CN1355448A - Photosensitive lithographic printing plate - Google Patents

Photosensitive lithographic printing plate Download PDF

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CN1355448A
CN1355448A CN 00133306 CN00133306A CN1355448A CN 1355448 A CN1355448 A CN 1355448A CN 00133306 CN00133306 CN 00133306 CN 00133306 A CN00133306 A CN 00133306A CN 1355448 A CN1355448 A CN 1355448A
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phenyl
acid
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lithographic printing
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CN1235089C (en
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藤田和男
丹史郎
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Fujifilm Corp
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Fujifilm Corp
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Abstract

A photosensitive planographic plate has a photosensitive layer which contains an o-naphthalene quione diazide compound and an vinyl copolymer soluble in alkaline aqueous solution but not in water. The vinyl copolymer contains at least one phenol-type hydroxy radical or at least one sulfinoamide radical and at least one polymerizable compound unit with unsaturated bond, or contains at least one alcohol-type hydroxy radical and at least one polymerizable compound unit with unsaturated bond.

Description

Photosensitive lithographic printing plate
The present invention relates to photosensitive lithographic printing plate.Exactly, the present invention with have a photosensitive layer and guarantee large-scale development conditions and provide the photosensitive lithographic printing plate of the lithographic printing-plate that the scumming phenomenon do not occur relevant that wherein photosensitive layer comprises the positive-type light-sensitive compound and has the outstanding anti-wear performance and the macromolecular compound of chemical-resistance.
The photosensitive composition that comprises adjacent naphthoquinones two triazo-compounds and phenolic varnish type phenolics is used as very outstanding lithographic printing-plate plate-making with photosensitive composition and photoresist photosensitive composition industrial.
But, at its aspect of performance many weak points are arranged as the phenolic varnish type phenolics of wherein a kind of principal ingredient use.For example, their sheet base adhesion property difference and its film are crisp and frangible, but its paintability and anti-wear performance are also poor, and such phenolics can not guarantee to use their lithographic printing-plate to have the sufficiently long printing life-span, especially when using UV printing ink to print, this is because their chemically-resistant materials not.
As the method for improving above-mentioned various performances, extensively adopted a kind of calcination to handle (thermal treatment of behind exposure imaging, carrying out).But, this processing cause the low molecular compound that obtains by photosensitive layer area of image distillation to stick on the non-area of image and thereby formed forme scumming (being stain) can appear.
In order to solve those problems, various macromolecular compounds have been carried out experiment and made bonding agent to determine them whether to be suitable for.For example, JP-B-52-41050 (at this used term " JP-B " expression " the open text of the Jap.P. of having examined ") described poly-(hydroxy styrenes) and hydroxy styrenes multipolymer can improve film performance, but its shortcoming is that anti-wear performance and chemical-resistance are poor.On the other hand, JP-A-51-34711 (at this used term " JP-A " expression " the open text of unexamined Jap.P. ") has proposed the macromolecular compound that contains acrylic acid derivative as its main component units is used as bonding agent.But those macromolecular compounds have such shortcoming, and promptly they only allow suitable development conditions among a small circle and have given strong inadequately anti-wear performance.In addition, JP-A-63-89864, JP-A-1-35436, JP-A-1-52139, JP-A-8-339082 have proposed to comprise that the macromolecular compound of the acrylic acid derivative unit that contains phenolic hydroxyl is as bonding agent in its molecular structure, but the anti-wear performance of those macromolecular compounds is still strong inadequately and they have such problem, and the scumming phenomenon can appear in the forme that promptly contains this bonding agent.
In addition, the macromolecular compound that JP-A-2-866 has proposed to contain sulfonamido is as bonding agent, but the anti-wear performance of these compounds is also strong inadequately and can produce the scumming problem.
Therefore, the objective of the invention is to provide that the enough alkaline developer solutions of a kind of energy develop to it and have strong anti-wear performance and guarantee the photosensitive lithographic printing plate in long printing life-span.
Another object of the present invention provides a kind of photosensitive lithographic printing plate, need not accept calcination when it has outstanding chemical-resistance and can be formed in printing UV printing ink (UV cured printing ink) and handle the lithographic printing-plate that just shows the long printing life-span.
Another object of the present invention is that a kind of photosensitive lithographic printing plate that does not occur the lithographic printing-plate of scumming phenomenon on a large scale when development conditions also can be formed in printing that has will be provided.
Another object of the present invention be to provide a kind of comprise one that have a good basic adhesion property and become the flexible film shape and in organic solvent, have the photosensitive lithographic printing plate of the photosensitive layer of highly dissoluble.
We have studied the composition of ethylenic copolymer closely, found that and utilize a kind of its photosensitive layer to adopt the photosensitive lithographic printing plate of such photosensitive composition just to realize above-mentioned purpose, promptly except the photosensitive compound beyond the region of objective existence, it also comprises the macromolecular compound (being abbreviated as " polyvinyl ") based on vinyl polymerization, wherein there are at least two kinds of specific functional groups, realized the present invention thus.
Exactly, in a kind of photosensitive lithographic printing plate that contains such photosensitive layer, realized the present invention, be that described photosensitive layer comprises water insoluble but dissolves in adjacent naphthoquinones two triazo-compounds and the polyvinyl of alkaline aqueous solution, the therein ethylene based polyalcohol is a kind of multipolymer, and it comprises that (A) contains the compound unit (being abbreviated as " monomer (A) ") of at least one phenolic hydroxyl or at least one sulfonamido and at least one polymerizable unsaturated bond and (B) contain the compound unit (abbreviating " monomer (B) " as) of at least one alcoholic hydroxyl and at least one polymerizable unsaturated bond.
By the photosensitive composition that contains the multipolymer that constitutes by monomer (A) unit and monomer (B) unit at least as its photosensitive layer, photosensitive lithographic printing plate of the present invention can have adhesiveness between gratifying printing forme sheet base and the photosensitive layer, have by force as the photosensitive layer of mantle and because of the dissolubility of multipolymer in organic solvent good sheet base apply tendency and by apply, dry and then make in the exposure region that the photosensitive composition exposure forms outstanding ability with the alkaline developer solution development by image.In addition, the positive that forms on forme of the present invention has strong anti-wear performance and good sheet base adhesion property, thereby the forme of the present invention of accepting precompressed can be printed out many superior in quality printed documents when carrying out printing operation.
In addition, forme of the present invention has outstanding chemical-resistance, thereby it can provide a kind of and have the outstanding printing life-span (i.e. long printing life-span), and when accepting the UV ink printing, the lithographic printing-plate of scumming also can not appear in no calcination processing.
Below understand the composition of the photosensitive complex of photosensitive lithographic printing plate of the present invention specifically.
Water insoluble but polyvinyl of the present invention that dissolve in alkaline aqueous solution is the macromolecular compound that uses well-known at least one monomer of polymerization initiator polymerization (A) and monomer (B) to make by in appropriate solvent, described monomer (A) comprises a kind of complex that contains at least one phenolic hydroxyl or at least one sulfonamido and at least one polymerizable unsaturated bond, and described monomer (B) comprises a kind of complex that comprises at least one alcoholic hydroxyl and at least one polymerizable unsaturated bond.
Water insoluble but suitable example that dissolve in the polyvinyl of the present invention of alkaline aqueous solution comprises acrylate copolymer, styrene polymer and vinethene polymkeric substance.
Containing at least one phenolic hydroxyl in each molecule is represented by following formula (I0) with at least one polymerizable unsaturated bond and compound that belong to monomer (A) category:
Figure A0013330600051
Wherein, X represent-O-or-NR 3-; R 1Expression-H or-CH 2R 2Represent a C who does not replace or replace 1-12Alkylidene, ring alkylidene, arlydene or arylmethylene alkyl; R 3Expression or a hydrogen atom or a C who does not replace or replace 1-12Alkyl, naphthenic base or aralkyl; Y represents-NHCOOR 4,-OCONHR 4-or-NHCONHR 4-; R 4Represent a singly-bound or a C who replaces or do not replace 1-12Alkylidene or ring alkylidene; Z represents an arlydene that replaces or do not replace; A natural number between the n ' expression 1-3.
By formula (I o) representative low molecular compound in, contain a C respectively 1-8Arlydene is as R 2, ring alkylidene or one is replaced to the phenylene that do not replace or naphthylene as R 2,, contain a hydrogen atom as R 3With contain a singly-bound or a C particular preferredly 1-6Arlydene is as R 4Following compound (M1)-(M10) is exemplified to especially being preferred for the example of low molecular compound of the present invention:
Figure A0013330600061
Of the present invention water insoluble but dissolve in the multipolymer of alkaline aqueous solution, in a copolymer molecule, the proper proportion that contains the compound monomer (monomer (A)) of at least one phenolic hydroxyl and at least one polymerizable unsaturated bond is 1%-40% (molar percentage) and is preferably 10%-35%.
When the ratio of monomer (A) unit during less than 1% (molar percentage), formed multipolymer to lose efficacy for developing and scumming responsible.And when the ratio of monomer (A) unit was higher than 40% (molar percentage), formed multipolymer caused to develop and floats and the printing lost of life.
Contain at least one sulfonamido and comprise the compound of representing by following formula (I)-(V) with at least one polymerizable unsaturated bond and example that also belong to the compound of monomer (A) category: Wherein, X 1And X 2Respectively expression-O-or-NR 7-; R 1And R 4Respectively expression-H or-CH 3R 2And R 5Represent a C who does not replace or replace respectively 1-12Alkylidene, ring alkylidene, arlydene or arylmethylene alkyl; R 3Represent a hydrogen atom or a C who does not replace or replace 1-12Alkyl, naphthenic base or aralkyl; R 6Represent a C who does not replace or replace 1-12Alkyl, naphthenic base, aralkyl; R 7Represent a hydrogen atom or a C who does not replace or replace 1-12Alkyl, naphthenic base or aralkyl; Z 1, Z 2And Z 3Expression-NHCOOR respectively 18,-OCONHR 19-or-NHCONHR 20-; R 18, R 19And R 20Represent a C who replaces or do not replace respectively 1-12Alkylidene, ring alkylidene, arlydene or arylmethylene alkyl; Y 1And Y 2Represent respectively a singly-bound or-C (=O)-; R 8, R 10And R 14Represent a hydrogen atom, a halogen atom or a methyl respectively; R 9Represent a C who replaces or do not replace 1-12Alkylidene, ring alkylidene, arlydene or arylmethylene alkyl; R 11And R 15Represent a singly-bound or a C who does not replace or replace respectively 1-12Alkylidene, ring alkylidene, arlydene or arylmethylene alkyl; R 12And R 16Represent a C who does not replace or replace respectively 1-12Alkylidene, ring alkylidene, arlydene or arylmethylene alkyl; R 13Represent a hydrogen atom or a C who does not replace or replace 1-12Alkyl, naphthenic base or aralkyl; R 17Represent a C who replaces or do not replace 1-12Alkyl, naphthenic base, arlydene or aralkyl.
