JP2003063166A - Support for lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a support for a lithographic printing plate which is especially improved in fouling resistance during printing by being provided with a hydrophilic surface having high, durable hydrophilicity and can obtain lots of prints high in image quality even in severe printing conditions. SOLUTION: On an aluminum substrate, the hydrophilic surface in which a hydrophilic polymer having reactive groups capable of chemical bonding to the surface of the substrate directly or through a component having crosslinking structure is provided. The hydrophilic surface preferably has the crosslinking structure formed by the hydrolysis or condensation polymerization of an alkoxide compound containing an element selected from Si, Ti, Zr, and Al.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a support for a lithographic printing plate, which has a highly hydrophilic surface,
The present invention relates to a lithographic printing plate support capable of forming an image with excellent image quality.

[0002]

2. Description of the Related Art Lithographic printing is a printing method which utilizes a plate material having an oleophilic region for receiving ink and an ink repellent region (hydrophilic region) for receiving dampening water without receiving ink. In general, a photosensitive lithographic printing plate precursor (PS plate) is used. As the PS plate, one having a photosensitive layer provided on a support such as an aluminum plate has been put into practical use and widely used. In such a PS plate, the photosensitive layer in the non-image area is removed by imagewise exposure and development, and printing is performed by utilizing the hydrophilicity of the substrate surface and the lipophilicity of the photosensitive layer in the image area.
In such a plate material, the substrate surface is required to have high hydrophilicity in order to prevent stains on the non-image area.

Conventionally, as a hydrophilic substrate or hydrophilic layer used for a lithographic printing plate, an anodized aluminum substrate,
Alternatively, in order to further increase the hydrophilicity, it is common practice to subject the anodized aluminum substrate to a silicate treatment. Furthermore, researches on hydrophilic substrates or hydrophilic layers using these aluminum supports have been actively conducted. For example, Japanese Patent Laid-Open No. 7-1853 discloses a substrate treated with polyvinylphosphonic acid as an undercoating agent. Further, JP-A-59-101651 discloses a technique of using a polymer having a sulfonic acid group as an undercoat layer of a photosensitive layer.
A technique of using polyvinyl benzoic acid or the like as an undercoating agent has also been proposed.

These hydrophilic layers provide a lithographic printing plate which has improved hydrophilicity as compared with the conventional ones and gives a printed matter free from stains at the start of printing. Even if the printing conditions are more severe, the hydrophilic layer does not peel off from the support or the hydrophilicity of the surface does not decrease, and a number of stain-free printed products can be obtained. A lithographic printing plate precursor has been desired. In addition, from the practical viewpoint, it is the current situation that further improvement in hydrophilicity is required.

[0005]

SUMMARY OF THE INVENTION An object of the present invention, which has been made to solve the above-mentioned various problems, is to provide a hydrophilic surface having high hydrophilicity and excellent durability. Is improved and even in severe printing conditions,
It is intended to provide a support for a lithographic printing plate, which can obtain a large number of high-quality printed matter.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, have found that a hydrophilic group having a reactive group capable of chemically bonding to the surface of the aluminum substrate is provided on the aluminum substrate. The inventors have found that the above object can be achieved by binding a polymer, and have completed the present invention.

That is, the lithographic printing plate support of the present invention has a hydrophilic group having a reactive group which can be chemically bonded to the surface of the aluminum substrate directly or through a component having a crosslinked structure. The polymer has a hydrophilic surface formed by chemical bonding.

The hydrophilic polymer preferably has a reactive group at the polymer end which can be chemically bonded to the surface of the aluminum substrate directly or through a constituent having a crosslinked structure. Further, among these, as a preferable specific embodiment of the hydrophilic surface chemically bonded to the surface of the aluminum base material through the constituent having a crosslinked structure, the hydrophilic surface is formed of Si, Ti, Zr, or Al. Examples include an embodiment having a crosslinked structure formed by hydrolysis or polycondensation of an alkoxide compound containing a selected element.

As the hydrophilic polymer used in the present invention, more specifically, a polymer compound represented by the following general formula (1) or (2) is preferably exemplified.

[0010]

[Chemical 3]

The polymer represented by the formula (1) has a structure in which the terminals of the polymer units represented by the structural units (i) and (ii) are
It has a silane coupling group represented by the structural unit (iii). In the formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶
Each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, m represents 0, 1 or 2, n represents an integer of 1 to 8, and x and y are x + y = 100. X: y represents a composition ratio of 1: 0 to 1:99. L ¹ , L ² and L ³ each independently represent a single bond or an organic linking group, and Y ¹ and Y ² are independently -N (R ⁷ ).
^{(R 8), - OH,} -NHCOR 7, -COR 7, -CO 2
Represents M or -SO ₃ M, wherein, R ^7, R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
M represents a hydrogen atom, an alkali metal, an alkaline earth metal or onium.

The hydrophilic polymer has the following general formula (2):
It is characterized by being represented by.

[0013]

[Chemical 4]

In the above formula (2), R ¹ , R ² , R ³ , R ⁴ and R
⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, m represents 0, 1 or 2, x and y represent a composition ratio when x + y = 100, x: y
Represents a range of 99: 1 to 50:50. L ^1, L ² each independently represents a single bond or an organic linking group, Y ¹ are each independently ^{-N (R 7) (R 8} ), - OH, -NHCO
R ^7, -COR ^7, represents a -CO ₂ M or -SO ₃ M, wherein, R ^7, R ⁸ represents a hydrogen atom or a carbon number 1 to independently
8 represents an alkyl group, M is a hydrogen atom, an alkali metal,
Represents an alkaline earth metal or onium.

More preferably, a hydrophilic coating liquid containing a cross-linking component represented by the following general formula (3) is prepared together with the above hydrophilic polymer, and the hydrophilic coating liquid is coated on the surface of an aluminum substrate,
By drying, a hydrophilic surface having a strong crosslinked structure can be easily formed.

[0016]

[Chemical 5]

In the formula (3), R ⁹ and R ¹⁰ each independently represent an alkyl group, and X represents Si, Al, Ti, or Zr.
And m represents an integer of 0 to 2.

Although the action of the present invention is not clear, a polymer having a hydrophilic group is chemically bonded directly to the surface of an aluminum substrate in its molecule, or is chemically bonded via a component having a crosslinked structure. Since it has a reactive group capable of reacting, such a hydrophilic polymer causes a coupling reaction with a functional group such as —Al ³⁺ or —OH existing on the surface of the aluminum base material to firmly bond. On the other hand, the hydrophilic group does not participate in the binding reaction with the aluminum base material and exists in a relatively free state, so that both strong binding and high hydrophilicity are compatible with each other. Furthermore, in a preferred embodiment, the hydrophilic group has a graft structure, and Si, T
Since the alkoxide compound containing an element selected from i, Zr, and Al is adsorbed to the aluminum base material through the cross-linking structure formed by hydrolysis and condensation polymerization, this hydrophilic surface is introduced in the state of a graft chain. The hydrophilic functional groups are unevenly distributed on the surface in a free state, and the organic-inorganic composite film having a high-density crosslinked structure is formed by the hydrolysis and polycondensation of the alkoxide. It is considered to be a high-strength film.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The lithographic printing plate support of the present invention comprises:
An aluminum base material (hereinafter, abbreviated as "base material" as appropriate) is chemically bonded to the surface of the base material through a reactive group capable of directly chemically bonding, or to the surface of the base material via a component having a crosslinked structure. Of the reactive groups that can be reacted with each other (hereinafter, appropriately referred to as “specific hydrophilic polymer”) has a hydrophilic surface. First, the specific hydrophilic polymer will be described.

The specific hydrophilic polymer used here has a reactive group which can be chemically bonded to the surface of the substrate directly or through a constituent having a crosslinked structure, at the end or side chain of the hydrophilic polymer. However, there is no particular limitation as long as it has a hydrophilic functional group. As such a specific hydrophilic polymer, those having a crosslinkable group such as an alkoxy group as the reactive group are preferable, and the crosslinkable group exists directly on the surface of the base material such as -Al ³⁺ or -OH. May be bound by a coupling reaction with a functional group, or by preparing a hydrophilic coating solution containing a specific hydrophilic polymer, by coating and drying on the surface of the substrate, hydrolysis of the crosslinkable group, It may be one that is formed by a polycondensation to form a crosslinked structure and is bonded to the substrate via the crosslinked structure. The crosslinked structure formed in the latter manner can easily form a hydrophilic surface which is strong and has excellent durability, and thus can be said to be a preferred embodiment in the present invention. In the present invention, such a crosslinked structure will be appropriately referred to as a “sol-gel crosslinked structure” hereinafter.

Further, as the crosslinkable group, Si, T
An alkoxide compound containing an element selected from i, Zr, and Al is preferable, and an alkoxide of Si is preferable from the viewpoint of reactivity and easy availability. Specifically, a compound used as a silane coupling agent is preferably used. can do. Hereinafter, each aspect of the hydrophilic surface of the support of the present invention and the method for forming the hydrophilic surface will be described in detail.

