CN1210613C - Photosensitive lithographic printing plate - Google Patents

Abstract

The present invention relates to a photosensitive planographic printing plate developable with an aqueous alkali developing solution, excellent in wear resistance, having high printing durability, excellent also in chemical resistance, having high printing durability even when printing with UV-curing ink is carried out without burning, adaptable to a wide range of development conditions and causing no scumming in printing. The photosensitive planographic printing plate has a photosensitive layer containing a vinyl polymeric high molecular compound insoluble in water and soluble in an alkaline aqueous solution and o-naphthoquinone diazide. The vinyl polymeric high molecular compound is a copolymer containing specified two monomer components.

Description

Photosensitive lithographic plate

The present invention relates to photosensitive lithographic plate.More detailed saying relates to and has the photographic layer that is formed by the photosensitive compounds that acts on positive type and mar proof, the good macromolecular compound of drug resistance, and the video picture condition and range is wide, do not produce the photosensitive lithographic of pollution during printing.

Photosensitive composite by the phenolics of O-naphthoquinones two triazo-compounds and phenolic resin type forms as very good photosensitive composite, has been used for the manufacturing and the photoresist of lithographic plate in industry.

Yet, as the novolac type phenolic resin of main body, with regard to its character, adherence to substrate is very poor, and epithelium is very fragile, and coating is poor, mar proof is poor, printability resistance when being used for lithographic plate is also undesirable, and then, lack drug resistance, when particularly using UV to deceive juice, anti-printing capability is extremely undesirable, or the like, all these haves much room for improvement.

As the method that improves these performances, generally adopt printing down to handle (after exposure, the video picture, heat treated), yet the problem of existence is, when carrying out the printing down processing, from the photographic layer of the image section low molecular compound that distils out, on non-image part, be easy to during printing pollute.

In order to address this is that,, various macromolecular compounds are studied as bonding agent, for example, polycarboxylated styrene or the hydroxy styrenes multipolymer put down in writing in the special public clear 52-41050 communique have improved tunicle really, but still there is wearing quality, the shortcoming of drug resistance difference.The spy opens and proposes to have the macromolecular compound of acrylic acid derivative unibody construction in the clear 51-34711 communique in molecular structure, as bonding agent.But this macromolecular compound still exists suitable video picture condition and range very narrow, and the unfavorable problem of mar proof.Propose to have the macromolecular compound of sulfoamido in the Te Kaiping 2-866 communique as bonding agent.And open clear 63-89864 communique the spy, the flat 1-52139 communique of Te Kaiping 1-35436 communique and Te Kai, spy open in the flat 8-339082 communique, and the macromolecular compound that proposes to have the acrylic acid derivative of band phenolic aldehyde hydroxyl in the molecular structure is used as bonding agent.Yet it is undesirable that the problem of existence is still mar proof, is easy to generate pollution during printing.

Therefore, the purpose of this invention is to provide can video picture in alkaline video picture aqueous solution, and mar proof is good, and the big photosensitive lithographic plate of anti-printing capability.

It is good that another object of the present invention provides drug resistance, do not carry out that printing down handles, even use UV to deceive the printing of juice (UV cured black juice), the photosensitive lithographic plate that anti-printing capability is big.

It is wide that a further object of the present invention provides the video picture condition and range, do not produce the photosensitive lithographic plate of pollution during printing.

It is good that another purpose of the present invention provides the substrate adherence, pays soft epithelium, has the photosensitive lithographic plate of the good photographic layer of organic solvent dissolution.

Present inventors have carried out all research to polyvinyl copolymerization composition, found that, to have the compound of solubility alkalescence base and N-displacement () acrylic acid amide compound makes the ethylene copolymer of monomer component, add in the photosensitive compounds, this photosensitive composite is used as the photosensitive lithographic plate that photographic layer is made, can achieve the above object, and so far finish the present invention.

Promptly, photosensitive lithographic plate of the present invention, it is characterized in that have moisture insoluble and in alkaline aqueous solution soluble vinyl polymerization be in the photosensitive lithographic plate of photographic layer of macromolecular compound and O-naphthoquinone two azide, this vinyl polymerization is that macromolecular compound is to contain with following (A) and the co-polymer of monomer component (B).