By formula (I) or (II) expression low molecular compound in, being particularly useful for compound of the present invention is that those contain a C respectively 2-6Alkylidene, phenylene that ring alkylidene or one replace or do not replace or naphthylene respectively as R 2And R 5, contain a hydrogen atom, a C 1-6Alkyl, naphthenic base or a phenyl or naphthyl that replaces or do not replace as R 3, contain an alkyl, naphthenic base or a phenyl or naphthyl that does not replace or replace as R 6, contain a hydrogen atom as R 7Compound.The example of the compound of these particularly suitables comprises Methacrylamide, as N-(adjacent aminosulfonyl phenyl) Methacrylamide, N-(an aminosulfonyl phenyl) Methacrylamide, N-(to the aminosulfonyl phenyl) Methacrylamide, N-(adjacent methylamino sulfonyl-phenyl) Methacrylamide, N-(a methylamino sulfonyl-phenyl) Methacrylamide, N-(to the methylamino sulfonyl-phenyl) Methacrylamide, N-(adjacent ethylamino sulfonyl-phenyl) Methacrylamide, N-(an ethylamino sulfonyl-phenyl) Methacrylamide, N-(to the ethylamino sulfonyl-phenyl) Methacrylamide, N-(adjacent n-propylamine base sulfonyl-phenyl) Methacrylamide, N-(a n-propylamine base sulfonyl-phenyl) Methacrylamide, N-(aligning the third aminosulfonyl phenyl) Methacrylamide, N-(adjacent isopropylamino sulfonyl-phenyl) Methacrylamide, N-(an isopropylamino sulfonyl-phenyl) Methacrylamide, N-(to the isopropylamino sulfonyl-phenyl) Methacrylamide, N-(adjacent n-butyl amine base sulfonyl-phenyl) Methacrylamide, N-(a n-butyl amine base sulfonyl-phenyl) Methacrylamide, N-(aligning fourth aminosulfonyl phenyl) Methacrylamide, N-(adjacent isobutyl aminosulfonyl phenyl) Methacrylamide, N-(an isobutyl aminosulfonyl phenyl) Methacrylamide, N-(to isobutyl aminosulfonyl phenyl) Methacrylamide, N-(adjacent Zhong Ding aminosulfonyl phenyl) Methacrylamide, N-(a Zhong Ding aminosulfonyl phenyl) Methacrylamide, N-(to Zhong Ding aminosulfonyl phenyl) Methacrylamide, N-(adjacent uncle's fourth aminosulfonyl phenyl) Methacrylamide, N-(uncle's fourth aminosulfonyl phenyl) Methacrylamide, N-(to uncle's fourth aminosulfonyl phenyl) Methacrylamide, N-(adjacent phenylsulfamoyl phenyl) Methacrylamide, N-(a phenylsulfamoyl phenyl) Methacrylamide, N-(to the phenylsulfamoyl phenyl) Methacrylamide, N-{ neighbour (α-naphthylamino sulphonyl) phenyl } Methacrylamide, (α-naphthylamino sulphonyl) phenyl between N-{ } Methacrylamide, N-{ is to (℃-naphthylamino sulphonyl) phenyl } Methacrylamide, N-{ neighbour (β-naphthylamino sulphonyl) phenyl } Methacrylamide, (β-naphthylamino sulphonyl) phenyl between N-{ } Methacrylamide, N-{ is to (β-naphthylamino sulphonyl) phenyl } Methacrylamide, N-{1-(3-aminosulfonyl) phenyl } Methacrylamide, N-{1-(3-aminosulfonyl) phenyl } Methacrylamide, N-{1-(3-aminosulfonyl) phenyl } Methacrylamide, the amino benzyl acrylamide of the adjacent sulfonyloxy methyl of N-, the amino benzyl acrylamide of sulfonyloxy methyl between N-, N-is to the amino benzyl acrylamide of sulfonyloxy methyl, the adjacent ethyl sulfonamido of N-benzyl acrylamide, ethyl sulfonamido benzyl acrylamide between N-, N-is to ethyl sulfonamido benzyl acrylamide, the adjacent phenyl sulfonamido of N-benzyl acrylamide, phenyl sulfonamido benzyl acrylamide between N-, N-is to phenyl sulfonamido benzyl acrylamide, N-adjacency pair aminomethyl phenyl sulfonamido benzyl acrylamide, p-methylphenyl sulfonamido benzyl acrylamide between N-, N-is to p-methylphenyl sulfonamido benzyl acrylamide, N-{ is to (Alpha-Naphthyl sulfonamido) phenyl } Methacrylamide, N-{ is to (betanaphthyl sulfonamido) phenyl } Methacrylamide, N-(the amino ethyl of 2-sulfonyloxy methyl) Methacrylamide, N-(2-ethyl sulfonamido ethyl) Methacrylamide, N-(2-phenyl sulfonamido ethyl) Methacrylamide, N-(2-p-methylphenyl sulfonamido ethyl) Methacrylamide, N-(2-Alpha-Naphthyl sulfonamido ethyl) Methacrylamide, N-(2-betanaphthyl sulfonamido ethyl) Methacrylamide; Contain substituent acrylamide same as described above; Methacrylate is as adjacent aminosulfonyl phenyl methyl acrylate, between aminosulfonyl phenyl methyl acrylate, to aminosulfonyl phenyl methyl acrylate, adjacent methylamino sulfonyl-phenyl methacrylate, between methylamino sulfonyl-phenyl methacrylate, to methylamino sulfonyl-phenyl methacrylate, adjacent ethylamino sulfonyl-phenyl methacrylate, between ethylamino sulfonyl-phenyl methacrylate, to ethylamino sulfonyl-phenyl methacrylate, adjacent n-propylamine base sulfonyl-phenyl methacrylate, between n-propylamine base sulfonyl-phenyl methacrylate, align the third aminosulfonyl phenyl methyl acrylate, adjacent isopropylamino sulfonyl-phenyl methacrylate, between isopropylamino sulfonyl-phenyl methacrylate, to isopropylamino sulfonyl-phenyl methacrylate, adjacent n-butyl amine base sulfonyl-phenyl methacrylate, between n-butyl amine base sulfonyl-phenyl methacrylate, align fourth aminosulfonyl phenyl methyl acrylate, adjacent isobutyl aminosulfonyl phenyl methyl acrylate, between isobutyl aminosulfonyl phenyl methyl acrylate, to isobutyl aminosulfonyl phenyl methyl acrylate, between Zhong Ding aminosulfonyl phenyl methyl acrylate, to Zhong Ding aminosulfonyl phenyl methyl acrylate, between uncle's fourth aminosulfonyl phenyl methyl acrylate, to uncle's fourth aminosulfonyl phenyl methyl acrylate, adjacent phenylsulfamoyl phenyl methyl acrylate, between phenylsulfamoyl phenyl methyl acrylate, to phenylsulfamoyl phenyl methyl acrylate, between-(α-naphthylamino sulphonyl) phenyl methyl acrylate, to (α-naphthylamino sulphonyl) phenyl methyl acrylate, between-(β-naphthylamino sulphonyl) phenyl methyl acrylate, to (β-naphthylamino sulphonyl) phenyl methyl acrylate, 1-(3-aminosulfonyl) naphthyl methyl acrylate, 1-(3-methylamino sulphonyl) naphthyl methyl acrylate, 1-(3-ethylamino sulphonyl) naphthyl methyl acrylate, the amino benzyl acrylate of adjacent sulfonyloxy methyl, between the amino benzyl acrylate of sulfonyloxy methyl, to the amino benzyl acrylate of sulfonyloxy methyl, adjacent ethyl sulfonamido benzyl acrylate, between ethyl sulfonamido benzyl acrylate, to ethyl sulfonamido benzyl acrylate, adjacent phenyl sulfonamido benzyl acrylate, between phenyl sulfonamido benzyl acrylate, to phenyl sulfonamido benzyl acrylate, adjacent (p-methylphenyl sulfonamido) phenyl methyl acrylate, between (p-methylphenyl sulfonamido) phenyl methyl acrylate, to (p-methylphenyl sulfonamido) phenyl methyl acrylate, to (Alpha-Naphthyl sulfonamido) phenyl methyl acrylate, to (betanaphthyl sulfonamido) phenyl methyl acrylate, the amino ethyl-methyl acrylate of 2-sulfonyloxy methyl, 2-ethyl sulfonamido ethyl-methyl acrylate, 2-phenyl sulfonamido ethyl-methyl acrylate, 2-p-methylphenyl sulfonamido ethyl-methyl acrylate, 2-Alpha-Naphthyl sulfonamido ethyl-methyl acrylate, 2-betanaphthyl sulfonamido ethyl-methyl acrylate; Contain substituent acrylate same as described above.
As for being preferably in by the substituting group in the low molecular compound of formula (III)-(V) representative, R 8, R 10And R 14Be respectively a hydrogen atom, R 9Be methylene, phenylene or the naphthylene that does not replace or replace, R 11And R 15Be respectively a singly-bound or methylene, R 12And R 16Be respectively a C 1-6Alkylidene or a phenylene or a naphthylene that replaces or do not replace, R 13Be a hydrogen atom, a C 1-6Alkyl, a naphthenic base or a phenyl or naphthyl that replaces or do not replace, R 17Be a C 1-6Alkyl, a naphthenic base or a phenyl or naphthyl that replaces or do not replace.
Comprise to aminosulfonyl styrene, to aminosulfonyl-α-Jia Jibenyixi, to aminosulfonyl phenyl allyl ether, to (N-methylamino sulphonyl) phenyl allyl ether, the amino vinyl acetate of sulfonyloxy methyl, phenyl sulfonamido vinyl acetate, phenyl sulfonamido allyl acetate with to the amino phenyl allyl ether of sulfonyloxy methyl by the suitable example of the compound of formula (III)-(V) representative.