[Hydrophilic polymer having a reactive group capable of chemically bonding to the surface of an aluminum substrate directly or via a component having a crosslinked structure] Chemically bonded to the surface of an aluminum substrate directly or via a component having a crosslinked structure The hydrophilic polymer having a reactive group that can be bonded at the terminal or in the side chain (specific hydrophilic polymer), as long as it has at least a hydrophilic group and the specific reactive group in the molecule,
Although not particularly limited, preferred embodiments include those having a structure represented by the following general formula (1) or (2).

(Specific Hydrophilic Polymer Represented by General Formula (1)) The specific hydrophilic polymer represented by the following general formula (1) (hereinafter appropriately referred to as "specific hydrophilic polymer (1)") is And having a silane coupling group at the terminal.

[0024]

[Chemical 6]

The polymer compound represented by the formula (1) has a silane cup represented by the structural unit (iii) on at least one of both ends of the polymer unit represented by the structural units (i) and (ii). It may have a ring group, may have this functional group at the other terminal, and may have a hydrogen atom or a functional group capable of initiating polymerization. In the above general formula (1), m represents 0, 1 or 2, R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. Examples of the hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 8 or less carbon atoms is preferable. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group,
t-butyl group, isopentyl group, neopentyl group, 1-
Examples thereof include a methylbutyl group, an isohexyl group, a 2-ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group. R ^{1 to} R ⁶ are, from the viewpoint of effect and availability,
It is preferably a hydrogen atom, a methyl group or an ethyl group.

These hydrocarbon groups may further have a substituent. When the alkyl group has a substituent, the substituted alkyl group is composed of a bond between the substituent and an alkylene group, and as the substituent, a monovalent non-metal atomic group except hydrogen is used. Preferred examples are halogen atoms (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-
Diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, Ν-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyl Oxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group,
Acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'-dialkylureido group, N'-
Arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-
Alkylureido group,

N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureate group, N', N '-Dialkyl-N-arylureido group, N'-aryl-α-alkylureido group, N'-aryl-N-arylureido group, N',
N'-diaryl-N-alkylureido group, N ',
N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group,
N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group,

Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-aryl Rucarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-
SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonato group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N
-Arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N
- arylsulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group phosphono group (-PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group) , dialkyl phosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (-PO ₃ H (alkyl))
And a conjugate base group thereof (hereinafter referred to as an alkylphosphonate group), a monoarylphosphono group (—PO ₃ H (ar
yl)) and a conjugated base group (hereinafter referred to as aryl phosphonophenyl group), phosphonooxy group (-OPO ₃ H ₂₎
And its conjugate base group (hereinafter referred to as a phosphonatoxy group), a dialkylphosphonooxy group (-OPO ₃ (a
lkyl) ₂ ), diarylphosphonooxy group (-O
PO ₃ (aryl) _2), alkylaryl phosphonooxy group (-OPO (alkyl) (aryl) ), monoalkyl phosphonooxy group (-OPO ₃ H (alky
l)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphonooxy group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphite Hona preparative group ), A morpholino group, a cyano group, a nitro group, an aryl group, an alkenyl group, and an alkynyl group.

Specific examples of the alkyl group in these substituents include the above-mentioned alkyl groups, and specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl 2 group, xylyl group and mesityl group. Group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group,
Acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonyl group Examples thereof include a phenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group and phosphonatophenyl group. Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like, and examples of alkynyl group include ethynyl group, 1- A propynyl group,
Examples thereof include 1-butynyl group and trimethylsilylethynyl group. Examples of G ¹ in the acyl group (G ¹ CO-),
Examples thereof include hydrogen, and the above-mentioned alkyl group and aryl group.

Of these substituents, more preferable ones are halogen atoms (-F, -Br, -Cl, -I),
Alkoxy group, aryloxy group, alkylthio group, arylthio group, N-alkylamino group, N, N-dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcapamoyloxy group, acylamino group, formyl group, Acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-
Dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonato group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-aryl Sulfamoyl group, N-alkyl-N
-Arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphosphonato group, phosphonooxy group, Examples thereof include a phosphonatoxy group, an aryl group, and an alkenyl group.

On the other hand, examples of the alkylene group in the substituted alkyl group include a divalent organic residue obtained by removing one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Examples thereof include linear alkylene groups having 1 to 12 carbon atoms, branched alkylene groups having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. Preferred specific examples of the substituted alkyl group obtained by combining the substituent and the alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, a methoxyethoxyethyl group, and allyl. Oxymethyl group, phenoxymethyl group, methylthiomethyl and tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N- Phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxyethyl group, 2-oxypropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxy group Carbonyl butyl group,

Chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N-
(Methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbavamoylmethyl group,
Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N
-Dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonathexyl group, diethylphosphonobutyl group, Diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatooxybutyl group, benzyl group, phenethyl group, α-methyl group Benzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2
-Methylpropenylmethyl group, 2-propynyl group, 2-
Examples include butynyl group and 3-butynyl group.

L ¹ and L ² represent a single bond or an organic linking group. Here, the organic linking group refers to a polyvalent linking group composed of non-metal atoms, and specifically, 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50
Up to oxygen atoms, 1 to 100 hydrogen atoms,
And 0 to 20 sulfur atoms. Examples of more specific linking groups include the following structural units or those formed by combining these.

[0034]

[Chemical 7]

L ³ represents a single bond or an organic linking group. Here, the organic linking group refers to a polyvalent linking group composed of a non-metal atom, and specific examples thereof include those similar to the above L ¹ and L ² . Among them, particularly preferred structure, - (CH ₂₎ a _n -S- (n is an integer of 1 to 8).

Further, Y ¹ and Y ² are --NHCOR ⁷ ,
^{_{-CONH 2, -CON (R 7)}} (R 8), - COR 7, -
OH, —CO ₂ M or —SO ₃ M, where R
⁷ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Further, for —CON (R ⁷ ) (R ⁸ ), R ⁷ ,
R ⁸ may combine with each other to form a ring, and
The formed ring may be a hetero ring containing a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. R ⁷ and R ⁸ may further have a substituent, and examples of the substituent which can be introduced here include the same substituents as those which can be introduced when R ^{1 to} R ⁶ are alkyl groups. Can be listed in.

Specific examples of R ⁷ and R ⁸ include a methyl group,
Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group , 2-ethylhexyl group, 2-methylhexyl group,
A cyclopentyl group and the like are preferred. As M,
Hydrogen atom; alkali metal such as lithium, sodium and potassium; alkaline earth metal such as calcium and barium,
Alternatively, onium such as ammonium, iodonium, and sulfonium can be given. Further, as Y ¹ and Y ² , specifically, —NHCOCH ₃ , —CONH ₂ , —COOH,
-SO ₃ ^- NMe ₄ ^+, a morpholino group, etc. are preferable.

X and y represent composition ratios when x + y = 100, x: y represents a range of 100: 0 to 1:99, and more preferably 100: 0 to 5:95.

The molecular weight of the specific hydrophilic polymer (1) is preferably 1,000 to 100,000, and 1,000.
0 to 50,000 is more preferable, 1,000 to 3
Most preferred is 10,000.

Specific examples (1-1) to (1-23) of the specific hydrophilic polymer (1) which can be preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0041]

[Chemical 8]

[0042]

[Chemical 9]

[0043]

[Chemical 10]

<Synthesis Method> The specific hydrophilic polymer (1) according to the present invention comprises a radically polymerizable monomer represented by the following structural units (i) and (ii) and the following structural unit (ii)
The radical polymerization represented by i) can be synthesized by radical polymerization using a silane coupling agent having a chain transfer ability. Since the silane coupling agent has chain transfer ability, it is possible to synthesize a polymer in which a silane coupling group is introduced at the terminal of the polymer main chain in radical polymerization. The reaction mode is not particularly limited, but bulk reaction, solution reaction, suspension reaction and the like may be performed in the presence of a radical polymerization initiator or under irradiation of a high pressure mercury lamp.

In the polymerization reaction, the introduced amount of the structural unit represented by (iii) is controlled so that the structural unit (i)
Alternatively, in order to effectively suppress homopolymerization with (ii), it is preferable to carry out the same polymerization method using a divisional addition method or a sequential addition method of the unsaturated compound. The reaction ratio of the structural units (i) and (ii) to the structural unit (iii) is not particularly limited, but the structural units (i) and (ii) are 0 per mole of the structural unit (iii). From the viewpoint of suppressing side reactions and improving the yield of the hydrolyzable silane compound, it is preferably in the range of 5 to 50 mol, more preferably in the range of 1 to 45 mol, and in the range of 5 to 40 mol. Is most preferred.

[0046]

[Chemical 11]

The above structural units (i), (ii) and (iii)
In the formula, R ^{1 to} R ⁶ , L ^{1 to} L ³ , Y ¹ , Y ² and m have the same meaning as in the general formula (1). In addition, these compounds are
It is commercially available and can be easily synthesized.

