. 48-63803, No. 48-96575, No. 49-38701, No. 48-
13354, JP-B-37-18015, 41-1
No. 1222, No. 45-9610, No. 49-17481
JP-A-5-11444, JP-A-5-19477
JP-A-5-19478, JP-A-5-107755
No. 2,797,213 and No. 3,45.
No. 4,400, No. 3,544,323, No. 3,5
No. 73,917, No. 3,674,495, No. 3,
785,825, British Patent No. 1,227,602,
Nos. 1,251,345 and 1,267,005
No. 1,329,888, No. 1,330,93
No. 2, German Patent No. 854,890, and the like.

As another o-quinonediazide compound, an o-naphthoquinonediazide compound 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-51-13940
No. 2, No. 58-150948, No. 58-203434
No., 59-165053, 60-12445
No. 60-134235, No. 60-16343
No. 61-118744, No. 62-10645,
No. 62-10646, No. 62-153950, No. 6
2-178562, 64-76047, U.S. Pat. Nos. 3,102,809 and 3,126,281,
No. 3,130,047, No. 3,148,983
No. 3,184,310, No. 3,188,21
No. 0, No. 4,639, 406, and the like, and those described in each gazette or specification.

When synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2 to 1.2 equivalents of 1,2-diazonaphthoquinonesulfonic acid chloride with respect to the hydroxyl groups of the polyhydroxy compound. More preferably, the reaction is performed in an amount of 0.3 to 1.0 equivalent. As the 1,2-diazonaphthoquinone sulfonic acid chloride, 1,2-diazonaphthoquinone-5-sulfonic acid chloride is preferable, but 1,2-diazonaphthoquinone-sulfonic acid chloride is preferred.
4-sulfonic acid chloride can also be used. The obtained o-naphthoquinonediazide compound is a mixture of various compounds having different positions and introduced amounts of 1,2-diazonaphthoquinonesulfonic acid ester groups. 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, etc.) can also be used in the present invention. Further, a compound capable of generating an acid by photolysis (JP-A-4-121748, JP-A-4-3650)
No. 43), a C—O—C group or a C— group dissociated by an acid.
A combination system with a compound having an O-Si group can also be used in the present invention. For example, a combination of a compound which generates an acid by photolysis and an acetal or an O, N-acetal compound (Japanese Patent Application Laid-Open No. 48-89003), a combination with an orthoester or amide acetal compound (Japanese Patent Application Laid-Open No. 51-120714) ), In combination with a polymer having an acetal or ketal group in the main chain
-133429, etc.), and a combination with an enol ether compound (JP-A-55-12995, JP-A-4-19).
748, JP-A-6-230574, etc.) and a combination with an N-acylimino carbon compound (JP-A-55-126).
236), a combination with a polymer having an orthoester group in the main chain (JP-A-56-17345, etc.),
Combination with a polymer having a silyl ester group (JP-A-60-10247, etc.) and combination with a silyl ether compound (JP-A-60-37549, JP-A-60-37549)
No. 0-112446, JP-A-63-236028, JP-A-63-236029, JP-A-63-276046
No. etc.). Further, as a photosensitive compound which acts positively without using an o-naphthoquinonediazide compound, an aromatic sulfone compound, an onium-containing compound and the like can be used in the present invention. In these cases, the compound absorbs near-infrared light from infrared light and efficiently acts as a positive type by combining with a compound that generates heat. In addition, as a compound that absorbs near infrared light from infrared light and generates heat,
Compounds such as carbon black, cyanine dyes, methine dyes and naphthoquinone dyes are known. The amount of these positive-acting photosensitive compounds (including the combinations described above) in the photosensitive composition of the present invention is 1 to 50.
% By weight, more preferably from 10 to 40% by weight.
It is.

Of the above-mentioned positive-acting photosensitive compounds, especially the o-quinonediazide compound alone can constitute the photosensitive layer. It is preferable to use together with the resin soluble in alkaline water as the above). Such resins soluble in alkaline water include novolak resins having this property, such as phenol formaldehyde resin, m-cresol formaldehyde resin,
Cresol formaldehyde such as p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, o- or m- / p- / o-mixed) mixed formaldehyde resin Resins. These alkali-soluble polymer compounds have a weight average molecular weight of 50.
Those having 0 to 100,000 are preferred. In addition, resol type phenol resins are also preferably used, and phenol / cresol (m-, p-, o- or m- / p- / o-
Mixed formaldehyde resins are preferred, and phenol resins described in JP-A-61-217034 are particularly preferred.