Of the present invention water insoluble but be dissolved in the multipolymer of alkaline aqueous solution, in a molecule of multipolymer, the proper proportion that comprises the compound unit (monomer (A) unit) of at least one sulfoamido and at least one polymerizable unsaturated bond is 1%40% (molar percentage) and is preferably 10%-35%.
When the ratio of monomer (A) unit during less than 1% (molar percentage), formed multipolymer will lose efficacy to developing and scumming is responsible for, and when it is higher than 40%, and formed multipolymer causes and develops unsteady or print the lost of life.
The alcoholic hydroxyl of monomer (B) compound of at least one alcoholic hydroxyl and at least one polymerizable unsaturated bond (or contain) can any one-level, secondary and tertiary alcohol formula hydroxyl, but the alcoholic hydroxyl of preferred one-level, secondary.Monomer (B) can comprise any amount of alcoholic hydroxyl, but the right quantity of contained alcoholic hydroxyl is 1-3.As half monomer (B) that contains polymerizable unsaturated bond, can be with reference to acryloyl group, styryl, vinyl.Preferably monomer (B) contains such functional group.Exactly, the compound by following formula (VI)-(IX) representative is applicable to monomer (B):
Figure A0013330600121
X 3And X 4Respectively representative-O-or-NR 23-; R 18And R 20Respectively representative-H or-CH 3R 19And R 22Represent a C who does not replace or replace respectively 1-12Alkylidene, ring alkylidene or arylmethylene alkyl; R 21Representative contains the residual hydrocarbon of at least two carbon atoms, wherein can contain a different in nature atom; R 23Represent a hydrogen atom or a C who does not replace or replace 1-12Alkyl, naphthenic base, aryl or aralkyl; R 24, R 26Represent a hydrogen atom, a halogen atom or a methyl respectively; R 25Represent a singly-bound or a C who does not replace or replace 1-12Alkylidene, ring alkylidene or arylmethylene alkyl; R 27Represent a singly-bound or a C who replaces or do not replace 1-12Alkylidene, ring alkylidene or arylmethylene alkyl; R 28Represent one to be replaced to the C that does not replace 1-12Alkylidene, ring alkylidene or arylmethylene alkyl; L, m, n represent an integer among the 1-20 respectively.
In the low molecular compound by formula (VI)-(VII) representative, being specially adapted to compound of the present invention is that those have C 1-6Alkylidene or ring alkylidene are respectively as R 19, R 22, have a C 2-6Phenylene that alkylidene, ring alkylidene or one replace or do not replace or naphthylene are as R 21, have a hydrogen atom as R 23, have a integer among the 1-10 as I, have a integer among the 1-3 as the compound of m.
The example of those compounds comprises acrylate, as hydroxymethyl acrylate, 2-hydroxy ethyl methacrylate, 3-hydroxypropyl acrylate, 4-hydroxyl butylacrylic acid ester, 5-hydroxyl amyl group acrylate, 3-hydroxyl amyl group acrylate, 2,2-dimethyl hydroxypropyl acrylate, trihydroxymethyl propane one acrylate, diglycol acrylate, tetraethylene glycol one acrylate, dipropylene glycol one acrylate; Methacrylate, as methylol methacrylate, 2-hydroxyethyl meth acrylate, 3-hydroxypropyl methyl acrylate, 4-hydroxyl butyl methyl acrylate, 5-hydroxyl amyl group methacrylate, 3-hydroxyl amyl group methacrylate, 2,2-dimethyl hydroxypropyl methyl acrylate, trihydroxymethyl propane monomethyl acrylate, diglycol methacrylate, tetraethylene glycol monomethyl acrylate, dipropylene glycol monomethyl acrylate; Acrylamide, as N hydroxymethyl acrylamide, N-(2-hydroxyethyl) acrylamide, N-(3-hydroxypropyl) acrylamide, N-(4-hydroxyl butyl) acrylamide, N-(5-hydroxyl amyl group) acrylamide, N-(3-hydroxyl amyl group) acrylamide, N-(2,2-dimethyl hydroxypropyl) acrylamide; Methacrylamide, for example N-methylol methacrylamide, N-(2-hydroxyethyl) Methacrylamide, N-(3-hydroxypropyl) Methacrylamide, N-(4-hydroxyl butyl) Methacrylamide, N-(5-hydroxyl amyl group) Methacrylamide, N-(3-hydroxyl amyl group) Methacrylamide, N-(2,2-dimethyl hydroxypropyl) Methacrylamide.
In the low molecular compound by formula (VIII)-(X) representative, being particularly useful for compound of the present invention is that those have a hydrogen atom respectively as R 24, R 26, have a singly-bound, a methylene or a C who replaces or do not replace 7-12Arylmethylene alkyl is as R 25, have phenylene that a singly-bound, replacement or not or naphthylene as R 27, have a C 1-6Alkylidene is as R 28, have a integer among the 1-10 as the compound of n.
Suitable example by the compound of formula (VIII)-(IX) representative comprises methylol styrene, a methylol--methyl styrene, vinyl alcohol, hydroxyethyl vinethene, diglycol vinethene, hydroxyethyl allyl ether.
In multipolymer of the present invention, the proper proportion that contains the compound unit (monomer (B) unit) of at least one alcoholic hydroxyl and at least one polymerizable unsaturated bond is 1%-50% (molar percentage) and is preferably 5%-30%.
When the ratio of monomer (B) unit during less than 1% (molar percentage), formed multipolymer will lose efficacy to developing and scumming is responsible for, and when it greater than 50% the time, formed multipolymer causes development unsteady.
Although macromolecular compound of the present invention can be by at least one contain at least one phenolic hydroxyl or sulfoamido and at least one polymerizable unsaturated bond compound monomer (A) and contain the multipolymer that the compound monomer (B) of at least one alcoholic hydroxyl and at least one unsaturated link constitutes by at least one, macromolecular compound preferably has at least one polymerizable unsaturated bond by at least one but does not contain the multipolymer (being abbreviated as " monomer (C) ") that compound unit (A), (B), (C) of phenolic hydroxyl, sulfoamido or alcoholic hydroxyl constitute.
Monomer (C) is polymerisable unsaturated compound, and it for example is selected from acrylic acid, methacrylic acid, acrylate, acrylamide, methacrylate, Methacrylamide, allyl compound, vinyl ether, vinyl esters, styrene or butenoate.
The example that can be used as the acrylate of monomer (C) comprises: alkyl acrylate (its moieties preferably contains 1-10 carbon atom) is as methacrylate, the ethyl propylene acid esters, the propyl group acrylate, the butylacrylic acid ester, the amyl group acrylate, ethylhexyl acrylate, the octyl group acrylate, t-octyl group acrylate, the chloroethyl acrylate, pentaerythrite one acrylate, epihydric alcohol acrylic ester, the benzyl acrylate, the methoxybenzyl acrylate, the furfuryl group acrylate, the tetrahydrofurfuryl acrylate; Aryl-acrylic acid esters is as phenyl acrylate.The example that can be used as the methacrylate of monomer (C) comprises alkylmethacrylate (its moieties preferably contains 1-10 carbon atom), as methyl acrylate, ethyl-methyl acrylate, propyl methyl acid esters, isopropyl methyl acrylate, amyl group methacrylate, hexyl methacrylate, cyclohexyl methyl acrylate, benzyl methacrylate, chlorophenylmethyl methacrylate, octyl group methacrylate, epihydric alcohol methylpropenoic acid ester, furfuryl group methacrylate, tetrahydrofurfuryl methacrylate; The aryl methyl acrylate is as phenyl methyl acrylate, tolyl methacrylate, naphthyl methyl acrylate.The example that can be used as the acrylamide of monomer (C) comprises that (its moieties is the alkyl with 1-10 carbon atom for acrylamide, N-alkyl acrylamide, as methyl, ethyl, propyl group, butyl, the tert-butyl group, heptyl, octyl group, cyclohexyl, hydroxyethyl, benzyl), N-aryl acrylamide (aryl moiety for example is phenyl, tolyl, nitre phenyl, naphthyl, hydroxy phenyl), N, (moieties for example is C to N-dialkyl group acrylamide 1-10Alkyl is as methyl, ethyl, butyl, isobutyl, ethylhexyl, cyclohexyl), N, (aryl moiety for example is C to N-diaryl acrylamide 1-10Aryl, ethyl, propyl group, butyl), N, N-diaryl Methacrylamide (aryl moiety for example is a phenyl), N-methyl-N-phenyl methyl acrylamide and N-ethyl-N-phenyl methyl acrylamide.The example that can be used as the allyl compound of monomer (C) comprises allyl ester (as allyl acetic acid ester, allyl capronate, allyl decylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetic ester, allyl lactate) and alkoxyethanol.The example that can be used as the vinyl ether of monomer (C) comprises that alkyl vinyl ether is (as the hexyl vinyl ether, the octyl group vinyl ether, decave, the ethylhexyl vinyl ether, the methoxyethyl vinyl ether, the ethoxyethyl vinyl ether, the chloroethyl vinyl ether, 1 methoxy-2,2-dimethylpropyl vinyl ether, 2-ethyl-butyl vinyl ether, diformazan aminoethyl vinyl ether, the diethyl amino ethyl group vinyl ether, fourth aminoethyl vinyl ether, the benzyl vinyl ether, the tetrahydrofurfuryl vinyl ether), the vinyl allyl ether is (as vinyl phenyl ether, vinyltoluene base ether, the vinyl chloride phenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, the adjacent first lactam ethers of vinyl benzene).The example that can be used as the vinyl esters of monomer (C) comprises vinyl butyrate, the vinyl isobutyrate, vinyl pivalic ester, vinyl diethyl acetate ester, the vinyl valerate, the vinyl capronate, vinyl chloroacetate ester, vinyl dichloroacetic acid ester, vinyl methoxyimino acetic acid ester, vinyl fourth fluoroacetic acid ester, the ethenylphenylacetic acid ester, the vinyl acetoacetic ester, the vinyl lactate, vinyl beta-phenyl butyric ester, vinyl cyclohexane carboxylic ester, the vinyl benzoate, the vinyl salicylate, the vinyl chloride benzoate, vinyl tetrachloro benzoate, the vinyl naphthalene formic ether.The cinnamic example that can be used as monomer (C) is a styrene, ring-alkylated styrenes is (as methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, diethylbenzene ethene, cumene ethene, this styrene of butyl, hexyl benzene ethene, cyclohexyl benzene ethene, decyl styrene, styryl phenyl, 1-chloro-4-methyl-benzene, trifluoromethyl styrene, ethoxymethyl styrene and acetate methyl styrene), alkoxystyrene is (as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene) and halogenated styrenes (as chlorostyrene, dichlorobenzene ethene, trichlorobenzene ethene, phenyl tetrachloride ethene, phenyl-pentachloride ethene, bromostyrene, dibromo-benzene ethene, iodobenzene ethene, fluorostyrene, trifluoro-benzene ethene, 2-bromo-4-trifluoromethyl styrene, 4-fluoro-3-trifluoromethyl styrene).The example that can be used as the butenoate of monomer (C) comprises that other examples of compounds that can be used as monomer (C) of alkyl butenoate (as butyl butenoate, hexyl butenoate, glycerine one butenoate) comprises dialkyl group itaconate (as dimethyl itaconate, diethyl itaconate, dibutyl itaconate), dialkyl group maleate (as the dimethyl maleic acid ester), dialkyl group fumarate (as the dibutyl fumarate), vinyl cyanide and methacrylonitrile.