As the radical polymerization method for synthesizing the specific hydrophilic polymer (1), any conventionally known method can be used. Specifically, general radical polymerization methods include, for example, New Polymer Experiments 3, Polymer Synthesis and Reactions 1 (edited by The Polymer Society of Japan, Kyoritsu Shuppan), New Experimental Chemistry Course 1.
9, Polymer Chemistry (I) (edited by The Chemical Society of Japan, Maruzen), Material Engineering Course, Synthetic Polymer Chemistry (Tokyo Denki University Press), etc., and these can be applied.

The specific hydrophilic polymer (1) is
It may be a copolymer with other monomers as described below. Other monomers used include, for example, acrylic acid esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile,
Known monomers such as maleic anhydride and maleic imide are also included. By copolymerizing such monomers, various physical properties such as film-forming property, film strength, hydrophilicity, hydrophobicity, solubility, reactivity and stability can be improved.

Specific examples of acrylic acid esters include:
Methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec-
Or t-) butyl acrylate, amyl acrylate,
2-ethylhexyl acrylate, dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
2-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, chlorobenzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphenethyl acrylate, furfuryl acrylate, Examples thereof include tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, and 2- (hydroxyphenylcarbonyloxy) ethyl acrylate.

Specific examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate,
(N- or i-) propyl methacrylate, (n-, i
-, Sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate,
Dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate,
Benzyl methacrylate, methoxybenzyl methacrylate, chlorobenzyl methacrylate, hydroxybenzyl methacrylate, hydroxyphenethyl methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate, 2- (Hydroxyphenylcarbonyloxy) ethyl methacrylate and the like can be mentioned.

Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, N-.
Hydroxyethylacrylamide, N-phenylacrylamide, N-tolylacrylamide, N- (hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl)
Acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-
N-phenylacrylamide, N-hydroxyethyl-
N-methyl acrylamide etc. are mentioned.

Specific examples of methacrylamides include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, N-benzylmethacrylamide and N-hydroxyethylmethacrylamide. Amide,
N-phenyl methacrylamide, N-tolyl methacrylamide, N- (hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N
-(Tolylsulfonyl) methacrylamide, N, N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like can be mentioned.

Specific examples of the vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like. Specific examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, propylstyrene, cyclohexylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, dimethoxystyrene. , Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.

The proportion of these other monomers used in the synthesis of the copolymer must be sufficient to improve the physical properties, but if the proportion is too high, it will be a support for a lithographic printing plate. Function is insufficient. Therefore, the preferable total ratio of other monomers in the specific hydrophilic polymer (1) is 8
It is preferably 0% by weight or less, and more preferably 50% by weight or less.

(Specific Hydrophilic Polymer Represented by General Formula (2)) The specific hydrophilic polymer represented by the following general formula (2) (hereinafter appropriately referred to as "specific hydrophilic polymer (2)") is , And has a silane coupling group in the side chain.

[0057]

[Chemical 12]

In the above general formula (2), m and R ^{1
~R 6, L 1, L 2} , Y 1 are all the general formula (1) synonymous. x and y represent the composition ratio when x + y = 100, x: y represents the range of 99: 1 to 50:50,
The range of 99: 1 to 60:40 is preferable, and 98: 2 to 7
The range of 0:30 is more preferable. The molecular weight of the specific hydrophilic polymer (2) is 1,000 to 100,000.
Is preferred, 1,000 to 50,000 is more preferred, and 1,000 to 30,000 is most preferred. Here, the specific hydrophilic polymer (2) that can be preferably used in the present invention
Specific examples (2-1) to (2-7) of are shown below, but the present invention is not limited thereto.

[0059]

[Chemical 13]

<Synthesis Method> As the radical polymerization method for synthesizing the specific hydrophilic polymer (2), any conventionally known method can be used. Specifically, general radical polymerization methods include, for example, New Polymer Experiments 3, Polymer Synthesis and Reactions 1 (edited by The Polymer Society of Japan, Kyoritsu Shuppan), New Experimental Chemistry Course 19, Polymer Chemistry (I). (Edited by The Chemical Society of Japan, Maruzen), Material Engineering Course, Synthetic Polymer Chemistry (Tokyo Denki University Press), etc., and these can be applied. Further, the specific hydrophilic polymer (2) may be a copolymer with another monomer, and as the other monomer to be used, the same ones as those mentioned above in the specific hydrophilic polymer (1) can be used. Can be used.

[Crosslinkable Component Represented by General Formula (3)] In the hydrophilic surface according to the present invention, the crosslinkable group in the above specific hydrophilic polymer is —Al ³⁺ directly on the surface of the aluminum substrate, or Chemically bonded to a functional group such as --OH group, or
Prepare a hydrophilic coating liquid containing a specific hydrophilic polymer,
It may also be one in which a crosslinked structure (sol-gel crosslinked structure) is formed by hydrolysis and polycondensation of the crosslinkable group by coating and drying on the surface of the substrate. In forming the sol-gel crosslinked structure, it is preferable to mix the specific hydrophilic polymer and the crosslinking component represented by the following general formula (3), and apply and dry the mixture on the surface of the substrate. The cross-linking component represented by the following general formula (3) is a compound having a polymerizable functional group in its structure and serving as a cross-linking agent, and by polycondensing with the specific hydrophilic polymer. , Forms a strong film having a cross-linked structure.

[0062]

[Chemical 14]

In the general formula (3), R ⁹ represents a hydrogen atom, an alkyl group or an aryl group, R ¹⁰ represents an alkyl group or an aryl group, X represents Si, Al, Ti or Zr,
m represents an integer of 0 to 2. When R ⁹ and R ¹⁰ represent an alkyl group, the number of carbon atoms is preferably 1 to 4. The alkyl group or aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an amino group and a mercapto group. This compound is a low molecular weight compound, and preferably has a molecular weight of 1,000 or less.

Specific examples of the crosslinking component represented by the general formula (3) are shown below, but the invention is not limited thereto. When X is Si, that is, when the hydrolyzable compound contains silicon, examples thereof include trimethoxysilane, triethoxysilane, tripropoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and methyltrimethoxy. Silane, ethyltriethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane,
Diethyldiethoxysilane, γ-chloroprepyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ
-Aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, diphenyldimethoxysilane,
Examples thereof include diphenyldiethoxysilane.
Among these, particularly preferable are tetramethoxysilane, tetraethoxysilane, methyltoluymethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, and phenyltriethoxy. Examples thereof include silane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like.

When X is Al, that is, when the hydrolyzable compound contains aluminum, for example, trimethoxyaluminate, triethoxyaluminate, tripropoxyaluminate, tetraethoxyaluminate, etc. Can be mentioned. When X is Ti, that is, as titanium, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethyl trititanate. Examples thereof include methoxy titanate, methyl triethoxy titanate, ethyl triethoxy titanate, diethyl diethoxy titanate, phenyl trimethoxy titanate and phenyl triethoxy titanate. When X is Zr, that is, as a material containing zirconium, for example, a zirconate corresponding to the compounds exemplified as the material containing titanium can be mentioned.

[Formation of Hydrophilic Surface] (Preparation of Hydrophilic Coating Solution) In preparing a hydrophilic coating solution composition containing the specific hydrophilic polymer, the content of the specific hydrophilic polymer is calculated as solid content, 10% by weight or more,
It is preferably less than 50% by weight. When the content is 50% by weight or more, the film strength tends to decrease, and
If it is less than 10% by weight, the film characteristics are deteriorated and the possibility of cracks in the film is increased, which is not preferable.

When the crosslinking component is added in the preparation of the hydrophilic coating liquid composition which is a preferred embodiment, the amount of the crosslinking component added is 5 mol% or more based on the silane coupling group in the specific hydrophilic polymer. , 10 mol%
The amount is preferably the above amount or more. The upper limit of the amount of the cross-linking component added is not particularly limited as long as it is sufficiently cross-linkable with the hydrophilic polymer, but when added in a large excess, the cross-linking component not involved in the cross-linking causes a problem such as stickiness of the prepared hydrophilic surface. there is a possibility.

A hydrophilic polymer having a silane coupling group at its end, preferably a crosslinking component, is dissolved in a solvent and stirred well to hydrolyze these components, resulting in polycondensation. The organic-inorganic composite sol liquid serves as the hydrophilic coating liquid according to the present invention, whereby a surface hydrophilic layer having high hydrophilicity and high film strength is formed. In the preparation of the organic-inorganic composite sol liquid, in order to accelerate the hydrolysis and polycondensation reactions, it is preferable to use an acidic catalyst or a basic catalyst in combination, and in order to obtain a practically preferable reaction efficiency, the catalyst is essential. Is.

As the catalyst, an acid or a basic compound is used as it is, or a catalyst dissolved in a solvent such as water or alcohol (hereinafter referred to as an acidic catalyst or a basic catalyst) is used. The concentration when dissolved in a solvent is not particularly limited, and may be appropriately selected depending on the properties of the acid or basic compound used, the desired content of the catalyst, etc. The condensation rate tends to increase. However, when a basic catalyst having a high concentration is used, a precipitate may be generated in the sol solution. Therefore, when the basic catalyst is used, its concentration is preferably 1N or less in terms of concentration in an aqueous solution.