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

(1) N- (4-hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) methacrylamide, o-, m- or p-hydroxystyrene, o- or m-bromo-p-hydroxystyrene, o- or m-chloro-p-hydroxystyrene,
Acrylamides, methacrylamides, acrylates, methacrylates and vidroxystyrenes having an aromatic hydroxyl group such as o-, m- or p-hydroxyphenyl acrylate or methacrylate, (2) acrylic acid, methacrylic acid , Maleic acid, 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, 1- (3-aminosulfonylphenylnaphthyl) methacrylate;

(4) phenylsulfonylacrylamide which may have a substituent such as tosylacrylamide;
And phenylsulfonyl methacrylamide which may have a substituent such as tosyl methacrylamide. Further, in addition to these alkali-soluble group-containing monomers, a film-forming resin obtained by copolymerizing the following monomers (5) to (14) is preferably used. (5) Acrylic esters and methacrylic esters having an aliphatic hydroxyl group, for example, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (6) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate , Amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, phenyl acrylate, benzyl acrylate, acrylic acid-2-
(Substituted) acrylates such as chloroethyl, 4-hydroxybutyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, (7) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, (Substituted) methacrylic acid such as hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate ester,

(8) Acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide, N-hexyl acrylamide, N
-Hexyl methacrylamide, N-cyclohexyl acrylamide, N-cyclohexyl methacrylamide, N
-Hydroxyethylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N
Acrylamides such as -phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide, N-ethyl-N-phenylacrylamide and N-ethyl-N-phenylmethacrylamide Or methacrylamide, (9) 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, and are used in an amount of 99% by weight or less, preferably 98% by weight or less of the total composition. Further, in a photosensitive lithographic printing plate which is not exposed to infrared light to near infrared light, the more preferable addition range of the alkali-soluble polymer compound as described above is 30 to 80% by weight of the whole composition. This range is preferred from the viewpoint of developability and printing durability.

Further, as described in US Pat. No. 4,123,279, an alkyl group having 3 to 8 carbon atoms as a substituent, such as a t-butylphenol formaldehyde resin or an octylphenol formaldehyde resin, is used. It is preferable to use a condensate with phenol 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 of the present invention in order to increase sensitivity and improve developability. As cyclic acid anhydrides, US Pat.
Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride described in US Pat. No. 5,128;
3,6-Endoxy-Δ ⁴ -tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. Examples of phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone,
4,4 ', 4 "-trihydroxy-triphenylmethane, 4,4', 3", 4 "-tetrahydroxy-3,
5,3 ', 5'-tetramethyltriphenylmethane and the like can be mentioned.

Further, as the organic acids, JP-A-60-8
No. 8942, JP-A-2-96755 and the like, there are sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphoric esters and carboxylic acids, and specifically, p-toluene sulfone Acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid,
3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 1,4-cyclohexene-2,2-dicarboxylic acid,
Erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and the like can be mentioned. The proportion of the above cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

(Development Stabilizer) In the photosensitive composition of the present invention, JP-A-62-2517 is used in order to increase the stability of processing under development conditions (so-called development tolerance).
Non-ionic surfactants described in JP-A No. 40 and JP-A-4-68355, JP-A-59-1210
No. 44 and JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene nonyl phenyl ether. Specific examples of the amphoteric surfactant include alkyldi (aminoethyl)
Glycine, alkyl polyaminoethyl glycine hydrochloride,
2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-
N, N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and alkylimidazoline type (for example, trade name Levon 15, manufactured by Sanyo Chemical Co., Ltd.) and the like can be mentioned. The ratio of the nonionic surfactant and the amphoteric surfactant in the photosensitive composition is 0.05 to 1%.
5% by weight is preferred, more preferably 0.1 to 5% by weight
It is.

(Print-Out Agent, Dye, Others) In the photosensitive composition of the present invention, a print-out agent for obtaining a visible image immediately after exposure, and a dye or other filler as an image coloring agent are added. be able to. As the dye that can be used in the present invention, a cation having a basic dye skeleton described in JP-A-5-313359 and a sulfonic acid group having only one exchange group and having 1 to 3 hydroxyl groups A basic dye comprising a salt with an organic anion having 10 or more carbon atoms can be used. The amount of addition is 0.2 to 5% by weight of the total photosensitive composition.