In the above-mentioned compound that contains polymerizable unsaturated bond, preferable methyl acryloyl ester, acryloyl ester, Methacrylamide, acrylamide, vinyl cyanide, methacrylonitrile, methacrylic acid, acrylic acid.Especially, advantageously adopt vinyl cyanide and methacrylonitrile.
Containing the multipolymer of the present invention that the compound of an above-mentioned polymerizable unsaturated bond, compound (A) that at least one contains at least one phenolic hydroxyl or sulfoamido and compound (B) that at least one contains at least one alcoholic hydroxyl constitute by at least one can be segmented copolymer, random copolymers or graft copolymer.
The suitable example of the solvent of using when synthesizing such macromolecular compound by vinyl polymerization comprises vinyl dichloro compound, cyclohexanone, MEK, acetone, methyl alcohol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-Ethyl Methyl Ether acetate, 1-methoxyl-2-propyl alcohol, 1-methoxyl-2-propyl acetic acid esters, N, N-dicarbaldehyde, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), toluene, ethane acetic acid esters, methyllactic acid ester, ethane lactate.
These solvents can use separately or according to being used by the mode of two kinds of potpourris of forming at least wherein.
The weight-average molecular weight of the suitable molecular weight of macromolecular compound of the present invention is at least 2000, and number-average molecular weight is at least 1000, and weight-average molecular weight is preferably 5000-300000, and number-average molecular weight is preferably 2000-25000.The preference degree of polydispersity (ratio of weight-average molecular weight/number-average molecular weight) equals 1 and be preferably 1.1-10 at least.
In addition, the used macromolecular compound of the present invention can comprise the monomer that does not still have polymerization.In this case, the permission content of such monomer is for being no more than 15% (percentage by weight).
Can use macromolecular compound of the present invention separately, perhaps can use in the mode of the potpourri that constitutes by two kinds of macromolecular compounds at least.
The suitable content of the macromolecular compound in these photosensitive layers at light light lithographic printing-plate (photosensitive composition) is about 5%-95% and preferably is about 10%-85%.
An example of the adjacent naphthoquinone two azide compound that the present invention is suitable for is described 1 as JP-A-43-28403, the ester of 2-diazo naphthoquinones sulfonic acid chloride and pyrogaelol-acetone resin.
The example of another adjacent naphthoquinone two azide compound that the present invention is suitable for is US3, and 046,120 is described 1, the ester of 2-diazo naphthoquinones sulfonic acid chloride and phenyl formaldehyde resin.Other useful adjacent naphthoquinone two azide compound discloses in many publication applications.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, JP-A-37-18015, JP-A-41-11222, JP-A-45-9610, JP-B-49-17481, US2,797,213, US3,454,400, US3,544,323, US3,573,917, US3,674,495, US3,785,825, GB1,227,602, GB1,251,345, GB1,267,005, GB1,329,888, GB1,330,932, the described adjacent naphthoquinone two azide compound of DE854890 is just useful to the present invention.
The adjacent naphthoquinone two azide compound that particularly advantageously uses is by making molecular weight be 1000 polyol and 1 to the maximum in the present invention, and 2-diazo naphthoquinones sulfonic acid chloride reacts and obtains.The example of anti-product like this comprises JP-A-51-139402, JP-A-58-150948, JP-A-58-203434, JP-A-59-165053, JP-A-60-121445, JP-A-60-124235, JP-A-60-163043, JP-A-61-118744, JP-A-62-10645, JP-A-62-10646, JP-A-62-153950, JP-A-62-178562, JP-A-62-233292, US3,102,809, US3,126,281, US3,130,047, US3,148,983, US3,184,310, US3,188,210, US4,639,406 described compounds.
When preparing adjacent naphthoquinone two azide compound as described above, use be the 0.2-1.2 of the hydroxyl in the poly hydroxyl compound and preferably 0.3-1.0 equivalent 1,2-diazo naphthoquinones sulfonic acid chloride and reacting with polyol.
The product that is obtained by above-mentioned reaction is the potpourri of adjacent naphthoquinone two azide compound, it added 1, the position of 2-diazo-naphthalene-based diazide sulfonic acid ester base is different with the number aspect.In this potpourri, convert 1 to by hydroxyl, 2-diazo-naphthalene-based diazide sulfonic acid ester base (being the compound of complete esterification) and the proper proportion of the compound that forms is at least 5% (molar percentage) and is preferably 20%-99% with all polyols.
The proper proportion of the adjacent naphthoquinone two azide compound in the photosensitive layer of photosensitive lithographic printing plate of the present invention is 5%-50% (percentage by weight) and is preferably 15%-40%.
Except containing macromolecular compound of the present invention, the photosensitive layer of photosensitive lithographic printing plate of the present invention can contain well-known alkali solubility macromolecular compound such as phenol-formaldehyde resin, cresols-formaldehyde numerical value (is metacresol-formaldehyde resin, paracresol-formaldehyde numerical value ,/paracresol compound-formaldehyde resin, phenol/formaldehyde (metacresol, paracresol or/the paracresol potpourri) potpourri-formaldehyde resin, phenol improvement xylene resin, poly-(hydroxy styrenes) and gather (halogenation hydroxy styrenes)).
In above-mentioned alkali solubility macromolecular compound, preferred compound is that those weight-average molecular weight are that 500-20000, number-average molecular weight are the compound of 200-60000.
Ratio with 70% (percentage by weight) that account for the total composition of photosensitive layer is at most used such alkali solubility macromolecular compound.
As US4,123,279 is described such, uses to have C 3-8Phenyl, formaldehyde such as the tert-butyl benzene resinox that alkyl replaces and the concentrated product of octyl phenol formaldehyde resin and those alkali solubility macromolecular compounds are very effective to improving image appearance China ink.
Add cyclic acid anhydride, phenol preferably for the used photosensitive composition of photosensitive lithographic printing plate of the present invention or/and organic acid so that improve its photosensitive property.
As US4,115,128 is described, and the example that is used for the cyclic acid anhydride of such purpose comprises anhydride phthalic acid, tetrahydrophthalic anhydride, hexahydro phthalic anhydride, 3, oxo-Δ in the 6- 4-tetrahydrophthalic anhydride, tetrachloro phthalic anhydride, maleic anhydride, chloromaleic acid acid anhydride, α-benzene are for maleic anhydride, succinic anhydride and pyromellitic acid dianhydride.
The phenol that is applicable to above-mentioned purpose comprises bisphenol-A, to pyridine phenol, to thanatol, 2,3,4-trihydroxy benzene ketone, 4-Viosorb 110,2,4,4 '-trihydroxy benzene ketone, 4,4,4 " trihydroxy-trimethylbenzene and 4; 4 '; 3 ", 4 " and tetrahydroxy-3,5; 3 ', 5 '-tetramethyl triphenyl-methane..
As for the organic acid that is applicable to above-mentioned purpose, JP-A-60-88942, JP-A-2-96755 have described sulfonic acid, sulfinic acid, alkyl sulfonic ester, phosphonic acids, phosphonous acid, phosphonate ester, carboxylic acid.The example of such acid comprises p-toluenesulfonic acid, dodecylbenzene sulfonic acid, to toluenesulfinic acid, ethyl-sulfate, phenyl-phosphonic acid, phenyl sulfinic acid, Phenylphosphine acid esters, biphenyl phosphonate ester, benzoic acid, different phthalic acid, fatty acid, to toluic acid, 3,4-dimethoxy-benzoic acid, phthalic acid, three phthalic acids, 1,4-cyclohexene-2,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid and ascorbic acid.
Cyclic acid anhydride in photosensitive composition, phenol or/and the organic acid proper proportion be 0.05%-15% and be preferably 0.1%-15% (percentage by weight).
Add as the described non-ionic surfactant of JP-A-62-251740, JP-A-4-68355 for the photosensitive layer of photosensitive lithographic printing plate of the present invention or/and the described amphoteric surfactant of JP-A-59-121044, JP-A-4-13149, so that expansion development permissibility.The example of such non-ionic surfactant comprises that sorb gathers the chaff tristearate, sorb gathers the chaff palmitin, sorb gathers the chaff trioleate, the stearic acid monoglyceride, polyoxyethylene-sorb gathers the chaff monooleate, polyoxyethylene nonylplenyl ether, the example of such amphoteric surfactant comprises alkyl two (amino-ethyl) glycocoll, alkyl gathers aminoethyl glycine ester acidulants, N-tetradecyl-N, N-betaine type surfactant " Amorgen K " (trade name, Sanyo chemical industry company limited produces), 2-alkyl-N-carboxyethyl-N-hydroxyethyl imidazole quinoline betaine and alkyl imidazoline type surfactant " Revon15 " (trade name is produced by Sanyo chemical industry company limited).These non-ionic surfactants or/and the proper proportion of amphoteric surfactant in photosensitive composition be 0.05%-15% (percentage by weight) and be preferably 0.1%-5%.