(A) has the basic compound of the alkalescence of solubility shown in the following formula (I)

(in the formula, X ¹Table-O-or-NR ³-.R ¹Expression-H or-CH ₃R ²The organic group of expression singly-bound or divalent.Y ¹The expression arylene.Z ¹Expression has the base of acid hydrogen atom.N represents 0 or 1.R ²When singly-bound, and Z ¹During for-OH, n is 1.M represents the integer more than 1.R ³Expression can have alkyl, naphthenic base, the aryl or aralkyl of hydrogen atom or substituent 1～12 carbon atom.)

(B) with following formula (II) expression () the acrylic amine compound

(in the formula, R ¹⁶Expression-H or CH ₃, R ¹⁷, R ¹⁸Expression can have hydrogen atom respectively, or alkyl, naphthenic base, the aryl or aralkyl of a substituent 1-12 carbon atom.)

Below each composition of the photosensitive composition that is used for photosensitive lithographic plate photographic layer of the present invention is elaborated.

The so-called water that uses among the present invention is insoluble, and soluble vinyl polymerization is a macromolecular compound in alkaline aqueous solution, be that (A) had the compound of solubility alkalescence base and (B)) the N-displacement () acrylic acid amide compound, use known polymerization initiator, in appropriate solvent, carry out the macromolecular compound that polymerization obtains.

Among the present invention,, the compound of formula (I) expression is arranged as compound (A) with solubility alkalescence base.

(in the formula, X ¹Expression-0-or-NR ³-, R ¹Expression-H or-CH ₃, R ²The organic group of expression singly-bound or divalent, Y ¹The expression arylene, Z ¹Expression-OH ,-COCH ,-SO ₂NHR ⁴,-NHSO ₂R ⁵, CONHSO ₂R ⁶,-SO ₂NHCOR ⁷,-NHCONHSO ₂R ⁸,-SO ₂NHCONHR ⁹,-CONHSO ₂NHR ¹⁰, NHSO ₂NHCOR ¹¹,-SO ₂NHSO ₂R ¹²,-COCH ₂COR ¹³,-OCONHSO ₂R ¹⁴, SO ₂NHCOOR ¹⁵N represents 0 or 1, R ²During for singly-bound and Z ¹During for-OH, n is 1, and m represents the integer more than 1.R ³Expression can have alkyl, naphthenic base, the aryl or aralkyl of a hydrogen atom or a substituent 1-12 carbon atom.R ⁴, R ⁹, R ¹⁰Expression can have alkyl, naphthenic base, fragrance or the aralkyl of a hydrogen atom or a substituent 1-12 carbon atom.R ⁵, R ⁶, R ⁷, R ⁸, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵Expression can have alkyl, naphthenic base, the aryl or aralkyl of substituent 1-12 carbon atom.)

In the compound of formula (I) expression, being specially adapted to of the present invention is following compound, i.e. Y ¹Be phenylene, naphthylene, Z ¹Be-OH ,-COOH ,-SO ₂NHR ⁴,-NH ₂SO ₂R ⁵, n is 1, m is 1 or 2.X ¹For-NR ³-time, R ³Be hydrogen atom, R ⁴For having hydrogen atom, C ₁～C ₃Alkyl or phenylene, the R of displacement ⁵For having C ₁～C ₃Alkyl or substituent phenylene.R ²Be X ¹And Y ¹Or n is 0 o'clock, and if Z ¹The words that link, though there is not particular determination, but example as divalent organic base, have and can have substituent alkylidene, ring alkylidene, arylene and and then can contain the base of ester concatenating group, acid amides concatenating group, inferior acid amides concatenating group, ether concatenating group, carbamate concatenating group, urea concatenating group.The suitable R that uses among the present invention ²Be singly-bound, alkylidene, have an alkylidene of concatenating group.

The low molecular compound of formula (I) expression for example has the spy to open clear 63-89864 communique, spy and opens clear 68-226641 communique, spy and open flat 2-866 communique, spy and open flat 8-39082 communique, specially be willing to the compound put down in writing in the flat 11-49769 communique.As this low molecular compound, preferably following (M ₁)～(M ₂₀) compound.