The type of acidic catalyst or basic catalyst is not particularly limited, but when it is necessary to use a catalyst having a high concentration, a catalyst composed of an element that hardly remains in the coating film after drying is preferable. Specifically, the acidic catalyst is represented by hydrogen halide such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acid such as formic acid and acetic acid, and RCOOH thereof. Substituted carboxylic acids obtained by substituting R of the structural formula with other elements or substituents, sulfonic acids such as benzene sulfonic acid, and the like can be cited. As the basic catalyst, ammoniacal bases such as aqueous ammonia, amines such as ethylamine and aniline can be used. And so on.

The hydrophilic coating liquid can be prepared by dissolving a hydrophilic polymer having a silane coupling group at the terminal, preferably a crosslinking component, in a solvent such as ethanol, and then optionally adding the above catalyst and stirring. . The reaction temperature is room temperature to 80 ° C., and the reaction time, that is, the time for which stirring is continued is preferably in the range of 1 to 72 hours. By this stirring, hydrolysis and polycondensation of both components are advanced, and A composite sol liquid can be obtained.

The solvent used when preparing the hydrophilic coating liquid composition containing the hydrophilic polymer and preferably the crosslinking component is not particularly limited as long as it can uniformly dissolve and disperse these. However, for example, an aqueous solvent such as methanol, ethanol or water is preferable.

As described above, the sol-gel method is used for the preparation of the organic-inorganic composite sol liquid (hydrophilic coating liquid composition) for forming the hydrophilic surface according to the present invention. For the sol-gel method, see Sakuhana "Sol-gel method science"
It is described in detail in publications such as Agne Jofusha (published) (1988), Shira Hirashima "Technology for functional thin film formation by the latest sol-gel method" General Technology Center (published) (1992). The methods described therein can be applied to the preparation of the hydrophilic coating liquid composition according to the present invention.

Various additives can be used in the hydrophilic coating liquid composition according to the present invention depending on the purpose, as long as the effects of the present invention are not impaired. For example, a surfactant can be added to improve the uniformity of the coating liquid.

A hydrophilic surface can be formed by applying the hydrophilic coating liquid composition prepared as described above to the substrate of the support and drying. The film thickness of the hydrophilic surface can be selected depending on the purpose, but in general, the coating amount after drying is 0.5
To 5.0 g / m ² , preferably 1.0 to
It is in the range of 3.0 g / m ² . Coating amount is 0.5g / m ²
If it is less, the hydrophilic effect is less likely to be exhibited, and 5.0
If it exceeds g / m ² , both sensitivity and film strength tend to decrease, which is not preferable.

(Support Substrate) The aluminum support used in the present invention is required to form a dimensionally stable plate-like material suitable for use in a lithographic printing plate precursor as a base material, which is strong. The outermost surface is required to be aluminum from the viewpoint of forming a hydrophilic surface, and in consideration of these, the required strength,
It is preferable to select one having characteristics such as durability and flexibility. For example, in addition to typical aluminum plates, plastic films (for example, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polycarbonate, polyvinyl acetal, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, butyrate acetic acid). Cellulose, cellulose nitrate, etc.), metal plates other than aluminum (eg, zinc, copper, etc.), or papers laminated with these plastics, etc., on which aluminum is vapor-deposited or laminated, are included.

The preferred aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and a slight amount of a foreign element, and may be a plastic film on which aluminum is laminated or vapor-deposited as described above. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc,
Examples include bismuth, nickel, and titanium. The content of foreign elements in the alloy is at most 10% by weight. Aluminum which is particularly preferred in the present invention is pure aluminum, but completely pure aluminum is difficult to produce in terms of refining technology, and thus may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and conventionally known and publicly known aluminum plates can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 m.
m to about 0.6 mm, preferably 0.15 mm to 0.4
mm, particularly preferably 0.2 mm to 0.3 mm.

The aluminum plate used as the substrate may be subjected to surface treatment such as surface roughening treatment and anodizing treatment, if necessary. Such surface treatment will be briefly described. Prior to roughening the aluminum plate, if desired, a degreasing treatment for removing rolling oil on the surface is performed, for example, with a surfactant, an organic solvent, or an alkaline aqueous solution. The surface roughening treatment of the aluminum plate is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically melting the surface and a method of selectively melting the surface chemically. It is performed by the method. As the mechanical method, known methods such as a ball polishing method, a brush polishing method, a blast polishing method and a buff polishing method can be used. Further, as an electrochemical graining method, there is a method of performing alternating current or direct current in a hydrochloric acid or nitric acid electrolytic solution. Further, as disclosed in Japanese Patent Laid-Open No. 54-63902, a method in which both are combined can be used.
The thus roughened aluminum plate is subjected to an alkali etching treatment and a neutralization treatment, if necessary, and then subjected to anodizing treatment if desired to enhance the water retention and abrasion resistance of the surface. As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used, and sulfuric acid, phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is generally used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte.

The treatment conditions for anodization vary depending on the electrolyte used and cannot be specified unconditionally. Generally, however, the electrolyte concentration is 1 to 80% by weight solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A. / Dm ² , voltage 1 to 100 V, electrolysis time 10 seconds to 5 minutes are suitable. If the amount of the anodic oxide film is less than 1.0 g / m ² , printing durability may be insufficient, or the non-image area of the planographic printing plate may be easily scratched.
So-called "scratch stains" tend to occur in which ink adheres to the scratched portion during printing.

When a plastic film such as a polyester film, which is another preferred embodiment, is used, the hydrophilic surface is formed from the viewpoint of the hydrophilic surface forming property or the adhesiveness with the recording layer provided thereon. It is preferable to use a roughened surface. Hereinafter, examples of preferable surface properties of the support surface (solid surface) used in the present invention will be described. The preferred surface roughening condition of the support material used in the present invention is as follows: center line average roughness (Ra) of the two-dimensional roughness parameter is 0.1 to 1 μm, maximum height (Ry) is 1 to 10 μm, The ten-point average roughness (Rz) is 1 to 10 μm, and the average interval (Sm) of the irregularities is 5 to 80 μm.
m, the average distance (S) between local peaks is 5 to 80 μm, the maximum height (Rt) is 1 to 10 μm, and the center line mountain height (Rp) is 1
A range of 10 to 10 μm and a center line valley depth (Rv) of 1 to 10 μm can be mentioned, and one satisfying one or more of these conditions is preferable, and all of them are more preferable.

The above two-dimensional roughness parameter is based on the following definition. [Center line average roughness (Ra)] A value obtained by extracting a portion of the measurement length L from the roughness curve in the direction of the center line and arithmetically averaging the absolute values of the deviations between the extracted center line and the roughness curve. [Maximum height (Ry)] A value obtained by extracting a reference length in the direction of the average line from the roughness curve, and measuring the interval between the peak line and the valley bottom line of this extracted portion in the direction of the longitudinal magnification of the roughness curve. [Ten-point average roughness (Rz)] From the highest peak to the fifth peak, measured from the roughness curve by the reference length in the direction of the average value and measured in the direction of longitudinal magnification from the average line of this extracted portion. The value of the sum of the average absolute value of the elevations (YP) and the average absolute value of the elevations (Yv) of the 5th to the lowest valley bottoms expressed in micrometers (μm). [Average interval of irregularities (Sm)] A reference length is extracted from the roughness curve in the direction of the average line, and the sum of the average lines corresponding to one peak and one valley adjacent thereto is obtained in this extracted portion. A value that represents the arithmetic average value of the intervals of a large number of irregularities in micrometers (μm).

[Average interval between local peaks (S)] A reference length is extracted from the roughness curve in the direction of the average line, and the length of the average line corresponding to the distance between adjacent local peaks at this extracted portion is determined. A value that represents the arithmetic average value of the intervals between many local peaks in micrometers (μm). [Maximum height (Rt)] The value of the interval between two straight lines when the extracted portion is sandwiched by two straight lines parallel to the center line of the portion extracted from the roughness curve by the reference length. [Center line height (Rp)] The value of the distance from the roughness curve to the straight line that passes through the highest peak parallel to the center line of the extracted portion by extracting the measurement length L in the direction of the center line. [Center line valley depth (Rv)] Measured length L from the roughness curve in the direction of the center line
The value of the distance from the straight line that passes through the deepest valley bottom parallel to the center line of this extracted portion.

(Surface Roughening Treatment Method) As a method of roughening the surface of the substrate, the aluminum surface treatment method described above can be mentioned as a typical one, but particularly, a chemical or electrical treatment method. The treatment method can be applied only when the aluminum plate itself is used as the base material. For example, as a method for surface-treating a composite base material such as aluminum-deposited plastic, the mechanical surface roughening described above is used. It is preferable to adopt other known surface roughening means including the method. Examples of such a roughening means include a method of mechanically rubbing the surface of the base material by sandblasting, brushing, etc., shaving the surface to form recesses, and roughening the surface. These means may be carried out not only individually but also by combining a plurality of methods. Among them, sandblasting is particularly preferable.