Can be used as and print off or image is gone up toner ground and added dyestuff or filler so that horse back obtains the visual image effect after exposure for the photosensitive layer of photosensitive lithographic printing plate of the present invention.The present invention can with the dyestuff example comprise that the described basic-dyeable fibre of JP-A-5-313359 promptly has basic-dyeable fibre backbone's cationic salts and has sulfonic group separately and have at least 10 carbon atoms and the organic anion of 1-3 hydroxyl as separately exchange base respectively.
Can add such basic-dyeable fibre according to the ratio of the 0.2%-5% that accounts for the total composition of photoactive substance (percentage by weight).In addition, generation can interact with the described dyestuff of JP-A-5-313359 and the compound that change the photolytic product of its tone can be added in the photosensitive composition of the present invention.The example of such compound comprises as JP-A-50-36209 (corresponding to US3,969,118) described adjacent naphthoquinone two azide-4-sulfamic acid halide, as JP-A-53-36223 (corresponding to US4,160,671) described trihalomethyl-2-pyrone and trihalomethyl triazine, as JP-A-55-62444 (corresponding to US2,038,801) described all kinds of adjacent naphthoquinone two azide compound and as JP-A-55-77742 (corresponding to US4,279,982) described 2-trihalomethyl-5-aryl-1,3, the 5-oxadiazoles.These compounds can use separately or as being used by at least two kinds of potpourris of forming wherein.
Dyestuff except that the described dyestuff of JP-A-5-31359 also can be used as image and go up toner.Be suitable for the dyestuff of doing image colouring agent and not only comprise the salify organic dyestuff, and comprise oil-soluble dyes and basic-dyeable fibre.
For example, Green BG oil, Blue BOS oil, Blue#603 oil (these are products of Orient KagakuKogyo K.K.), the pure blue BOH of Victoria (Hodogaya Chemical Co., the product of Ltd), rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI52015) can suitably be used as coloring agent.
In preparation during photosensitive lithographic printing plate of the present invention, have the aluminium flake that holds water-based such as silicate through handling and handle aluminium flake, anodic alumina film, roughening aluminium flake or silicate and electroplate long-pending aluminium flake and can be used as its sheet base.In addition, zinc metal sheet, stainless steel substrates, dyeing steel disc, have the plastic sheet and the scraps of paper that hold water-based through handling and also can be used as the sheet base.
In these sheet bases, preferred aluminium flake.Be meant at this used term " aluminium flake " and comprise fine aluminium sheet and aluminum alloy sheet.The example of available aluminium alloy comprises the alloy of aluminium and various metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel.Except some iron and titanium, these alloying components have also comprised negligible small amount of impurities.
If desired, aluminium flake is accepted surface treatment.The surface-treated example that is suitable for comprises surperficial roughening processing, the immersion treatment in sodium silicate, fluorine potassium zincate or aqueous phosphatic, anodized.In addition, can advantageously use as US2,714,066 have describedly accepted the aluminium flake of the immersion treatment in sodium silicate aqueous solution and as US3 after roughening is handled, 181,461 is described at the aluminium flake of having accepted the immersion treatment in the alkaline metal silicate aqueous solution after the anodized.Above-mentioned anodized can be carried out as the electrolytic solution that anode is placed into wherein through aluminium flake by making electric current.As available electrolytic solution example, can be with reference to the aqueous solution of the salt of inorganic aqueous acid or non-aqueous solution such as phosphoric acid, chromic acid, sulfuric acid, boric acid or organic acid aqueous solution or non-aqueous solution such as the acid of jealous woman slurry, amine sulfonylamino acid or above-mentioned acid or the mixed liquor of non-aqueous solution and above-mentioned at least two kinds of solution.
In addition, as US3,658,662 described silicate electrodepositions also are effective.
Carry out above-mentioned surface treatment and be not only in order to make the sheet primary surface have the appearance water-based, and be to produce adverse reaction between thereon the photosensitive composition and improve adhesiveness between sheet base and the photosensitive layer in order to prevent at the sheet base and to cover.
If desired, pre-service can be accepted so that remove ROLLING OIL and expose clean aluminium flake surface in the aluminium flake surface before roughening.In order to remove ROLLING OIL, used solvent such as triclene and surfactant, and, used alkaline etching such as NaOH and potassium hydroxide usually in order to expose clean aluminium flake surface.
The surface roughening is handled and can be undertaken by any machinery, chemistry, electrochemical means.As mechanical system, exist the brushing method of the water sample dispersion slurries of well-known ball grinding method, shot-peening abrasion method, usefulness nylon bruss obliterating abrasive substance.As chemical mode, can advantageously adopt the described method of JP-A54-31187, wherein aluminium flake is soaked in the saturated aqueous solution of mineral acid aluminium salt.As the electrochemical roughening mode, be suitable for by the shaggy method that makes of giving the sour electrolytic solution indirect current that contains sour example hydrochloric acid, nitric acid or its potpourri.In these roughening methods, preferably unite use as described mechanical roughening method of JP-A-55-137993 and electrochemical roughening method, because can and holding at the sheet base, this produces very strong adhesiveness between black image.
Utilize any said method to carry out roughening effectively and handle, thereby the aluminium flake surface has 0.3 micron-1.0 microns center line average roughness (Ra).
If necessary, the aluminium flake through roughening like this also carries out chemical etching subsequently through cleaning.
Etching solution be selected from usually can dissolved aluminum aqueous slkali or acid solution.But, require formation other film except that the aluminium film on etched surfaces of etching solution.The example that satisfies the etchant of such requirement comprises alkaline matter such as NaOH, potassium hydroxide, tertiary sodium phosphate, disodium hydrogen phosphate, tripotassium phosphate, dikalium phosphate and acidic materials such as sulfuric acid, persulfuric acid, phosphoric acid, hydrochloric acid and salt thereof.On the other hand, the salt that its ionization tendency is weaker than the metal of aluminium such as zinc, chromium, cobalt, nickel, copper is unfavorable, because they have formed unnecessary film on etched surfaces.
In etch processes, it would be desirable the temperature that will so determine etchant concentration and used etching solution, promptly the dissolution velocity of used aluminum or aluminum alloy is 0.3g/m in the per minute soak time 2-40g/m 2But dissolution velocity can be higher or lower than above-mentioned scope.
Be covered with above-mentioned etching solution and carry out etch processes by aluminium flake being immersed in the above-mentioned etching solution or being coated with to aluminium flake, etched suitable aluminium amount is 0.5g/m by this processing 2-10g/m 2
Although above alkali is preferably as etchant, this is that they cause the generation of stain because its aqueous solution has high rate of etch.Therefore, accepting decontamination usually with the etched aluminium flake of the aqueous solution of alkali handles.Nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid, hydrofluorite or boron fluoric acid can be carried out decontamination handles.
If desired, the etching aluminium flake is accepted to clean and anodized.Anodized can realize by any traditional approach.Exactly, the aluminium flake surface can be by coming oxidation to logical direct current of aluminium flake or alternating current in sulfuric acid, phosphoric acid, hydrochloric acid, the acid of jealous woman slurry, sulfuric acid or wherein two or more potpourri.
The anodized condition is according to the difference of used electrolytic solution and difference, thereby can not sum up such treatment conditions.But below be the condition of particularly suitable: electrolysis concentration equals 1%-80% (percentage by weight), and solution temperature is 5 ℃-70 ℃, and current density is 0.5A/dm 2-60A/dm 2, voltage is 1 volt-100 volts, electrolysis time is 0.5 minute-50 minutes.
Especially, as GB1,412,768 is described, utilizes in sulfuric acid to feed the mode of high current density electric current and advantageously carry out anodic oxidation to aluminium flake, and perhaps as US3,511,661 is described, is that electrolytic cell carries out anodic oxidation with phosphoric acid.
If necessary, be roughened in the manner described above and the aluminium flake crossed of anodizing accepts to make sheet surface to have the processing of holding water-based.A kind of suitable mode as this processing, can adopt US2,714,006, US3,181,461 described modes promptly use alkali silicate (as the water sodium silicate aqueous solution) to handle, perhaps promptly handle with potassium fluorozirconate with the described method of JP-A-36-22063, perhaps US4,153,461 described modes are promptly handled with polyvinyl sulfuric acid.
Reaching if desired also through coarse, anodizing, the aluminium flake of process tax water capacity processing can be coated on the moisture glue-line that dissolves compound.The water soluble compounds that can be used for glue-line is those disclosed compounds in JP-B-57-16349.Other compound that is applicable to glue-line comprises that the compound of water-soluble slaine and water-absorption fiber element is (as the compound of zinc chloride and carboxymethyl cellulose, the perhaps compound of manganese chloride and carboxyethyl cellulose), US3,511,661 described polyacrylic acid amide, the described polyvinyl phosphonic acids of JP-A-46-35685, the described amino acid of JP-A-60-149491 and salt thereof (as alkali metal salt such as sodium salt, sylvite, ammonium salt, hydrochloride, oxalates, acetate and phosphoro-amidate), the described hydroxyl amine of JP-A-60-232998 and salt thereof.In these compounds, the especially amine of preferred amino acid and salt thereof and hydroxyl and salt thereof.When forming glue-line, suitably with the 1mg/m on the solid basis 2-80mg/m 2Coated weight apply above-mentioned water soluble compounds.
The compound dissolution of above-mentioned ingredient as photosensitive composition of the present invention is in appropriate solvent and be applied to subsequently on the above-mentioned base so that prepare photosensitive lithographic printing plate.Example at this solvent for use comprises gamma-butyrolacton, ethylene dichloride, cyclohexane ketone, MEK, the ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyacetic acid ethyl ester, 1-methoxyl-2-propyl alcohol, 1-methoxyl-2-propyl acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide (DMSO), dimethyl acetamide, dimethyl formamide, water, N-Methyl pyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methyl alcohol, ethanol, isopropyl alcohol and diethylene glycol dimethyl ether.These solvents can use or use wherein at least two kinds potpourri separately.The debita spissitudo of the composition in coating solution (solid) is 5%-50% (percentage by weight).The suitable coated weight of photosensitive composition of the present invention is the 0.5g/m on the solid basis 2-3.0mg/m 2Although reducing, the photosensitive composition coated weight cause photosensitivity to strengthen the deterioration in physical properties of formed photosensitive film.