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

As a colorant for an image, the above-mentioned JP-A-5-313 is used.
Other dyes besides the dyes described in JP-A-359-359 can be used. Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. More specifically, Oil Green BG, Oil Blue BOS, Oil Blue # 603 (all manufactured by Orient Chemical Industries, Ltd.), Victoria Pure Blue BOH, Victoria Pure Blue NAPS, Ethyl Violet 6HNAP
S (above, Hodogaya Chemical Industry Co., Ltd.), Rhodamine B
[C145170B], malachite green (C142
000), methylene blue (C152015) and the like.

Further, in the photosensitive composition of the present invention,
The following yellow dyes can be added. Represented by the general formula [I], [II] or [III];
yellow dye whose absorbance at m is 70% or more of the absorbance at 436 nm

[0082]

Embedded image

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 or 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, at least _one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , G ₁ and G ₂ has at least one sulfonic acid group, carboxyl group, sulfonamide group, imide group, N-sulfonylamido group , A phenolic hydroxyl group, a sulfonimide group, or a metal salt thereof, or an inorganic or organic ammonium salt. 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
- it indicates over divalent atomic group selected, n ₁ is 0 or 1.

[0084]

Embedded image

In the formula [II], R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocyclic group, a substituted heterocyclic group, an allyl group or a substituted allyl group. And R ₆ and R ₇ may form a ring together with the carbon atom to which they are attached. n ₂ represents 0, 1 or 2. G ₃ and G ₄ are each independently a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an aryloxycarbonyl group, a substituted aryloxycarbonyl group, an acyl group, a substituted acyl group, an arylcarbonyl group, a substituted arylcarbonyl Represents 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. Further, G ₃ and G ₄ may form a ring composed of a nonmetallic atom together with the carbon atom to which they are bonded. Furthermore, R ₆ , R ₇ , G
_3, one or more sulfonic acid groups to one or more of G _4, a carboxyl group, a sulfonamide group, an imide group, N- sulfonyl amide group, a phenolic hydroxyl group, a sulfonimide group, or a metal salt thereof, an inorganic or organic Has an ammonium salt.

[0086]

Embedded image

In the formula [III], R ₈ , R ₉ , R ₁₀ , R ₁₁ ,
R ₁₂ and R ₁₃ may be the same or different and 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, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl Group, nitro group, carboxyl group, chloro group and bromo group.

The photosensitive lithographic printing plate of the present invention can be obtained by dissolving the above-mentioned components of the photosensitive composition in a solvent capable of dissolving and coating the solution on a support. As described above, the solvent is water-insoluble contained in the intermediate layer of the present invention,
Those which do not dissolve the alkali-soluble polymer compound are selected. Specifically, for example, γ-butyrolactone,
Ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol,
-Methoxy-2-propyl acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, dimethylacetamide, dimethylformamide,
Water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, isopropanol, diethylene glycol dimethyl ether and a mixture of these solvents can be appropriately selected and used.

The concentration (solid content) of the above components is suitably from 2 to 50% by weight. 0.5 g / m ^2-
4.0 g / m ² is preferred. When the amount is less than 0.5 g / m ² , the printing durability deteriorates. When the amount is more than 4.0 g / m ² , the printing durability is improved, but the sensitivity is lowered.

In the photosensitive composition of the present invention, a surfactant for improving a coating method, for example, a surfactant described in
A fluorine-based surfactant as described in JP-A-170950 can be added. The preferred amount is
It is 0.01 to 1% by weight of the total photosensitive composition, and more preferably 0.05 to 0.5% by weight. With the lithographic printing plate obtained as described above, a printed matter faithful to the original picture film can be obtained, but the print blurring and the roughness of the printed matter are poor. As a method of improving the burning blur, there is a method of making the surface of the photosensitive amount provided as described above 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 solution and the particles are coated. Is not improved at all.

However, for example, JP-A-50-12580
No. 5, JP-B-57-6582, JP-B-61-28986
And Japanese Patent Application Laid-Open No. 62-62337, a method of forming a component having irregularities on the surface of a photosensitive amount can improve bokeh blur and improve the roughness of printed matter. Further, as described in JP-B-55-30619, when a light absorbing agent having absorption in the photosensitive wavelength region of the photosensitive material is contained in the mat layer, the burning blur and the roughness are further improved. In addition, an original film having a line number of 300 lines or more per inch and an original film obtained by FM screening, which is more easily burned out than an original film having a line number of 175 lines per inch and which easily gives a sense of roughness of a printed material, is used. Thus, a good printed matter can be obtained. As described above, the following minute patterns are desirably provided on the surface of the photosensitive layer of the photosensitive printing plate. That is, the height of the applied portion is preferably in the range of 1 to 40 μm, particularly 2 to 20 μm, and the size (width) is 10 to 10000 μm, especially 20
The range of -200 µm is preferred. The amount is 1 to 1000
Pieces / mm ² , preferably in the range of 5 to 500 pieces / mm ² .