<Sandblasting Method> Sandblasting is a method in which an abrasive material having a fine grain size is projected onto the surface of a base material at a high speed so as to make unevenness on the surface. Specifically, sandblasting is performed by compressing the abrasive material with compressed air. The surface treatment is performed by spraying on the surface of the material, and the irregularities formed thereby are adjusted by the conditions of the sandblast treatment. The sand blast treatment may be performed by a known method, for example, carborundum (silicon carbide powder), metal particles and the like are strongly blown onto the surface together with compressed air, and then the object can be achieved by washing with water and drying. The centerline average surface roughness of the base material by sandblasting can be controlled by the particle size of the particles to be sprayed and the amount of treatment (the frequency of treatment per area). The larger the particle size of the particles, or the amount of treatment. The greater the value, the greater the centerline average surface roughness of the surface.

The processing conditions are such that the abrasive is blown from the sandblasting nozzle and blown onto the surface. It is necessary to adjust the distance). Then, the abrasive in the hopper is blown out from the sandblast blowing nozzle by the compressed air sent from the air champer and blown onto the surface of the base material, so that the sandblasting process is performed under the optimized processing conditions. These methods are specifically described in, for example, JP-A-8-34866.
JP-A-11-90827, JP-A-11-90827
It is described as a known method in Japanese Patent No. 254590. Here, the treatment conditions in the sandblast treatment must be such that the abrasive and the object to be ground do not remain on the base material surface after the treatment, and the strength of the base material itself does not decrease. The conditions can be appropriately set empirically.

Specifically, silica sand and other abrasives are used as the abrasive, and it is preferable to use silica sand having a particle size of 0.05 to 10 mm, and silica sand having 0.1 to 11 mm. Is more preferable. Further, the blast distance is preferably 100 to 300 mm, and the blast angle is preferably 45 to 90 degrees, more preferably 45 to 60 degrees. The blast rate is preferably 1 to 10 kg / min. Such conditions are set in order to prevent the abrasive and the object to be ground from remaining on the surface of the base material by the sandblasting process and further to control the grinding depth. The grinding depth is preferably 0.01 to 0.1 μm. Within this range, it is possible to prevent the strength of the base material itself from being reduced due to grinding, which makes it impossible to maintain practical strength.

In the lithographic printing plate support of the present invention,
A lithographic printing plate precursor can be obtained by providing a predetermined recording layer (image forming layer) on the hydrophilic surface formed on the substrate. The image forming layer provided here is optional, but a typical one will be described below.

[Image Forming Layer] (Photosensitive or Thermosensitive Image Forming Layer) In the present invention, the image forming layer (photosensitive layer or thermosensitive layer) provided on the hydrophilic layer is a positive-working sensitive composition. Alternatively, it comprises a negative action sensitive composition.

(Positive Action Sensitive Composition) In the present invention, as the positive action sensitive composition, the following conventionally known positive action sensitive compositions [(a) and (b)] are preferably used. Is.

(A) A conventional positive-working photosensitive composition containing naphthoquinonediazide and a novolak resin. (B) A chemically amplified positive-working photosensitive composition comprising a combination of an alkali-soluble compound protected by an acid-decomposable group and an acid generator.

Both of the above (a) and (b) are well known in the art, and are used in combination with the following positive action-sensitive compositions ((c) to (f)). Is more preferred.

(C) It is possible to prepare a lithographic printing plate which does not require development processing described in JP-A-10-282672.
A laser-sensitive positive composition containing a sulfonic acid ester polymer and an infrared absorber. (D) Laser sensitization comprising a carboxylic acid ester polymer and an acid generator or infrared absorber capable of producing a lithographic printing plate which does not require development processing described in EP652483 and JP-A-6-502260. Positive composition. (E) A laser-sensitive positive composition containing the alkali-soluble compound described in JP-A-11-095421 and a substance which is thermally decomposable and which substantially reduces the solubility of the alkali-soluble compound when not decomposed. object. (F) An alkaline development eluting positive type composition containing an infrared absorber, a novolac resin, and a dissolution inhibitor, which is capable of producing an alkaline development eluting positive lithographic printing plate.

The compounds used in the positive-working sensitive compositions shown in (a) to (f) above will be described below. “Acid generator” The acid generator used in the positive-working sensitive composition is a compound that generates an acid by heat or light, and is generally a photoinitiator for photocationic polymerization or a photoradical for photoradical polymerization. Examples include initiators, photobleaching agents for dyes, photochromic agents, known light-generating compounds used for micro resists and the like, and mixtures thereof, which are appropriately selected and used. can do.

For example, S. I. Schlesinge
r, Photogr. Sci. Eng. , 18,387
(1974), T.S. S. Bal et al. , Po1
dimer, 21, 423 (1980) and the like, U.S. Pat. Nos. 4,069,055 and 4,0.
69,056, ammonium salts described in JP-A-3-140,140 and the like, D.I. C. Necker et a
l. , Macromolecules, 17, 2468
(1984), C.I. S. Wen et al. , Te
h, Proc. Conf. Rad. Curing AS
IA, p478, Tokyo, Oct (1988), U.S. Pat. Nos. 4,069,055 and 4,069,056.
Phosphonium salts described in J. V. Crivell
o et al. , Macromolecules, 1
0 (6), 1307 (1977), Chem. & En
g. News, Nov. 28, p31 (1988), European Patent 104,143, US Patent 339,049.
No. 410,201, JP-A-2-150,848.
And iodonium salts described in JP-A-2-296,514, J. V. Crivello et al. , Po
Lymer J. 17, 73 (1985), J. V. C
rivello et al. J. Org. Che
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et al. J. Polymer Sci. , Po
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J. V. Crivello et a
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14, European Patent Nos. 233,567 and 297,44.
3, 297,442, U.S. Pat. No. 4,933,3
77, 410, 201, 339, 049, 4,760, 013, 4,734, 444, 2,833, 827, German Patent No. 2,904, 626.
Nos. 3,604,580 and 3,604,581, and the like, sulfonium salts described in J. V. Crivello
et al. , Macromolecules, 10
(6), 1307 (1977), J. V. Crivel
lo et al. J. Polymer Sci. ，
Polymer Chem. Ed. , 17, 1047
(1979) and the like, selenonium salts, C.I. S, We
n et al. , Teh, Proc. Conf. Ra
d. Curing ASIA, p478, Tokyo,
Onium salts such as the arsonium salts described in Oct (1988).

US Pat. No. 3,905,815, JP-B-46-4605, JP-A-48-36281, JP-A-55-32070, JP-A-60-239736, and JP-A-61-169835. No. JP-A-61-169837
JP-A-62-58241, JP-A-62-2124
01, JP-A-63-70243, JP-A-63-29
8339 and the like, organic halogen compounds, K. Mei
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(4), 26 (1986), T.W. P. Gillet a
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No. 161445 and the like, organic metal / organic halides, S.I. Hayase et al. J. Polym
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(1985), Q.I. Q. Zhu et al. J. P
photochem. , 36, 85, 39, 317 (19
87), B. Amit et al. , Tetrahhe
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Chem. Soc. 3571 (1965), p. M.
Collins et al. J. Chem. So
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M. Rudinstein et a
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(1988), European Patent Nos. 0290,750 and 04.
No. 6,083, No. 156,535, No. 271,851
No. 0,388,343, US Pat. No. 3,901,
710, 4,181, 531 and JP-A-60-19.
8538, and o described in JP-A-53-133022
-A photoacid generator having a nitrobenzyl type protecting group, TUN
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(3), European Patent Nos. 0199,672 and 84515.
No. 199, 672, 044, 115, 01
No. 01,122, U.S. Pat. Nos. 4,618,554, 4,371,605, 4,431,774, JP-A-64-18143, JP-A-2-245756, and JP-A-3-34573. Examples thereof include compounds represented by iminosulfonates described in JP-A No. 140109 and the like, which generate sulfonic acid by photolysis, and disulfone compounds described in JP-A No. 61-166544.

Further, a compound in which an acid generator is introduced into the main chain or side chain of a polymer, such as M.I. E. Woodhouse
e et al. J. Am. Chem. Soc. , 1
04, 5586 (1982), S.I. P. Pappas
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(1979), U.S. Pat. No. 3,849,137, German Patent No. 3914407, JP-A-63-26653,
JP-A-55-164824, JP-A-62-69263
JP-A-63-14603, JP-A-63-1634
52, JP-A-62-153853, JP-A-63-1
The compounds described in 46029 and the like can be used.
In addition, V. N. R. Pillai, Synthesi
s, (1), 1 (1980), A.S. Abad et a
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4555 (1971), D.I. H. R. Barton e
t al. J. Chem. Soc. , (C), 329
(1970), U.S. Pat. No. 3,779,778, European Patent 126,712, and the like, compounds capable of generating an acid by light can also be used.