Add surfactant such as the described fluorochemical surfactant of JP-A-62-170950 that improves paintability can for the photosensitive layer of photosensitive lithographic printing plate of the present invention.It is effectively adding such surfactant with 0.01%-1% (percentage by weight) and the quantity that is preferably 0.05%-0.5%.The photosensitive layer surface that forms with said method preferably by delustering so that when utilizing the contact exposure of vacuum radiance, shorten the pumpdown time and prevent that print image is fuzzy.As a this example that makes the unglazed method in photosensitive layer surface, can be referring to respectively by JP-A50-125805, JP-B-57-6582, the unglazed layer method of the described generation of JP-B-61-28986 and as the described method of giving the surperficial melting welding solid particle of photosensitive layer of JP-B-62-62337.
The developer that is applicable to photosensitive lithographic printing plate of the present invention is the alkaline aqueous solution that is substantially free of organic solvent, for example the aqueous solution and the ammoniacal liquor of sodium silicate, potassium silicate, NaOH, potassium hydroxide, lithium hydroxide, tertiary sodium phosphate, disodium hydrogen phosphate, triammonium phosphate, Diammonium phosphate (DAP), sodium silicate (sodium metasilicate), sodium carbonate, sodium bicarbonate, sal tartari, saleratus.The debita spissitudo of these solution is 0.1%-10% (percentage by weight) and is preferably 0.5%-5%.In these developers, preferably contain the developer of alkaline silicate such as potassium silicate, lithium metasilicate, sodium silicate, because making through its processing forme, it is not easy to occur scumming.As for the composition of the contained alkaline silicate of developer, [SiO 2]/[M] ratio equal 0.5-2.5 (mol ratio, wherein [SiO 2] expression SiO 2Volumetric molar concentration, the volumetric molar concentration of the total alkaline metal of [M] expression), advantageously adopt its SiO 2Concentration is the developer of 0.8%-8% (percentage by weight).Add water-soluble sulfite such as sodium sulphite, potassium sulfite, manganous sulfite, resorcinol, methylresorcinol, p-dihydroxy-benzene and thiosalicylic acid can for such developer.The proper proportion of these adjuvants in developer is 0.002%-4% (percentage by weight) and is preferably 0.01%-1%.
Owing in developer, also contain just like the described positive surfactant of JP-A-50-51324, JP-A-59-94241 and amphoteric surfactant, at least a, can improve the wetting state and the stable developing (development permissibility) of the photosensitive composition of developer as JP-A-59-75255, JP-A-60-11246, the described non-ionic surfactant of JP-A-60-213943 or as the described polyeletrolyte of JP-A-55-95946, JP-A-56-142528.The proper content of these surfactants in developer is 0.001%-2% and is preferably 0.003%-0.5% (percentage by weight).In addition, potassium should be 20% (molar percentage) at least with the ratio of the total alkaline metal of the contained alkaline silicate of developer, and is at least 90% for better, and the best is 100%, and this is because can reduce the generation of the insoluble matter in developer.
Add a small amount of organic solvent such as alcohol, the described sequestrant of JP-A-58-190952, the described slaine of JP-B-1-30139 and antifoaming agent such as organic silane compound can also for the used developer of the present invention.
As exposure light source, can use carbon arc lamp, mercury vapor lamp, xenon lamp, tungsten lamp, metal halide lamp.
Much less, above-mentioned photosensitive lithographic printing plate can be accepted plate-making and handle according to JP-A-54-8002, JP-A-55-115045, described any method of JP-A-59-58431.Exactly, the photosensitive lithographic printing plate after the development can or need not to clean ground after cleaning and accept to deluster quick processing, perhaps can accept to deluster quick processing after containing the aqueous acid processing.Because alkaline aqueous solution is consumed pro rata with whole developer in development step and thereby reduced its alkali content, perhaps alkali content reduces in the long-term continuous working process of automatic visualizer because of being exposed in the air, so developer has run into the problem that development capability reduces.In this case, can regain development capability as the described supplementary material of JP-A-54-62004 by using.In this case, advantageously according to US4,882,246 described methods are replenished.Perhaps, advantageously utilization realizes the plate-making processing as the described automatic visualizer of JP-A-2-7054, JP-A-2-32357.
Under the situation of after to remove the work do not need area of image be to make photosensitive lithographic printing plate of the present invention accept visual exposure, development and cleaning or rinsing according to priority, carrying out, advantageously adopt the described removing liquid of JP-B-2-13293 for this reason.Be coated under the situation of light-sensitive emulsion in last plate-making process at photosensitive lithographic printing plate of the present invention, preferably adopt JP-B-62-16834, JP-B-62-25118, JP-B-63-52600, JP-A-62-7595, the described light-sensitive emulsion that goes of JP-A-62-83194, JP-A-62-11693.
Photosensitive lithographic printing plate of the present invention its successively accept visual exposure, development and cleaning or rinsing and image remove and clean (if necessary) after carry out under other situation that calcination handles, advantageously before calcination is handled and under JP-B-61-2518, JP-B-55-28062, the described condition of JP-A-62-31859, JP-A-61-159655, handle.
Now, more specifically describe the present invention, but these examples should not be considered to limitation or qualification to the scope of the invention referring to following synthesis example and example.
Example 1
Synthesis example I-1:
Be furnished with stirrer, concentrating in 1 liter of three-neck flask of utensil, the p methoxy phenol, 0.2 of putting into 62.1 gram (0.5 mole) 4-hydroxy benzenes methylols, 77.6 gram (0.5 mole) methacryl oxo ethane isocyanate, 0.04 gram (0.3 mole) restrains two normal-butyls two lauric acid, 700 milliliters of acetone of (0.3 mole) and stirs into solution.In addition, simultaneously under 50 ℃ with stirring 8 hours in the oil groove heating.When reaction finished, reaction mixture was poured in three premium on currency with being stirred and was stirred subsequent filtration again 30 minutes.Obtained 55.9 thus and digested compound M1.
4.19 gram (0.015 mole) so obtains compound M1,1.30 gram (0.01 mole) 2-hydroxyethyl methacrylates, 1.50 gram (0.015 mole) methyl acrylates, 3.18 gram (0.06 mole) vinyl cyanide and 20 gram N, N-dimethyl ethyl group acetamide is placed in 200 milliliters of three-neck flasks of a band stirring parts, tap funnel and by heating with hot water tank under 65 ℃.Adding initiating agent V-65 (trade name, Wako Pure chemical Industries company produces) was also stirring 2 hours in nitrogen stream under the situation of 65 ℃ of insulations.Utilize tap funnel and dropwise add 4.19 to formed reaction mixture and digest the potpourri that compound M1,1.30 gram 2-hydroxyethyl meth acrylates, 1.50 gram methyl acrylate, 3.18 gram vinyl cyanide and 20 gram N,N-dimethylacetamide, 0.25 restrain V-65 through two hours ground.After dropping liquid finished, potpourri was stirred 2 hours again under 65 ℃.After reaction finished, adding 40 gram methyl alcohol and cooling were also poured in 2 premium on currency with stirring.After having stirred 30 minutes again, filter and dry reaction mixture, thereby obtained 18 gram white solids.By the saturating chromatograph technology of glue, confirm that obtaining macromolecular compound (being called as macromolecular compound of the present invention (a), shown in Table I-1) thus has 52000 weight-average molecular weight (according to polystyrene standard).
Synthesis example I-2
The listed macromolecular compound (b)-(h) of Table I-1 is synthetic according to the mode identical with synthesis example I-1.
Table I-1
Figure A0013330600261
Example by following preferred embodiment further specifies the present invention.In addition, " % " in following example and Comparative Examples is percentage by weight, except as otherwise noted.
Example I-1 to I-9 and Comparative Examples I-1 are to I-3
With nylon bruss and 400 purpose float stone water slurries the aluminium flake rough surface and the water of 0.30 millimeters thick are thoroughly cleaned.Sheet material obtained etching in 60 seconds by soaking in 10% sodium hydrate aqueous solution of 70 ℃ of insulations, clean with tap water subsequently, then neutralized with 20% nitric acid rinsing, and cleaned at water.Then, so the sheet material that forms of etching is accepted electrolytic treatments so that coarse surface, and wherein 1% aqueous solution of nitric acid is used as electrolytic solution, and at V AFeed the alternating current of sinusoidal form under=12.7 volts the condition, thereby the anode current amount is 160 Columbus/dm 2Surface finish measurement is the result show, has the surfaceness of 0.6 micron (Ra) through the sheet material of so handling.Subsequently, aluminium flake carries out the disproportionation processing by being immersed in 55 ℃ of 30% aqueous sulfuric acids down of insulation 2 minutes, subsequently in 20% aqueous sulfuric acid and at 2A/dm 2The current density condition under carry out anodic oxidation, reach 2.7g/m up to anode coating thickness 2Made the sheet base thus.
On the surface of treated base in the manner described above, be coated with and be covered with the fixing glue composition of layer (A) that constitutes by following composition, and under 80 ℃, carry out 30 second drying.Dried coated weight is 30mg/m 2
Fixing glue composition of layer (A):
Ciliatine 0.10 gram
Phenyl-phosphonic acid 0.15 gram
Triethanolamine 0.05 gram
β-alanine 0.10 gram
Methyl alcohol 40 grams
Pure water 60 grams
The sheet base of making thus is by (I) in blocks.