<3> Development Processing Next, the development processing of the photosensitive lithographic printing plate of the present invention will be described. (Exposure) The photosensitive lithographic printing plate of the present invention is developed after being subjected to image exposure. The light source of the active light beam used for the image exposure includes a carbon arc lamp, a mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, a chemical lamp and the like. Examples of the radiation include an electron beam, an X-ray, an ion beam, and a far-infrared ray. Also, g-line, i-line, D
Eep-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.

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

(Non-Reducing Sugar and Base) This developer contains at least one compound selected from non-reducing sugars and at least one base, and the pH of the solution is 9.
It is characterized by being in the range of 0 to 13.5. Such non-reducing sugars have no free aldehyde or ketone groups,
It is a saccharide that does not show reducing properties, and is classified as a trehalose-type oligosaccharide in which reducing groups are bonded to each other, a glycoside in which a reducing group of a saccharide is bonded to a non-saccharide, and a sugar alcohol obtained by hydrogenating and reducing a saccharide. It is preferably used. Trehalose-type oligosaccharides include saccharose and trehalose, and examples of glycosides include alkyl glycosides, phenol glycosides, and mustard oil glycosides. Examples of sugar alcohols include D, L-arabit, ribit, xylit, D, L
-Sorbit, D, L-mannit, D, L-idit, D, L-tallit, zuricit and allozurcit. Further, maltitol obtained by hydrogenation of disaccharide and reductant (reduced starch syrup) obtained by hydrogenation of oligosaccharide are preferably used. Among these, non-reducing sugars which are particularly preferred are sugar alcohols and saccharose, and D-sorbitol, saccharose and reduced starch syrup are particularly preferred because they have a buffering action in an appropriate pH range and are inexpensive. These non-reducing sugars can be used alone or in combination of two or more kinds, and their ratio in the developing solution is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight. Below this range, a sufficient buffering effect cannot be obtained, and at concentrations higher than this range, it is difficult to achieve high concentration and the problem of increased cost arises. still,
When a reducing sugar is used in combination with a base, there is a problem that the color changes to brown over time, the pH gradually decreases, and the developability decreases.

As the base to be combined with the non-reducing sugar, a conventionally known alkali agent can be used. For example, sodium hydroxide, potassium, lithium, trisodium phosphate, potassium, ammonium, disodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium hydrogencarbonate, potassium, ammonium And inorganic alkali agents such as sodium borate, potassium and ammonium. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine and pyridine are also used. 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 to non-reducing sugars, pH
This is because adjustment becomes possible. Trisodium phosphate, potassium phosphate, sodium carbonate, potassium phosphate, etc. are also preferable because they have a buffering action by themselves. These alkaline agents are added so that the pH of the 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, but the more preferable pH is The range is from 10.0 to 13.2.

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

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

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

(Surfactant) To the developer, various surfactants and organic solvents can be added as necessary for the purpose of accelerating the developability, dispersing the development residue and improving the ink affinity of the printing plate image area. Preferred surfactants include anionic,
Cationic, nonionic and amphoteric surfactants are included. Preferred examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, and sorbitan. Fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol monofatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, poly Glycerin fatty acid partial esters, 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-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated tallow oil, sulfates of fatty acid alkyl esters, alkyl sulfates, polyoxyethylene alkyl ether sulfates, Fatty acid monoglyceride sulfates, polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, 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. Such fluorosurfactants include perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, anionic type such as perfluoroalkyl phosphate, amphoteric type such as perfluoroalkyl betaine,
Cationic and perfluoroalkylamine oxides such as perfluoroalkyltrimethylammonium salts, perfluoroalkylethylene oxide adducts, oligomers containing perfluoroalkyl groups and hydrophilic groups,
Non-ionic types such as oligomers containing perfluoroalkyl groups and lipophilic groups, oligomers containing perfluoroalkyl groups, hydrophilic groups and lipophilic groups, and urethanes containing perfluoroalkyl groups and lipophilic groups are included. The above surfactants can be used alone or in combination of two or more, and are added to the developer in an amount of 0.001 to 10% by weight, more preferably 0.01 to 5% by weight.