In the present invention, the amount of the acid generator added is usually 0.0 based on the total solid content of the photosensitive layer or the heat-sensitive layer.
It is about 01 to 40% by weight, preferably 0.01 to 20% by weight, and more preferably 0.1 to 5% by weight.

"Alkali-Soluble Compound" The alkali-soluble compound used in the positive action-sensitive composition, when applied to the positive type, has a reduced alkali solubility due to coexistence with a dissolution inhibitor, and thus a dissolution inhibitor. By the decomposition of
It is an alkali-soluble compound whose alkali solubility is restored.

Examples of the alkali-soluble compound used in the positive action-sensitive composition include novolac resin, polyhydroquinstyrene, acrylic resin and the like. The novolak resin used in the present invention is a resin obtained by condensing phenols and aldehydes under acidic conditions. Preferred novolac resins include, for example, novolac resins obtained from phenol and formaldehyde, novolac resins obtained from m-cresol and formaldehyde, novolac resins obtained from p-cresol and formaldehyde, novolac resins obtained from o-cresol and formaldehyde, Novolac resin obtained from octylphenol and formaldehyde, novolac resin obtained from m- / p-mixed cresol and formaldehyde, phenol / cresol (o
-, M-, p- or m- / p-, m- / o-, o- / p
-Which may be mixed) and a novolak resin obtained from formaldehyde. These novolac resins have a weight average molecular weight of 800 to 200,
000 and a number average molecular weight of 400 to 60,000 are preferred.

Examples of the alkali-soluble compound other than the novolak resin used in the positive action-sensitive composition include:
For example, polyhydroxystyrenes, hydroxystyrene-N-substituted maleimide copolymer, hydroxystyrene-
Examples thereof include maleic anhydride copolymers, acrylic polymers having an alkali-soluble group, and urethane type polymers having an alkali-soluble group. Here, examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a phosphonic acid group, and an imide group.

Further, hydroxystyrene-based compounds such as poly-p-hydroquinstyrene, poly-m-hydroquinstyrene, p-hydroxystyrene-N-substituted maleimide copolymer and p-hydroxystyrene-maleic anhydride copolymer. When using a polymer, the weight average molecular weight is 2,000.
~ 500,000, and further 4,000-300,000
0 is preferable.

Examples of the acrylic polymer having an alkali-soluble group include methacrylic acid-benzyl methacrylate copolymer, poly (hydroxyphenylmethacrylamide), poly (hydroxyphenylcarbonyloxyethyl acrylate), poly (2,4-dihydroxy). Phenylcarbonyloxyethyl acrylate), and the polymers described in Japanese Patent Application No. 8-211731. These acrylic polymers have a weight average molecular weight of 2,000 to 500,000, preferably 4,000 to
Those of 300,000 are preferable.

Examples of urethane type polymers having an alkali-soluble group include resins obtained by reacting diphenylmethane diisocyanate with hexamethylene diisocyanate, tetraethylene glycol, and 2,2-bis (hydroxymethyl) propionic acid. Among these alkali-soluble polymers, a hydroxystyrene-based polymer and an acrylic copolymer having an alkali-soluble group are preferable in terms of developability.

In the present invention, the alkali-soluble compound may be protected by an acid-decomposable group, and examples of the acid-decomposable group include an ester group and a carbamate group.

In the present invention, the content of these alkali-soluble compounds is about 10 to 90% by weight and 20 to 85% by weight based on the total solid content of the photosensitive layer or the heat-sensitive layer.
Is preferred, and 30-80 wt% is more preferred. When the content of the alkali-soluble compound is less than 10% by weight, the durability of the photosensitive layer or the heat-sensitive layer is deteriorated, and 90
If it exceeds 5% by weight, it is not preferable in terms of sensitivity and durability.
These alkali-soluble compounds may be used alone or in combination of two or more.

"Dissolution Inhibitor" The dissolution inhibitor used in the positive action sensitive composition is a compound which is decomposed by the action of an acid to be alkali-soluble. Examples of the dissolution inhibitor include t-butyl ester, t-butyl carbamate, alkoxyethyl ester, and other carboxylic acids protected by an acid-decomposable group of a chemical amplification system used in the resist field, and phenol compounds. Can be mentioned. In the present invention, the content of the dissolution inhibitor is about 5 to 90% by weight based on the total solid content of the photosensitive layer or the heat sensitive layer, and is 10 to 8%.
0% by weight is preferred.

Suitable quinonediazide compounds include:
Mention may be made of o-quinonediazide compounds. The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases alkali solubility by thermal decomposition, and compounds having various structures can be used. That is, o-quinonediazide assists the solubility of the light-sensitive material system by both the effect of losing the dissolution inhibiting ability of the alkali-soluble compound due to thermal decomposition and the effect of changing o-quinonediazide itself into an alkali-soluble substance. Examples of the o-quinonediazide compound used in the present invention include those described in J. Coser's "Light-Sensitive Systems" (John Wiley)
& Sons. Inc. Although the compounds described on pages 339 to 352 can be used, sulfonic acid esters or sulfonic acid amides of o-quinonediazide reacted with various aromatic polyhydroxy compounds or aromatic amino compounds are particularly preferable. In addition, benzoquinone- (1,2) -diazide sulfonic acid chloride or naphthoquinone- (1,
2) -Ester of diazide-5-sulfonic acid chloride and pyrogallol-acetone resin, US Pat. No. 3,043
Benzoquinone- (1,2) -diazide sulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride and pheno described in No. 6,120 and No. 3,188,210. Esters with ru formaldehyde resin are also preferably used.

Further, an ester of naphthoquinone- (1,2) -diazide-4-sulfonic acid chloride and a phenol-formaldehyde resin or a cresol-formaldehyde resin, naphthoquinone- (1,2) -diazide-4-sulfonic acid chloride and pyrogallol. Esters with acetone resins are likewise preferably used. Other useful o-quinonediazide compounds have been reported and known in numerous patent-related documents. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, JP-A-48-96575, JP-A-49-38701, JP-A-48-13354,
Japanese Patent Publication No. 41-11222, Japanese Patent Publication No. 45-9610,
JP-B-49-17481, U.S. Pat. No. 2,797,2
No. 13, No. 3,454,400, No. 3,544,
No. 323, No. 3,573,917, No. 3,67
4,495, 3,785,825, British Patents 1,227,602, 1,251,345, 1,267,005, 1,329,888. ,
No. 1,330,932, German Patent No. 854,89.
Examples thereof include those described in No. 0 and the like.

In the present invention, the content of the o-quinonediazide compound is about 1 to 50% by weight, preferably 5 to 30% by weight, and preferably 10 to 30% by weight, based on the total solid content of the photosensitive layer or the heat sensitive layer. Is more preferable. These compounds can be used alone, but may be used as a mixture of several kinds. When the content of the o-quinonediazide compound is less than 1% by weight, the image recording property is deteriorated, while
If it exceeds 50% by weight, the durability of the image area is deteriorated and the sensitivity is lowered.

In the present invention, the content of the above-mentioned compounds other than the o-quinonediazide compound is about 1 to 50% by weight based on the total solid content of the photosensitive layer or the heat-sensitive layer, and is 5 to 3%.
0 wt% is preferable, and 10 to 30 wt% is preferable.

(Negative-type sensitive composition) In the present invention,
As the negative action-sensitive composition, the following conventionally known negative action-sensitive compositions ((g) to (h)) can be used.

(G) A negative action-sensitive composition containing a photocrosslinkable group-containing polymer and an azide compound. (H) A negative action-sensitive composition containing the diazo compound described in JP-A-59-101651. (I) A photopolymerizable negative action-sensitive composition comprising a photopolymerization initiator described in US Pat. (H) A negative action-sensitive composition containing an alkali-soluble compound, an acid generator, and an acid-crosslinking compound described in JP-A-11-095421.

The compounds used in the negative action-sensitive composition shown in (g) to (h) above will be described below.

"Polymer having photocrosslinkable group" The polymer having a photocrosslinkable group used in the negative action-sensitive composition is a polymer having a photocrosslinkable group having an affinity for an aqueous alkaline developer. Preferably, for example, US5
No. 064747, the main chain or side chain of the molecule has -CH =
Polymers having a photocrosslinkable group such as CH-CO-; copolymers having a cinnamic acid group and a carboxyl group described in JP-B-54-15711; phenylenediacrylic acid described in JP-A-60-165646. Polyester resin having a residue and a carboxyl group; polyester resin having a phenylenediacrylic acid residue and a phenolic hydroxyl group described in JP-A-60-203630; JP-B-57-4285
A polyester resin having a phenylenediacrylic acid residue and a sodium iminodisulfonyl group described in No. 8; a polymer having an azide group and a carboxyl group in the side chain described in JP-A-59-208552 can be used. In the present invention, the content of the polymer having a photocrosslinkable group is about 5 to 100% by weight, preferably 10 to 95% by weight, and preferably 20 to 90% by weight based on the total solid content of the photosensitive layer or the heat-sensitive layer. % Is preferred.