On sheet base (I), by application bar with 25ml/m 2Coated weight coated with the composition that is classified as photosensitive composition (B) down and then 100 ℃ dry 1 minute down, thereby photosensitive lithographic printing plate [B]-1 of having made its sun version effect is to [B]-8.In addition, prepare, apply and be classified as the composition of photosensitive composition (C) below the drying, thereby the photosensitive lithographic printing plate [C]-1 that has obtained its sun version effect respectively is to [C]-4 according to the mode identical with above-mentioned photosensitive composition (B).The dried coated weight of each composition is 1.7g/m 2
In addition, the of the present invention macromolecular compound used and the macromolecular compound of contrast in Table I-1, have been listed in photosensitive lithographic printing plate [B]-1 to [B] 8-and [C]-1 to [C]-4.Photosensitive composition (B): 2,3,4-trihydroxybenzophenone and naphthoquinones-1, the esterification products of 2-diazide-5 sulfonic acid chloride (degree of esterification 90% mol ratio) 0.45 gram cresols-formaldehyde novolac type resin (/ contrast: 6/4, weight-average molecular weight: 3000, number-average molecular weight: 1100, unreacted cresols content: 0.2 gram metacresol-formaldehyde novolac type resin (weight-average molecular weight: 1,700 0.7%), number-average molecular weight: 600, the cresols content of end reaction: the concentrated product (weight-average molecular weight: 2200 of 0.3 gram pyrogaelol and acetone 1%), number-average molecular weight: 700,) 0.1 gram macromolecular compound of the present invention (or contrast macromolecular compound), 1.1 grams align octyl phenol-formaldehyde resin (US4,123,379 is described) 0.02 gram naphthoquinone two azide-1,2-diazide-4-sulfonic acid chloride 0.01 gram tetrahydro anhydride phthalic acid 0.02 gram benzoic acid 0.02 gram 4-[is right-N-(para hydroxybenzene formyl) aminophenyl] and-2, two (the trichloromethyl)-s-triazine 0.02 gram N-(1 of 6-, 2-naphthoquinones-2-nitrine-4-sulfonyloxy)-cyclohexane-1,2-dicarboxylic acid imides 0.01 gram turmeric, by negative ion being converted the pure blue BOH of Victoria (product of Hodogaya Chemical Co.Ltd.) to dyestuff 0.005 gram 1-[Alpha-Methyl-α-(4-hydroxyl-3 that 1-naphthalene sulfonic aicd obtains, 5-dihydroxymethyl-phenyl) ethyl]-4[-α, α-two (4-hydroxyl-3,5-dihydroxymethyl phenyl) ethyl] benzene (the described compound of JP-A-6-282067 (X)) 0.04 gram Megafac F-176 (fluorine-containing surfactant, produce by big Japanese ink chemical reagents corporation) 0.01 gram MEK, 10 gram gamma-butyrolactons, 5 gram 1-methoxyls-2-propyl alcohol 5 gram photosensitive compositions (C): 2,3,4-trihydroxybenzophenone and naphthoquinones-1,2-
Diazide-muriatic the esterification products of 5-sulfonyl (degree of esterification 90% mol ratio) 0.45 gram
Macromolecular compound of the present invention (or macromolecular compound of contrast) 1.7 grams
Align octyl phenol-formaldehyde resin (US4,123,379 is described) 0.02 gram
Naphthoquinone two azide-1,2-diazide-4-sulfonic acid chloride 0.01 gram
Tetrahydro anhydride phthalic acid 0.02 gram
Benzoic acid 0.02 gram
4-[is right-N-(para hydroxybenzene formyl) aminophenyl] and-2, two (trichloromethyl)-s-triazines 0.02 grams of 6-
N-(1,2-naphthoquinones 2-nitrine-4-sulfonyloxy)-cyclohexane-1,2-dicarboxylic acid imides 0.01 gram
Turmeric is by with the pure blue BOH of Victoria (product of Hodogaya Chemical Co.Ltd.)
Negative ion is converted to 1-naphthalene sulfonic aicd and the dyestuff that obtains 0.005 gram
1-[Alpha-Methyl-α-(4-hydroxyl-3,5-dihydroxymethyl-phenyl) ethyl]-
4[-α, α-two (4-hydroxyl-3,5-dihydroxymethyl phenyl) ethyl] benzene
(the described compound of JP-A-6-282067 (X)) 0.04 gram
Megafac F-176 (fluorine-containing surfactant agent, by
Big Japanese ink chemical reagents corporation produces) 0.01 gram
MEK 10 grams
Gamma-butyrolacton 5 grams
1-methoxyl-2-propyl alcohol 5 grams
Making the transparent positive original copy with lines and monotone image closely contact each photosensitive lithographic printing plate [B]-1 to the photosensitive layer of [B]-8 and [C]-1 to [C]-4 and 30 amperes carbon arc lamp by 70 centimetres of placements at interval exposes.
Develop by 60 seconds (diluting 8 times) in the aqueous solution that is immersed in DP-4 (trade name, the product of Fuji Photo film company limited) under 25 ℃ in photosensitive lithographic printing plate [B]-1 after each exposure to [B]-8 and [C]-1 to [C]-4.Thus obtained each lithographic printing-plate [B]-1-[B]-8 and [C]-1-[C]-4 be installed in the Heidelberg printing machine KOR type printing machine and use thus can be at common ink of having bought on the market or UV printing ink lines and monotone image under printing on the no wooden paper.By these operations,, check each forme according to printed document (being printing material) and the scumming situation that is produced that many parts are printed thus before printing last portion.Institute obtains and the results are shown in the Table I-2.
Can from Table I-2, see, (Comparative Examples I-1, I-2, I-3) compares with each lithographic printing-plate [B]-7, [B]-8 and [C]-4, adopt each lithographic printing-plate [B]-1 to [B]-6 and [C]-1 to [C]-3 (routine I-1 to I-6, routine I-8 to I-9) of macromolecular compound of the present invention under the situation of using common ink and UV printing ink, all to print out a large amount of printed documents.In other words, forme of the present invention is more even better than forme in comparison aspect the printing life-span.In addition, forme of the present invention also is better than the contrast forme at the aspect of performance of anti-the scumming.
Table I-2
Dull and stereotyped forme Used macromolecular compound Printed document quantity with the common ink generation Quantity with the generation of UV printing ink Anti-scumming
The routine I-1 in [B]-1 ??????(a) ????65,000 ???40,000 ????○
The routine I-2 in [B]-2 ??????(b) ????65,000 ???40,000 ????○
The routine I-3 in [B]-3 ??????(c) ????60,000 ???30,000 ????○
The routine I-4 in [B]-4 ??????(d) ????65,000 ???40,000 ????○
[B]-5 example 1 I-5 ??????(e) ????60,000 ???35,000 ????○
The routine I-6 in [B]-6 ??????(f) ????58,000 ???28,000 ????○
[B]-7 Comparative Examples I-1 ??????(g) ????36,000 ???12,000 ????×
[B]-8 Comparative Examples I-2 ??????(h) ????28,000 ???8,000 ????○
The routine I-7 in [C]-1 ??????(a) ????78,000 ???62,000 ????○
The routine I-8 in [C]-2 ??????(b) ????76,000 ???58,000 ????○
[℃]-3 routine I-9 ??????(f) ????68,000 ???56,000 ????○
[C]-4 Comparative Examples I-3 ??????(h) ????36,000 ???14,000 ????×
* visually rank zero: good *: very poor
Example 2
Synthesis example II-1:
Be furnished with stirrer, concentrating in 200 milliliters of three-neck flasks of utensil and tap funnel, put into and stir 3.60 gram (0.015 mole) N-(to the aminosulfonyl phenyl) methacrylic acid acid amides, 1.30 gram (0.01mole) 2-hydroxyethyl methacrylates, 1.50 gram (0.015 mole) methyl acrylic acid amides, 3.18 gram (0.06 mole) vinyl cyanide, 20 gram N, N-dimethacrylate acid amides heats with hot water tank under 65 ℃ simultaneously.Adding initiating agent V-65 (trade name, Wako Pure chemical Industries company produces) was also stirring 2 hours in nitrogen stream under the situation of 65 ℃ of insulations.Utilize tap funnel and dropwise add the potpourri of 3.60 gram N-(to the aminosulfonyl phenyl) methacrylic acid acid amides, 1.30 gram dihydroxy ethyl methacrylates, 1.50 gram methyl acrylates, 3.18 gram vinyl cyanide, 20 gram N,N-DMAAs and 0.25 gram V-65 for formed reaction mixture through two hours ground.After dripping end, potpourri is stirred 2 hours again under 65 ℃.After reaction finished, adding 40 gram methyl alcohol and cooling were also poured in 2 premium on currency with stirring.After stirring 30 minutes again, filter and dry reaction mixture, thereby obtained 18 gram white solids.By the saturating chromatograph technology of glue, confirm that obtaining macromolecular compound (being called as macromolecular compound of the present invention (a '), shown in Table II-1) thus has 45000 weight-average molecular weight (according to polystyrene standard).
Synthesis example II-2 to II-7
According to macromolecular compound (b ')-(i ') shown in the synthetic Table II-1 of the mode identical with synthesis example II-1.
Table II-1
Figure A0013330600321
Example by following preferred embodiment further specifies the present invention.In addition, " % " in following example and Comparative Examples is percentage by weight, except as otherwise noted.
Example II-1 to II-10 and Comparative Example II-1 are to II-3
With nylon bruss and 400 purpose float stone water slurries the aluminium flake rough surface and the water of 0.30 millimeters thick are thoroughly cleaned.Sheet material cleans with tap water subsequently by carrying out etching in 60 seconds in 10% aqueous solution that is soaked in 70 ℃ of NaOH down of insulation, subsequently with 20% also water cleaning again of nitric acid rinsing neutralization.Then, so the sheet material that forms of etching is accepted electrolytic treatments so that coarse surface, and wherein 1% aqueous solution of nitric acid is used as electrolytic solution, and at V AFeed the alternating current of sinusoidal form under=12.7 volts the condition, thereby the anode current amount is 160 Columbus/dm 2Surface finish measurement is the result show, has the surfaceness of 0.6 micron (Ra) through the sheet material of so handling.。Subsequently, aluminium flake 2 minutes Di carries out the disproportionation processing by being immersed in 30% aqueous sulfuric acid under being incubated 55 ℃, subsequently in 20% aqueous sulfuric acid and at 2A/dm 2The current density condition under carry out anodic oxidation, reach 2.7g/m up to anode coating thickness 2Made the sheet base thus.
On the surface of treated base in the manner described above, be coated be covered with the fixing glue composition of layer (A) that constitutes by following composition and under 80 ℃, carry out 30 second drying.Dried coated weight is 30mg/m 2
Fixing glue composition of layer (A):
Ciliatine 0.10 gram
Phenyl-phosphonic acid 0.15 gram
Triethanolamine 0.05 gram
β-alanine 0.10 gram
Methyl alcohol 40 grams
Pure water 60 grams
The sheet base of making thus is by in flakes basic (I).