(Development Stabilizer) Various development stabilizers are used in the developer. Preferred examples thereof include polyethylene glycol adducts of sugar alcohols described in JP-A-6-282079, tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium such as diphenyliodonium chloride. Salts are mentioned as preferred examples. Further, anionic surfactants or amphoteric surfactants described in JP-A-50-51324, water-soluble cationic polymers described in JP-A-55-95946,
There is a water-soluble amphoteric polymer electrolyte described in 142,528. Further, an organic boron compound to which an alkylene glycol is 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-2-39157
And a water-soluble polyalkylene compound obtained by adding 4 moles or more of ethylene oxide to the acid or alcohol described in the publication.

(Organic Solvent) The developer of the present invention does not substantially contain an organic solvent, but an organic solvent is added if necessary. As such an organic solvent, those having a solubility in water of about 10% by weight or less are suitable, and preferably selected from those having a solubility of 5% by weight or less. 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-benzyloxyethanol, o-methoxybenzyl alcohol, m
-Methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N
-Phenylethanolamine and N-phenyldiethanolamine. "Substantially free of an organic solvent" in the developer of the present invention means that the content of the organic solvent is 5% by weight or less based on the total weight of the used solution. The amount used is closely related to the amount used of the surfactant, and it is preferable to increase the amount of the surfactant as the amount of the organic solvent increases. This is because when the amount of the surfactant is small and the amount of the organic solvent is large, the organic solvent is not completely dissolved, and therefore, it is impossible to expect good developing property.

(Reducing Agent) A reducing agent can be further added to the developer. This 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 phenolic compounds such as thiosalicylic acid, hydroquinone, methol, methoxyquinone, resorcinol and 2-methylresorcinol, phenylenediamine,
Amine compounds such as phenylhydrazine;
More preferred inorganic reducing agents include sulfurous acid, bisulfite, phosphorous acid, hydrogen phosphite, dihydrophosphite,
Examples thereof include sodium salts, potassium salts, and ammonium salts of inorganic acids such as thiosulfuric acid and dithionous acid. Among these reducing agents, sulfites are particularly excellent in the stain prevention effect. These reducing agents are preferably contained in a range of 0.05 to 5% by weight with respect to the developing solution at the time of use.

(Organic carboxylic acid) An organic carboxylic acid can be further added to the developer. Preferred organic carboxylic acids are aliphatic and aromatic carboxylic acids having 6 to 20 carbon atoms. Specific examples of the aliphatic carboxylic acid include caproic acid, enantiic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. . Further, unsaturated fatty acids having a double bond in the carbon chain or branched fatty acids may be used. The aromatic carboxylic acid is a compound in which a carboxyl group is substituted on a benzene ring, a naphthalene ring, an 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 used in the present invention is not particularly limited, but if the content is less than 0.1% by weight, the effect is not sufficient, and if it exceeds 10% by weight, the effect is further improved. Not only can it not be measured, but it can hinder dissolution when another additive is used in combination. Therefore, the preferable addition amount is 0.1 to 10% by weight, more preferably 0.5 to 4% by weight, based on the developer used.

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

The optimum value of such a water softener varies depending on the chelating power, the hardness of the hard water used and the amount of the hard water. 01 to 5% by weight, more preferably 0.01 to 5% by weight
It is in the range of 0.5% by weight. If the added amount is less than this range, the intended purpose is not sufficiently achieved, and if the added amount is 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.

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

(Development and Post-processing) A PS plate developed with a developer having such a composition may be washed with water, a rinsing solution containing a surfactant or the like, a finisher or a protective gum mainly containing gum arabic or a starch derivative. The liquid is post-treated.
In the post-processing of the PS plate of the present invention, these processings can be used in various combinations. In recent years, in the plate making / printing industry, automatic developing machines for PS plates have been widely used in order to rationalize and standardize plate making operations. This automatic developing machine generally comprises a developing section and a post-processing section, and comprises a device for transporting a PS plate, each processing solution tank and a spray device, and pumps the exposed PS plate horizontally while pumping it. Each processing liquid is sprayed from a spray nozzle to perform development and post-processing. Recently, a PS plate is immersed and conveyed in a processing solution tank filled with a processing solution by a guide roll or the like to carry out development processing, or a fixed amount of small amount of washing water is supplied to the plate surface after development for washing. There is also known a method of reusing the waste water as dilution water of 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.