"Azide Compound" As the azide compound used in the negative action-sensitive composition, 2,6-bis (4-azidobenzal) -4-methylcyclohexanone and 4,4'-diazidediphenylsulfate are exemplified. Id and the like. In the present invention, the content of the azide compound is 5 to 95% by weight based on the total solid content of the photosensitive layer or the heat sensitive layer.
It is about 10 to 90% by weight, and preferably 20 to 80% by weight.
Weight percent is even more preferred.

[Alkali-Soluble Compound] The alkali-soluble compound used in the negative action-sensitive composition is the same as the alkali-soluble compound used in the positive action-sensitive composition.

"Diazo Compound" As the diazo resin used in the negative action-sensitive composition, for example, there is a diazo resin represented by a salt of a condensate of a diazodiarylamine and an active carbonyl compound. Those that are insoluble and soluble in organic solvents are preferred. Particularly suitable diazo resins include, for example, 4-diazodiphenylamine, 4-diazo-3-methyldiphenylamine, 4-diazo-4 ′.
-Methyldiphenylamine, 4-diazo-3'-methyldiphenylamine, 4-diazo-4'-methoxydiphenylamine, 4-diazo-3-methyl-4'-ethoxydiphenylamine, 4-diazo-3-methoxydiphenylamine and formaldehyde, Paraformaldehyde, acetaldehyde, benzaldehyde, 4,4'-
It is an organic acid salt or an inorganic acid salt of a condensate with bis-methoxymethyldiphenyl ether or the like. Examples of the organic acid at this time include methanesulfonic acid, benzenesulfonic acid,
Toluenesulfonic acid, xylenesulfonic acid, mesitylenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, propylnaphthalenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 2-hydroxy −
4-methoxybenzophenone-5-sulfonic acid and the like can be mentioned, and as the inorganic acid, hexafluorophosphoric acid, tetrafluoroboric acid, thiocyanic acid and the like can be mentioned.

Further, a diazo resin whose main chain is a polyester group described in JP-A-54-30121;
Diazo resin obtained by reacting a polymer having a carboxylic acid anhydride residue described in JP-A 1-273538 with a diazo compound having a hydroxyl group; a diazo resin obtained by reacting a polyisocyanate compound with a diazo compound having a hydroxyl group Etc. can also be used.

In the present invention, the content of diazo resin is
0-40 based on the total solid content of the photosensitive layer or the heat-sensitive layer
About wt% is preferable. Moreover, you may use together 2 or more types of diazo resins as needed.

"Photopolymerization Initiator and Addition Polymerizable Unsaturated Compound" As the addition polymerizable unsaturated compound and the photopolymerization initiator used in the negative action-sensitive composition, US Pat. No. 2,760,863, Examples thereof include addition-polymerizable unsaturated compounds having two or more terminal ethylene groups and photopolymerization initiators described in JP-A No. 3,060,023 and JP-A No. 62-121448.

In the present invention, the content of the addition-polymerizable unsaturated compound is about 5 to 95% by weight, preferably 5 to 80% by weight, based on the total solid content of the photosensitive layer or the heat-sensitive layer. The content of the photopolymerization initiator is about 1 to 80% by weight, preferably 5 to 50% by weight, based on the total solid content of the photosensitive layer or the heat sensitive layer.

[Acid Generator] The acid generator used in the negative action-sensitive composition is the same as the acid generator used in the positive action-sensitive composition.

"Acid-crosslinkable compound" The acid-crosslinkable compound used in the negative action-sensitive composition refers to a compound that crosslinks in the presence of an acid, for example, a hydroxymethyl group,
Examples thereof include aromatic compounds and heterocyclic compounds which are poly-substituted with an acetoxymethyl group or an alkoxymethyl group. Among them, preferred examples include compounds in which phenols and aldehydes are bonded under basic conditions. . Among the above compounds, preferred ones include
For example, a compound obtained by condensing phenol and formaldehyde under basic conditions as described above, a compound similarly obtained from m-cresol and formaldehyde, a compound obtained from bisphenol A and formaldehyde,
Examples thereof include compounds obtained from 4,4′-bisphenol and formaldehyde, and compounds disclosed as a resol resin in GB No. 2,082,339. These acid-crosslinkable compounds have a weight average molecular weight of 500 to 1
Those having a number average molecular weight of 200,000 and a number average molecular weight of 200 to 50,000 are preferable.

Another preferable example is EP-A No. 0,
Aromatic compounds substituted with alkoxymethyl or oxiranylmethyl groups, disclosed in 212,482, E
PA No. 0,133,216, DE-A No. 3,63
4,671, monomeric and oligomeric melamine-formaldehyde condensates and urea-formaldehyde condensates disclosed in DE 3,711,264, alkoxy substitutions disclosed in EP-A 0,212,482. There are compounds, etc. Still other preferred examples are, for example, melamine-formaldehyde derivatives having at least two free N-hydroxymethyl, N-alkoxymethyl or N-acyloxymethyl groups. Among these, N-
Alkoxymethyl derivatives are especially preferred. Also, low molecular weight or oligomeric silanols can be used as silicon-containing crosslinkers. Examples of these are dimethyl- and diphenyl-silanediols, and oligomers which are already precondensed and contain these units, for example EP-
Those disclosed in A 0,377,155 can be used.

Produced by dissolving the components for a coating liquid of a desired layer such as the image forming optical layer (recording layer) on a support for a lithographic printing plate of the present invention in a solvent and coating on a suitable support. can do. Depending on the purpose, a protective layer, a resin intermediate layer, an undercoat layer, a back coat layer and the like can be formed in the same manner.

As the solvent used here, ethylene dichloride, cyclohexanone, methyl ethyl ketone,
Methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide,
N, N-dimethylformamide, tetramethylurea,
Examples thereof include N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyrolactone, and toluene, but are not limited thereto. These solvents may be used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1-5.
It is 0% by weight. The coating amount (solid content) on the support obtained after coating and drying varies depending on the use, but is generally 0.5 to 5.0 g / m ² for a photosensitive printing plate.
Is preferred. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the photosensitive film deteriorate. As a method for applying, various methods can be used,
For example, bar coater coating, spin coating, spray coating,
Curtain coating, dip coating, air knife coating, blade coating, roll coating and the like can be mentioned.

[0129]

The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to these.

Example 1 Positive type photosensitive lithographic printing plate precursor <Synthesis example 1: Synthesis of specific hydrophilic polymer> 50 g of acrylamide, 3.4 g of mercaptopropyltrimethoxysilane and 220 g of dimethylacetamide were placed in a 500 ml three-necked flask. Then, 0.5 g of 2,2-azobis (2,4-dimethylvaleronitrile) was added under a nitrogen stream at 65 ° C. After keeping the same temperature for 6 hours with stirring, the mixture was cooled to room temperature. It was put into 2 liters of ethyl acetate, and the precipitated solid was collected by filtration and washed with water to obtain a hydrophilic polymer (1).
The weight after drying was 52.4 g. It is a polymer having a weight average molecular weight of 3000 by GPC (polystyrene standard), and a trimethoxysilyl group (50.0 ppm) was introduced at the terminal by ¹³ C-NMR (DMSO-d ₆ ).
It was confirmed to be a polymer having the structure of the exemplified compound (1-1).

(Preparation of Support) An aluminum plate (material 1050) having a thickness of 0.3 mm was washed with trichlorethylene to degrease it, and then its surface was grained using a nylon brush and 400 mesh pumicetone-water suspension. After doing
Washed well with water. This plate was immersed in a 25% by weight aqueous solution of sodium hydroxide at 45 ° C for 9 seconds for etching, washed with water, and further immersed in 2% by weight nitric acid for 20 seconds and washed with water.
At this time, the etching amount of the grained surface was about 3 g / m ² . Next, this plate was treated with 7 wt% sulfuric acid as an electrolyte at a current density of 15 A / dm ² , and the thickness of the anodized film was 2.4.
After providing a direct current anodic oxide coating so that the g / m ² becomes,
It was washed with water and dried to obtain an aluminum substrate.

(Formation of Hydrophilic Surface) The following compositions were uniformly mixed and stirred at 20 ° C. for 2 hours to carry out hydrolysis,
A sol-like hydrophilic coating liquid composition 1 was obtained. (Hydrophilic coating liquid composition 1) -Hydrophilic polymer [Exemplified compound (1-1)] 0.21 g-Tetramethoxysilane 0.62 g-Ethanol 4.70 g-Water 4.70 g-Nitric acid aqueous solution (1N) 0. 10 g

After that, the hydrophilic coating liquid composition 1 was applied onto the aluminum substrate so that the coating amount after drying was 2 g / m ^2, and dried by heating at 100 ° C. for 10 minutes to prepare an organic-inorganic composite. A hydrophilic layer was formed to obtain a support for a lithographic printing plate. The contact angle (water droplets in the air) of the hydrophilic surface on the obtained support was measured using CA-Z manufactured by Kyowa Interface Science Co., Ltd., and it was 7.9 °, and had excellent hydrophilicity. Was confirmed.