Insoluble as water, and soluble vinyl polymerization is a macromolecular compound in alkaline aqueous solution, compound (A) content with solubility alkalescence base of suitable use is 1～40 mole of %, best 10～35 moles of %.Be lower than 1 mole of %, video picture is bad or form pollution, when a lot of above 40 moles of %, form video picture loss or printability resistance and worsens, and is not suitable for.

As N-displacement () acrylic acid amide compound (B), the compound shown in the following formula (II) is arranged.

(in the formula, R ¹⁶Expression-H or CH ₃, R ¹⁷, R ¹⁸Represent hydrogen atom respectively or have alkyl, naphthenic base, the aryl or aralkyl of a substituent 1-12 carbon atom.)

In the low molecular compound of formula (II) expression, that be suitable for the present invention's use is R ¹⁷, R ¹⁸Be respectively hydrogen atom or have substituent C ₁～C ₆The compound of alkyl, particularly suitable be R ¹⁷, R ¹⁸In a side or both sides be the compound of hydrogen atom.As this low molecular compound, acrylic acid amides is for example arranged, N-methacrylic acid acid amides, N-ethylacrylic acid acid amides, N-n-propyl group olefin(e) acid acid amides, N-iso-propyl group acrylic acid amides, N-n-butylacrylic acid acid amides, N-n-butylacrylic acid acid amides, N-iso-butylacrylic acid acid amides, N-Sec-butylacrylic acid acid amides, N-tert-butylacrylic acid acid amides, N-n-amyl group acrylic acid amides, N-n-hexyl acrylic acid amides, acrylic acid amides classes such as two acetone acrylic acid amides, Methacrylamide, N-methyl acrylamide, N-ethyl-methyl acrylamide, N-n-propyl methyl acid amides, N-iSO-propyl methyl acid amides, N-n-butyl methyl acrylamide, N-n-butyl methyl acrylamide, N-iSO-butyl methyl acrylamide, N-Sec-butyl methyl acrylamide, N-tert-butyl methyl acrylamide, N-n-amyl group Methacrylamide, N-n-hexyl methyl acrylamide, methacryl amines such as two acetone Methacrylamides.

Insoluble as water, and soluble vinyl polymerization is a macromolecular compound in alkaline aqueous solution, the suitable N-displacement of using () acrylic acid amide compound (B) content is 1～50 mole of %, best 5-30 mole %, be lower than 1 mole of %, the bad or pollution of video picture occur, when a lot of above 50 moles of %, the generation video picture is run off, and is not suitable for.

The macromolecular compound that uses among the present invention is respectively the compound that (A) has solubility alkalescence base, (B) N-displacement () more than one multipolymer in the acrylic acid amide compound, preferably contain more than one polymerisable insatiable hungers and close key, and and more than one do not contain shown in solubility base shown in the formula (I) and the formula (II) () multipolymer of the compound of acrylic acid amides base.

Close key as containing this polymerisable insatiable hunger, and do not contain shown in solubility shown in the formula (I) alkalescence base and the formula (II) () compound of acrylic acid amides base, be to have the compound that key is closed in the polymerism insatiable hunger of selecting from acrylic acid, methacrylic acid, esters of acrylic acid, methyl acrylic ester, phenylethylene, vinyl cyanide, methacrylonitrile etc.