[0110]

Next, embodiments of the present invention will be shown and described in detail. All percentages in the following examples are% by weight unless otherwise specified. (Examples 1 to 6, Comparative Examples 1 to 6) JI having a thickness of 0.24 mm
The surface of the SA1050 aluminum plate was grained using a nylon brush and an aqueous suspension of pumicestone of 400 mesh, and then thoroughly washed with water. After immersing in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds for etching,
After washing with running water, it was neutralized and washed with a 20% aqueous nitric acid solution and washed with water. This was converted to 260 coulombs / dm ² with a 1% nitric acid aqueous solution using a sinusoidal alternating current under the condition of VA = 12.7V.
The electrolytic surface roughening treatment was performed using the quantity of electricity at the time of anode. When the surface roughness was measured, it was 0.55 μm (Ra display). Then immersed in a 30% aqueous sulfuric acid solution,
After desmutting at 2 ° C. for 2 minutes, the current density was 14 A / dm ² in a 20% aqueous sulfuric acid solution, and the amount of anodized film was 2.5 g / m ^2.
Substantially anodized and washed with water to form a substrate [A].

The substrate [A] was treated with a 0.15% by weight aqueous solution of sodium silicate at 22 ° C. for 10 seconds, and washed with water to form a substrate [B]. Further, the substrate [A] was treated with a 2.5% by weight aqueous solution of sodium silicate at 30 ° C. for 10 seconds, and washed with water to prepare a substrate [C]. Further, the substrate [A] was treated with a 2.5% by weight aqueous solution of sodium silicate at 50 ° C. for 5 seconds, and washed with water to prepare a substrate [D]. In addition, as a method for hydrophilization other than sodium silicate, the substrate [A] was treated with 1% saponin.
The substrate [E] was treated with an aqueous solution at 40 ° C. for 30 seconds, washed with water, and
Similarly, the substrate [A] is treated with a 1% aqueous solution of glucopon at 70 ° C. for 30 minutes.
The substrate [F] was treated with water for 2 seconds, and the substrate [F] was similarly immersed in a 1% aqueous solution of rutin trihydrate at 50 ° C. for 30 seconds, followed by washing with water to form a substrate [G]. The polymer compounds found in the present invention shown in Table 1 and the additives shown in Table 2 were mixed and applied to the surfaces of the substrates [B] to [G] thus treated. An intermediate layer was prepared by drying for 10 seconds. The dry weight of the intermediate layer is 5-20 mg /
m ² .

High molecular compound in Table 1 (see Table 4) 0.10 to 0.45 g Additive in Table 2 below (see Table 4) 0.02 g Methanol 100 g Water 1.0 g

[0113]

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Next, the photosensitive liquids [A] and [B] are placed on the substrate.
Alternatively, a photosensitive layer was provided by applying [C]. The coating amount of the photosensitive layer after drying was 1.0 g / m ² with the photosensitive solution [A],
The ratio was 1.8 g / m ² for the photosensitive solutions [B] and [C]. Further, in order to shorten the vacuum contact time during exposure, a photosensitive lithographic printing plate was prepared by forming a mat layer by the method described in JP-B-61-28986.

[Photosensitive solution A] Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (as described in Example 1 of US Pat. No. 3,635,709) ) 0.8 g Cresol-formaldehyde novolak resin (meta-para ratio: 6: 4, weight average molecular weight 8000) 1.2 g Phenol-formaldehyde novolak resin (weight average molecular weight 10,000) 0.3 g Resin other than novolak 0.7 g

[0116]

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Naphthoquinone-1,2-diazide-4-sulfonic acid chloride 0.1 g Tetrahydroxyphthalic anhydride 0.2 g Pyrogallol 0.05 g Benzoic acid 0.02 g 4- [p-N, N-bis (ethoxycarbonylmethyl ) Amino phenyl] -2,6-bis (trichloromethyl) -s-triazine (hereinafter abbreviated as triazine A) 0.1 g Victoria Pure Blue BOH (the counter anion manufactured by Hodogaya Chemical Co., Ltd. was changed to 1-naphthalenesulfonic acid) 0.1 g Dye of structural formula (A) 0.01 g A solution of the polymer compound shown in Table 4 adjusted to 20% by weight by adding methyl ethyl ketone (see Table 3 below) 0.3 g F- 177 (fluorinated surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.1 g methyl ethyl ketone 30 g 1-meth Shi-2-propanol 15g

[0118]

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[0119]

[Table 1]

[0120]