On sheet base (I), by application bar with 25ml/m 2Coated weight coated with the composition that is classified as photosensitive composition (B ') down and then 100 ℃ dry 1 minute down, thereby made play the effect of sun version photosensitive lithographic printing plate [B ']-1 to [B ']-9.In addition, prepare, apply and be classified as the composition of photosensitive composition (C ') below the drying, thereby the photosensitive lithographic printing plate [C ']-1 that has obtained effective work respectively is to [C ']-4 according to the mode identical with above-mentioned photosensitive composition [B ').The dried coated weight of each composition is 1.7g/m 2
In addition, in Table II-1, listed at photosensitive lithographic printing plate [B ']-1 of the present invention macromolecular compound used and the macromolecular compound of contrast to [B ']-9 and [C ']-1 to [C ']-4.
Photosensitive composition (B '):
2,3,4-trihydroxybenzophenone and naphthoquinones-1,2-
The esterification products of two nitrine-5-sulfonic acid chloride (degree of esterification 90% mol ratio) 0.45 gram
Cresols-formaldehyde novolac type resin (/ contrast: 6/4, weight-average molecular weight:
3000, number-average molecular weight 1100, unreacted cresols content: 0.2 gram 0.7%)
Metacresol-formaldehyde novolac type resin (weight-average molecular weight:
1700, number-average molecular weight: 600, unreacted cresols content: 0.3 gram 1%)
The concentrated product of pyrogaelol and acetone (weight-average molecular weight:
2200, number-average molecular weight: 700) 0.1 gram
Macromolecular compound of the present invention (or macromolecular compound of contrast) 1.1 grams
Align octyl phenol-formaldehyde resin (US4,123,379 is described) 0.02 gram
Naphthoquinones two nitrine-1,2-two nitrine-4-sulfonic acid chloride 0.01 gram
Tetrahydro anhydride phthalic acid 0.02 gram
Benzoic acid 0.02 gram
4-[is to N-(para hydroxybenzene formyl) aminophenyl]-2,6-(trichloromethyl)-s-triazine 0.02 gram
N-(1,2-naphthoquinones-2-nitrine-4-sulfonyloxy)-cyclohexane-1,2-dicarboxylic acid imides 0.01 gram
Turmeric is by with the pure blue BOH of Victoria (product of Hodogaya Chemical Co.Ltd.)
Negative ion is converted to 1-naphthalene sulfonic aicd and the dyestuff that obtains 0.005 gram
1-[Alpha-Methyl-α-(4-hydroxyl-3,5-dihydroxymethyl-phenyl) ethyl]-
4-[α, α-two (4-hydroxyl-3,5-dihydroxymethyl phenyl) ethyl] benzene
(the described compound of JP-A-6-282067 (X)) 0.04 gram
Megafac F-176 (fluorine-containing surfactant, by
Big Japanese ink chemical reagents corporation produces) 0.01 gram
MEK 10 grams
Gamma-butyrolacton 5 grams
1-methoxyl-2-propyl alcohol 5 grams
Photosensitive composition (C '):
2,3,4-trihydroxybenzophenone and naphthoquinones-1,2-
The esterification products of two nitrine-5-sulfonic acid chloride (degree of esterification 90% mol ratio) 0.45 gram
Macromolecular compound of the present invention (or macromolecular compound of contrast) 1.7 grams
Align octyl phenol-formaldehyde resin (US4,123,379 is described) 0.02 gram
Naphthoquinones two nitrine-1,2-two nitrine-4-sulfonic acid chloride 0.01 gram
Tetrahydro anhydride phthalic acid 0.02 gram
Benzoic acid 0.02 gram
4-[is right-N-(para hydroxybenzene formyl) aminophenyl] and-2, two (trichloromethyl)-s-triazines 0.02 grams of 6-
N-(1,2-naphthoquinones-2-nitrine 4 sulfonyloxies)-cyclohexane-1,2-dicarboxylic acid imides 0.01 gram
Turmeric is by with the pure blue BOH of Victoria (product of Hodogaya Chemical Co.Ltd.)
Negative ion is converted to 1-naphthalene sulfonic aicd and the dyestuff that obtains 0.005 gram
1-[Alpha-Methyl-α-(4-hydroxyl-3,5-dihydroxymethyl-phenyl) ethyl]-
4-[α, α-two (4-hydroxyl-3,5-dihydroxymethyl phenyl) ethyl] benzene
(the described compound of JP-A-6-282067 (X)) 0.04 gram
Megafac F-176 (fluorine-containing surfactant agent, by
Big Japanese ink chemical reagents corporation produces) 0.01 gram
MEK 10 grams
Gamma-butyrolacton 5 grams
1-methoxyl-2-propyl alcohol 5 grams
Making the transparent positive original copy with lines and monotone image closely contact each photosensitive lithographic printing plate [B ']-1 to the photosensitive layer of [B ']-9 and [C ']-1 to [C ']-4 and 30 amperes of carbon arc lamps by 70 centimetres of placements at interval exposes.
Develop by 60 seconds (diluting 8 times) in the aqueous solution that is immersed in DP-4 (trade name, Fuji Photo film company limited produces) under 25 ℃ in photosensitive lithographic printing plate [B ']-1 after each exposure to [B ']-9 and [C ']-1 to [C ']-4.Thus obtained each lithographic printing-plate [B ']-1 to [B ']-9 and [C ']-1 to [C ']-4 be installed in the Heidelberg printing machine KOR type printing machine and use thus can be at common ink of having bought on the market or UV printing ink lines and monotone image under printing on the no wooden paper.By these operations,, check each forme according to printed document (being printing material) and the scumming situation that is produced that many parts are printed thus before printing last portion.Institute obtains and the results are shown in the Table II-2.
Can from Table II-2, see, (Comparative Example II-1, II-2, II-3) compares with each lithographic printing-plate [B ']-8, [B ']-9 and [C ']-4, each lithographic printing-plate [B ']-1 that adopts macromolecular compound of the present invention is to [B ']-7 and [C ']-1 to [C ']-3 (routine II-1 to II-7, example II-8 to II-10) under the situation of using common ink and UV printing ink, all prints out a large amount of printed documents, in other words, forme of the present invention is more even better than forme in comparison aspect the printing life-span.In addition, forme of the present invention also is better than the contrast forme at the aspect of performance of anti-the scumming.
Table II-2
Dull and stereotyped forme Used macromolecular compound Printed document quantity with the common ink generation Quantity with the generation of UV printing ink Anti-scumming *
The routine II-1 in [B ']-1 ????(a′) ????68,000 ????45,000 ????○
The routine II-2 in [B ']-2 ????(b′) ????65,000 ????40,000 ????○
The routine II-3 in [B ']-3 ????(c′) ????60,000 ????30,000 ????○
The routine II-4 in [B ']-4 ????(d′) ????65,000 ????40,000 ????○
The routine II-5 in [B ']-5 ????(e′) ????60,000 ????35,000 ????○
The routine II-6 in [B ']-6 ????(f′) ????58,000 ????28,000 ????○
The routine II-7 in [B ']-7 ????(g′) ????60,000 ????32,000 ????○
[B ']-8 Comparative Example II-1 ????(h) ????35,000 ????18,000 ????×
[B ']-9 Comparative Example II-2 ????(i′) ????40,000 ????12,000 ????○
The routine II-8 in [C ']-1 ????(a′) ????83,000 ????64,000 ????○
The routine II-9 in [C ']-2 ????(c′) ????78,000 ????52,000 ????○
The routine II-10 in [C ']-3 ????(g′) ????76,000 ????56,000 ????○
[C ']-4 Comparative Example II-3 ????(i′) ????42,000 ????23,000 ????×
* visually rank zero: good *: very poor
Because photosensitive lithographic printing plate of the present invention contains the special multipolymer by monomer (A) unit and monomer (B) unit formation at its photosensitive layer, so photosensitive layer can have good sheet base adhesiveness, gratifying flexibility and the strong solubility in organic solvent.As a result, photosensitive layer of the present invention is applicable to well and is applied on the sheet base and can effectively utilizes alkaline developer solution and develop it through the exposure region behind coating, drying and imaging exposure.The relief image that takes shape in this zone has very strong anti-wear performance and sheet base adhesion property, thereby when they are used as forme, can obtain a large amount of colory folders.
In addition, photosensitive layer of the present invention has outstanding chemical-resistance, even when it does not carry out the UV ink printing with carrying out the calcination processing, it also can print out a large amount of colory folders.In other words, photosensitive lithographic printing plate of the present invention can provide a kind of and has an outstanding printing life-span and do not produce the lithographic printing-plate of scumming.

Claims (3)

1. photosensitive lithographic printing plate with a photosensitive layer, described photosensitive layer comprises a kind of adjacent naphthoquinones two triazo-compounds and a kind of water insoluble but dissolve in the polyvinyl of alkaline aqueous solution, the therein ethylene based polyalcohol is a kind of multipolymer, and it comprises that (A) contains the compound unit and the compound unit that (B) contains at least one alcoholic hydroxyl and at least one polymerisable unsaturated link of at least one phenolic hydroxyl or at least one sulfonamido and at least one polymerisable unsaturated link.
2. photosensitive lithographic printing plate as claimed in claim 1, it is characterized in that described multipolymer is included in the compound unit (A) that contains at least one phenolic hydroxyl or at least one sulfonamido and at least one polymerisable unsaturated link in the copolymer molecule with the mol ratio of 1%-40%.
3. photosensitive lithographic printing plate as claimed in claim 1 is characterized in that, described multipolymer is included in the compound unit (B) that contains at least one alcoholic hydroxyl and at least one polymerisable unsaturated link in the copolymer molecule with the mol ratio of 1%-50%.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101122745A (en) * 2006-08-11 2008-02-13 成都科瑞聚数码科技有限公司 Positive printing heat-sensitive lithographic printing planography and its preparation method
CN102298262A (en) * 2011-06-16 2011-12-28 胡海波 Thermocuring photosensitive resin composition
CN102099748B (en) * 2008-07-16 2013-07-17 爱克发印艺公司 A method and apparatus for preparing lithographic printing plate precursors

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101122745A (en) * 2006-08-11 2008-02-13 成都科瑞聚数码科技有限公司 Positive printing heat-sensitive lithographic printing planography and its preparation method
CN102099748B (en) * 2008-07-16 2013-07-17 爱克发印艺公司 A method and apparatus for preparing lithographic printing plate precursors
CN102298262A (en) * 2011-06-16 2011-12-28 胡海波 Thermocuring photosensitive resin composition

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