(Formation of Image Forming Layer) <Positive Image Forming Coating Solution 1> • Ester compound of naphthoquinone-1,2-diazito-4-sulfonyl chloride and pyrogallol-acetone resin 0.9 g • Victoria Pure Blue BOH 0 .05 g-Novolak resin obtained from cresol and formaldehyde (meta: para = 6: 4, weight average molecular weight 1800) 2.0 g-Methyl ethyl ketone 20 g-Methyl alcohol 7 g Coating the above image-forming coating solution on the surface of a support after drying An amount of 1.5 g / m ² was applied, and the mixture was heated and dried at 100 ° C. for 30 minutes to form an image forming layer. The planographic printing plate precursor 1
Got

[Printing Evaluation] The positive lithographic printing plate precursor 1 thus obtained was exposed to PS light through a step guide manufactured by FUJIFILM Corporation, and then the developer DP-4 manufactured by FUJIFILM Corporation was used.
Processing was carried out through an automatic processor equipped with (1: 8). Then, by printing with a Heidel SOR-M printing machine, 5,000 good prints without stains on the non-image area were obtained.
It was confirmed that the lithographic printing plate using the support of the present invention had excellent printing durability and maintained high hydrophilicity in the non-image area.

Comparative Example 1 Positive-Type Photosensitive Lithographic Printing Plate Precursor In the hydrophilic coating liquid composition 1 used in Example 1 above,
Example 1 except that a polyacrylamide (weight average molecular weight 1,500) was blended instead of the hydrophilic polymer (1-1) having a silane coupling group at the terminal.
A positive type printing plate precursor was prepared by the same method as described above, and exposure, development and printing were performed under the same conditions. At the beginning of printing, a good printed matter was obtained with no stain on the non-image area, but it gradually began to stain and the image area and non-image area became indistinguishable at the 500th sheet, and the hydrophilicity of the non-image area was printed. It was found to be reduced by continuing.

Example 2 Negative-type photosensitive lithographic printing plate precursor (formation of hydrophilic surface) The following compositions were uniformly mixed, and 6
Hydrolysis was carried out by stirring at 0 ° C. for 2 hours to obtain a sol-like hydrophilic coating liquid composition 2. <Hydrophilic coating liquid composition 2> -Hydrophilic polymer [Exemplified compound (1-9)] 0.21 g-Tetramethoxysilane 0.62 g-Ethanol 4.70 g-Water 4.70 g-Nitric acid aqueous solution (1N) 0. 10 g

Thereafter, the same hydrophilic substrate as used in Example 1 was coated with the above hydrophilic coating liquid composition 2 so that the coating amount after drying was 2 g / m ^2, and the temperature was 100 ° C.
It was heated and dried for 10 minutes to form a hydrophilic layer composed of an organic-inorganic composite, and used as a lithographic printing plate support. The contact angle (water droplets in the air) on the hydrophilic surface of the obtained support was measured by Kyowa Interface Science Co., Ltd.
When manufactured by CA-Z, the measurement result was 8.3 °, and it was confirmed to have excellent hydrophilicity.

[0139] (Formation of image forming layer) <Negative image forming coating liquid>   ・ P-hydroxyphenylmethacrylamide / 2-hydroxyethyl       Methacrylate / acrylonitrile / methyl methacrylate /       Methacrylic acid = 10/20/25/35/10 (weight ratio) composition       Having a weight average molecular weight of 60,000 (5.0 g)   .Diazo compound represented by the following structure     (Weight average molecular weight 16,500) 0.5 g   ・ Victoria Pure Blue BOH 0.1g   ・ Cellulose ethyl ether 0.2g   ・ Tricresyl phosphate 0.5g   ・ Methyl cellosolve 95ml   ・ 5 ml of water

[0140]

[Chemical 15]

The above negative type image forming coating solution was applied onto the surface of the support so that the coating amount after drying was 1.7 g / m ^2, and dried by heating at 100 ° C. for 10 minutes to form an image forming layer. A lithographic printing plate precursor 2 was obtained.

[Printing Evaluation] The obtained lithographic printing plate precursor 2 was exposed to a jet printer 2000 (Oak Manufacturing Co., Ltd.) for 50 seconds through a step guide manufactured by FUJIFILM Corporation, and then developed with the following developer-1. did. Then, by printing with a Heidel SOR-M printing machine, 6,000 good prints with no stain on the non-image area were obtained, and the lithographic printing plate using the support of the present invention had excellent printing durability and It was confirmed that the high hydrophilicity of the image area was maintained.

[0143] <Developer-1>   ・ Benzyl alcohol 30ml   ・ Soda carbonate 5g   ・ Sulfite 5g   ・ Sodium dodecylbenzene sulfonate 10g   ・ Water 1L

(Examples 3 to 14) Positive-type photosensitive lithographic printing plate precursor Example 1 except that the composition of the hydrophilic coating liquid composition and its coating amount were changed as shown in Table 1 below. 1
A hydrophilic layer was formed in the same manner as above to obtain a support for a lithographic printing plate. Here, the contact angle (water droplets in the air) of the hydrophilic surface of the obtained support was measured using CA-Z manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Table 1. Further, a positive type image forming layer was provided on this support in the same manner as in Example 1,
Positive type planographic printing plate precursors 4 to 15 of Examples 4 to 15 were obtained.

[Printing Evaluation] The obtained lithographic printing plate precursors 3 to 14 of Examples 3 to 14 were exposed, developed and printed in the same manner as in Example 1. When any of the lithographic printing plate precursors of Examples 3 to 14 was used, a high-quality printed matter with no stain was obtained. After that, the printing was further continued, and the print stain property at the time of printing 9,000 sheets and 15,000 sheets was evaluated. The results are shown in Table 1. In addition, the following is used as the evaluation standard of the print stain property used here.

<Evaluation Criteria for Print Contamination> ○: No dirt △: Partially soiled ×: Entirely soiled

[0147]

[Table 1]

As described above, the lithographic printing plate support of the present invention has high hydrophilicity, and since the hydrophilicity is maintained even under severe printing conditions, when used as a lithographic printing plate precursor, Printing durability is good, and a large number of printed matter can be obtained without stains on the non-image area.

[0149]

The lithographic printing plate support of the present invention has a hydrophilic surface having high hydrophilicity and excellent durability, so that the stain resistance is improved especially under severe printing conditions. The advantage is that a large number of high-quality printed matter can be obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA00 AA14 AB03 AC01 AD01                       AD03 DA35 DA36                 2H096 AA06 BA01 CA03 CA05                 2H114 AA04 AA23 AA28 BA01 DA05                       DA62 EA04 FA11 GA32

Claims (5)

[Claims] 1. A hydrophilic surface formed by chemically bonding a hydrophilic polymer having a reactive group, which can be chemically bonded to the surface of the aluminum substrate directly or through a component having a crosslinked structure, to the surface of the aluminum substrate. A lithographic printing plate support to be provided. 2. The planographic printing plate according to claim 1, wherein the hydrophilic polymer has a reactive group at the end, which can be chemically bonded to the surface of the aluminum substrate directly or through a constituent having a crosslinked structure. Support for printing plates. 3. The hydrophilic surface comprises Si, Ti, Zr,
The support for a lithographic printing plate according to claim 1, which has a crosslinked structure formed by hydrolysis and polycondensation of an alkoxide compound containing an element selected from Al. . 4. The lithographic printing plate support according to claim 1, wherein the hydrophilic polymer is represented by the following general formula (1). [Chemical 1] The formula (1) is a polymer compound having a silane coupling group represented by the structural unit (iii) at the terminal of the polymer unit represented by the structural units (i) and (ii), and the formula (1) Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, m represents 0, 1 or 2, and n represents It represents an integer of 1 to 8, x and y represent composition ratios when x + y = 100, and x: y represents a range of 100: 0 to 1:99. L
¹ , L ² and L ³ each independently represent a single bond or an organic linking group, and Y ¹ and Y ² are independently -N (R ⁷ ) (R ⁸ ),
^{-OH, -NHCOR 7, -COR 7,} -CO 2 M or -
Represents SO ₃ M, wherein, R ^7, R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, M represents a hydrogen atom, an alkali metal, alkaline earth metal or an onium. 5. The lithographic printing plate support according to claim 1, wherein the hydrophilic polymer is represented by the following general formula (2). [Chemical 2] In formula (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and m is 0, 1 or 2. Where x and y are x + y =
It represents the composition ratio when 100 is set, and x: y is 99: 1 to 5
It represents the range of 0:50. L ¹ and L ² each independently represent a single bond or an organic linking group, and Y ¹ is independently -N.
^{(R 7) (R 8)} , - OH, -NHCOR 7, -COR 7,
Represents —CO ₂ M or —SO ₃ M, wherein R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and M represents a hydrogen atom, an alkali metal, or an alkaline earth metal. Or represents onium.