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[Photosensitive solution B] Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709) 0.9 g cresol-formaldehyde novolak resin (meta-para ratio: 6: 4, weight average molecular weight 8000) 1.9 g phenol-formaldehyde novolak resin (weight average molecular weight 10,000) 0.3 g p-normal octylphenol-formaldehyde resin (US patent) No. 4,123,279) 0.02 g naphthoquinone-1,2-diazide-4-sulfonic acid chloride 0.03 g tetrahydroxyphthalic anhydride 0.2 g pyrogallol 0.05 g benzoic acid 0 .02 g Triazine A g Victoria Pure Blue BOH (a dye manufactured by Hodogaya Chemical Co., Ltd. in which the counter anion is changed to 1-naphthalenesulfonic acid) 0.05 g Dye of the structural formula (A) 0.01 g The polymer compound solution shown in Table 4 was treated with methyl ethyl ketone. (See Table 3) 0.30 g F-176PF (a fluorosurfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.05 g methyl ethyl ketone 18.0 g 1-methoxy- 2-propanol 7.0 g water 0.5 g

[Photosensitive solution C] Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and 2,3,4-trihydroxybenzophenone (esterification rate 90%) 0.6 g N- (p-aminosulfonyl) Phenyl) methacrylamide / acrylonitrile / methyl methacrylate copolymer (molar ratio 45/30/25, weight average molecular weight 75000) 1.7 g cresol-formaldehyde novolak resin (meta, para ratio 6: 4, weight average molecular weight 3000) 0 0.7 g Tetrahydroxyphthalic anhydride 0.1 g Triazine A 0.1 g Victoria Pure Blue BOH (a dye manufactured by Hodogaya Chemical Co., Ltd. in which the counter anion is changed to 1-naphthalenesulfonic acid) 0.05 g Dye of structural formula (A) 0.01g F-176PF (Dainippon Ink Chemical Industry Co., Ltd. ) Fluorinated surfactant) 0.05 g Polymer solution shown in Table 4 adjusted to 20 wt% by adding methyl ethyl ketone (see Table 3) 0.20 g γ-butyrolactone 8.0 g Methyl ethyl ketone 12 1.0 g 1-methoxy-2-propanol 10.0 g

The photosensitive lithographic printing plate thus prepared was evaluated by the following method. The exposure latitude was measured using a step wedge manufactured by Fuji Photo Film Co., Ltd.
15), exposure was performed from a distance of 1 m with a 3 kW metal halide lamp, and development was performed at 30 ° C. for 12 seconds using a PS processor 900VR manufactured by Fuji Photo Film Co., Ltd. using the following developer. However, the exposure time was adjusted so that the number of clear stages was 5.0. The number of solid steps at this time was expressed as exposure latitude. The lower the number of solid steps, the higher the resistance of the image portion to minute light exposure, that is, the higher the exposure latitude. At the same time, the lower the solid number, the higher the resistance of the image portion when the alkali is excessively replenished, that is, the higher the development latitude. Furthermore, after the above evaluation, the printing was performed by Heidel printing machine SOR-M for 20 hours.
After printing 00 sheets, the printing plate was removed from the printing press and left for 60 minutes, and then printing was restarted again. At this time, the manner in which the non-image area was washed with ink was evaluated as follows. …: The ink was quickly dispensed in the non-image area X: The ink was dispensed in the non-image area was slow Table 4 shows the evaluation results.

Developer A: 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 Developer B: [SiO ₂ ] / [Na ₂ O] molar ratio 1.2 SiO ₂ 1.4% by weight aqueous solution of sodium silicate 100 parts by weight Ethylenediamine / ethylene oxide adduct (30 mol) 0.03 parts by weight

[0125]

[Table 2]

From the results shown in Table 4, it was found that an intermediate layer containing a polymer compound having an acid group-containing component and an onium group-containing component was provided on an aluminum support that had been subjected to a hydrophilic treatment, and Tg was increased. By using a photosensitive lithographic printing plate provided with a photosensitive layer containing a fluoroaliphatic group-containing polymer compound having a temperature higher than room temperature, the solid sensitivity when the clear sensitivity is kept constant is clearly reduced, and the photosensitive composition of the present invention is used. It can be seen that the lithographic printing plate is extremely excellent in the exposure latitude and the development latitude. Moreover, it is clear that the stain resistance is good even in the developer A in which the non-image portion is not subjected to the hydrophilic treatment.

Examples of the present invention in which another photosensitive solution is used will be described in detail. All percentages in the following examples are% by weight unless otherwise specified. (Examples 7 to 10, Comparative Examples 7 to 10) Previous Examples 1 to 6
Substrates [A] to [G] were prepared in the same manner as described above. A polymer compound found in the present invention shown in Table 1 and an additive shown in Table 2 were mixed and applied to the surfaces of these substrates.
For 10 seconds to form an intermediate layer. Dry weight of the intermediate layer was in the range of 5 to 20 mg / m ^2.