Specifically, esters of acrylic acid is for example arranged, as the alkyl acrylate (carbon number of this alkyl, be preferably 1～10) (for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, the acrylic acid pentyl ester, EHA, 2-ethyl hexyl acrylate, acrylic acid-t-monooctyl ester, the chloroethyl acrylate, 2,2-dimethyl hydroxypropyl acrylate, 5-hydroxyl amyl group acrylate, the trimethylolpropane mono acrylic ester, the pentaerythrite mono acrylic ester, epihydric alcohol acrylic ester, the benzyl acrylate, the methoxybenzyl acrylate, the furfuryl group acrylate, the tetrahydrofurfuryl acrylate, Deng), aryl-acrylic acid esters (for example phenyl acrylate etc.), methyl acrylic ester, alkylmethacrylate (the carbon number of this alkyl for example, be preferably 1-10) (for example, the methyl acrylate, the ethyl-methyl acrylate, the propyl methyl acid esters, the isopropyl methyl acrylate, the amyl group methacrylate, hexyl methacrylate, the cyclohexyl methyl acrylate, the benzyl methacrylate, the methyl acrylate, the chlorophenylmethyl methacrylate, the octyl group methacrylate, 4-hydroxyl butyl methyl acrylate, 5-hydroxyl amyl group methacrylate, 2,2-dimethyl-3-hydroxypropyl methylene acid esters, the trimethylolpropane monomethacrylates, the pentaerythrite monomethacrylates, epihydric alcohol methylpropenoic acid ester, the furfuryl group methacrylate, tetrahydrofurfuryl methacrylate etc.), aryl methyl acrylate (phenyl methyl acrylate for example, the tolyl methacrylate, naphthyl methyl acrylate etc.); Phenylethylene, for example styrene, ring-alkylated styrenes, (methyl styrene for example, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, diethylbenzene ethene, cumene ethene, butylstyrene, diethylbenzene ethene, cumene ethene, butylstyrene, diethylbenzene ethene, cyclohexyl benzene ethene, decyl styrene, benzyl styrene, 1-chloro-4-methyl-benzene, trifluoromethyl styrene, benzyl styrene, 1-chloro-4-methyl-benzene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxy-methyl styrene etc.), alkoxystyrene (methoxybenzene alkene for example, 4-methoxyl methyl styrene, dimethoxy styrene etc.), halobenzene ethene (chlorostyrene for example, dichlorostyrene, trichloro-benzenes ethene, tetrachlorobenzene ethene, pentachlorobenzene ethene, bromstyrol, Dowspray 9, iodobenzene ethene, fluorobenzene ethene, trifluorostyrene, 2-bromo-4-trifluoromethyl styrene, 4-fluoro-3-trifluoromethyl styrene etc.): vinyl cyanide, methacrylonitrile etc.

Have in these polymerism insatiable hunger compounds, the suitable compound that uses is methyl acrylic ester, esters of acrylic acid, vinyl cyanide, methacrylonitrile, methacrylic acid, acrylic acid.Handy especially is vinyl cyanide, methacrylonitrile.

These compounds can use wherein one or more, and the optimum quantum of utilization of these copolymer compositions is 0～80 mole of %, are preferably 30-80 mole %.

These have in the polymerism insatiable hunger compound shown in more than one and formula (I) or the formula (II) more than one multipolymer in the low molecular compound, can use blocks, random any in body, the grafting body etc.

The solvent that uses during as synthetic this macromolecular compound, dichloroethylene, cyclohexanone, methyl ethyl ketone, acetone, methyl alcohol, ethanol, ethylene glycol monomethyl ether, ethylene glycol list ethylether, this acid esters of 2-methoxy ethyl second, 1-methyl-2-propyl alcohol, 1-methoxy-propyl acetonyl ester, N are for example arranged, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), toluene, ethyl acetate, methyl lactate, ethyl lactate etc.

These solvents can be used alone or mixed use of two or more.

The molecular weight of macromolecular compound of the present invention, weight average is best more than 2000, and number is average best more than 1000, weight average more preferably 5000～300,000, number on average more preferably 2000～250,000, polydispersity (weight average molecular weight/number mean molecular weight) is best more than 1, and more preferably 1.1～10.

Can contain unreacted monomer in macromolecular compound of the present invention, at this moment monomer shared ratio in macromolecular compound is preferably in below the 15 weight %.

Macromolecular compound of the present invention can use separately, also can mix use more than two kinds.Content 5～95 weight % of contained these macromolecular compounds are preferably 10～85 weight % in the photosensitive composite.

As O-naphthoquinones two triazo-compounds that use among the present invention, put down in writing in the preferably special public clear 43-28403 communique 1, the ester of 2-diazo naphthoquinone sulfonic acid chloride and 1,2,3,-thrihydroxy-benzene-acetone resin.