High molecular compound in Table 1 (see Table 5) 0.10 to 0.45 g Additive in Table 2 (see Table 5) 0 to 0.075 g Methanol 100 g Water 1.0 g

Next, a photosensitive layer was provided by applying a photosensitive solution [D] or [E] on the substrate. The coated amount of the photosensitive layer after drying was 1.8 g / m ² .

[Photosensitive solution D] Cresol-formaldehyde novolak resin (meta-para ratio: 6: 4, weight average molecular weight 8000) 0.4 g Phenol-formaldehyde novolak resin (weight average molecular weight 10,000) 0.1 g N- (p-amino) Sulfonylphenyl) methacrylamide / acrylonitrile / methyl methacrylate copolymer (molar ratio 45/30/25, weight average molecular weight 75,000) 1.4 g p-toluenesulfonic acid 0.01 g tetrahydroxyphthalic anhydride 0.08 g diphenylsulfone 0 0.3 g Cyanine dye A 0.04 g

[0131]

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Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd., a dye in which the counter anion was changed to 1-naphthalenesulfonic acid) 0.02 g 20% by weight of the polymer compound solution shown in Table 5 was added with methyl ethyl ketone. (See Table 3) 0.20 g F-176PF (fluorinated surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.05 g γ-butyrolactone 8 g Methyl ethyl ketone 12 g 1-methoxy-2-propanol 10 g

[Photosensitive solution E] Cresol-formaldehyde novolak resin (meta-para ratio: 6: 4, weight average molecular weight 3000) 0.9 g N- (p-aminosulfonylphenyl) methacrylamide / acrylonitrile / methyl methacrylate copolymer (Molar ratio 45/30/25, weight average molecular weight 75000) 0.9 g p-toluenesulfonic acid 0.02 g n-dodecyl stearate 0.05 g maleic anhydride 0.1 g dimethyl sulfone 0.5 g cyanine dye A 0.04 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd., a dye in which the counter anion was changed to 1-naphthalenesulfonic acid) 0.04 g The polymer compound solution shown in Table 5 was adjusted to 20% by weight by adding methyl ethyl ketone. (See Table 3) 0.20g F-177 (Dainichi 0.03 g γ-butyrolactone 8 g Methyl ethyl ketone 12 g 1-methoxy-2-propanol 10 g

The photosensitive lithographic printing plate thus prepared was output at a power of 500 mW, a wavelength of 830 nm, and a beam diameter of 17 μm (1
/ E2) using a semiconductor laser at a main scanning speed of 5 m /
After exposure in seconds, using the developing solution shown above, developing using the PS processor 900VR manufactured by Fuji Photo Film Co., Ltd. at 33 ° C. for various times, and the longest development in which the image area is normally maintained Time was evaluated. The longer the maximum development time, the wider the development latitude. In addition, stainability was evaluated in the same manner as in Examples 1 to 6. Table 5 shows the results.

[0135]

[Table 3]

From the results shown in Table 5, it was found that an intermediate layer containing a polymer compound having an acid group-containing component and an onium group-containing component was provided on an aluminum support that had been subjected to a hydrophilic treatment, and Tg was increased. By using a photosensitive lithographic printing plate provided with a photosensitive layer containing a fluoroaliphatic group-containing polymer compound higher than room temperature, the longest development time is clearly increased,
It can be seen that the photosensitive lithographic printing plate of the present invention is extremely excellent in developing latitude. Moreover, it is clear that the stain resistance is good even in the developer A in which the non-image portion is not subjected to the hydrophilic treatment.

[0137]

As described above, according to the present invention, it is possible to provide a photosensitive lithographic printing plate having good exposure latitude and development latitude while maintaining stain resistance. Also,
According to the present invention, even when development is performed using a developer containing no silicate, that is, even when there is no hydrophilization treatment of the non-image area with the developer, good positiveness of stainability, exposure latitude, and development latitude is achieved. A photosensitive lithographic printing plate can be provided.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Keisa Akiyama 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Pref. CB60 DA14 DA18 DA36 2H096 AA06 BA11 CA03 EA04

Claims (1)

[Claims] An intermediate layer containing a polymer compound having a component having an acid group and a component having an onium group is provided on an aluminum support which has been subjected to a hydrophilization treatment after an anodization treatment. A photosensitive lithographic printing plate comprising a photosensitive layer containing a polymer having a fluoroaliphatic group and a glass transition point of 25 ° C. or higher.