As other suitable former quinone di-azido compounds, be put down in writing in No. the 3046120th, United States Patent (USP) and No. 3188210 instructionss 1, the ester of 2-diazo naphthoquinone sulfonic acid chloride and phenolics.As other available O-naphthoquinones two triazo-compounds, known in a lot of patents report to some extent.For example, have and put down in writing in the following instructions, the spy opens clear 47-5303 number, spy and opens clear 48-62802 number, spy and open clear 48-63803 number, spy and open clear 48-96575 number, and the spy opens clear 49-38701 number, spy and opens clear 48-13354 number, public clear 37-18015 number, special public clear 41-11222 number, special public clear 45-9610 number, special public clear 49-17481 communique.United States Patent (USP) the 2797213rd, No. 3454400, No. 3544323, the 3573917th, No. 3674495, the 3785825th, BrP No. 1227602, No. 1251345, the 1267005th, No. 1329888, No. 1330932, No. the 854890th, Deutsche Bundespatent etc.

Good especially O-naphthoquinones two triazo-compounds are by the polyol and 1 of molecular weight below 1000 among the present invention, the compound that the muriatic reaction of 2-diazo naphthoquinone sulfonic acid obtains.The instantiation of this compound is to put down in writing in following each communique or the instructions, and promptly the spy opens clear 51-139402 number, the spy opens clear 58-150948 number, the spy opens clear 58-203434 number, the spy opens clear 59-165053 number, the spy opens clear 60-121445 number, the spy opens clear 60-134235 number, the spy opens clear 60-163043 number, the spy opens clear 61-118744 number, the spy opens clear 62-10645 number, the spy opens clear 62-10646 number, the spy opens clear 62-153950 number, the spy opens clear 62-178562 number, special former clear 72-233292 number, No. the 3102809th, United States Patent (USP), No. 3126281, No. 3130047, No. 3148983, No. 3184310, No. 3188210, No. 4639406 etc.

When synthesizing these O-naphthoquinones two triazo-compounds, for the hydroxyl of polyol, preferably with 1 of 0.2～1.2 equivalent, 2-diazo naphthoquinone sulfonic acid chloride reacts, and better reacts with 0.3～1.0 equivalent.

O-naphthoquinones two triazo-compounds that obtain, though what form is 1, the position of 2-diazonium naphthoquinone sulphonate base and all different potpourris of import volume, but hydroxyl is all by 1, the compound of 2-diazonium naphthoquinone sulphonate conversion, the ratio that occupies in this potpourri (content of esterification compound fully) is preferably in 5 moles more than the %, more preferably 20～99 moles of %.

In the photographic layer of photosensitive lithographic plate of the present invention, O-naphthoquinone two azide occupancy is 5～50 weight %, is preferably 15～40 weight %.

In the photographic layer of photosensitive lithographic plate of the present invention, except above-mentioned macromolecular compound with amido link, the macromolecular compound that also can contain other known solvable alkalescence is as cresol-novolak resin, phenol sex change xylene resin, many oxybenzenes ethene, many halogenations hydroxy styrenes etc. such as phenolics, m-cresol-novolak resin, P-cresol-novolak resin, m-/P-cresols urea formaldehyde, phenol/cresols (any that m-.P-or m-/P-mix) mixed phenol urea formaldehydes.

These dissolve in the macromolecular compound of alkalescence, and weight average molecular weight is 500～20000, and the number mean molecular weight is 200～60000.

This addition that dissolves in the macromolecular compound of alkalescence is below the 70 weight % of whole composition.

As putting down in writing in No. 4123279 instructions of United States Patent (USP), as t-butylphenol urea formaldehyde, octyl phenol urea formaldehyde, make the condensation product and the usefulness of substituent phenol and aldehyde with alkyl with 3-8 carbon atom, can improve the resin photonasty of image.

Being used for the photosensitive composite of photosensitive lithographic plate photographic layer in the present invention, is to improve light sensitivity, preferably adds ring-type acid anhydride class, phenols, organic acid.As ring-type acid anhydride, as anhydrous phthalic acid, tetrahydrochysene anhydrous phthalic acid, six hydrogen anhydrous phthalic acids, the 36-bridging oxygen Δ put down in writing in No. 4115128 instructions of United States Patent (USP) ⁴-tetrahydrochysene anhydrous phthalic acid, tetrachloro anhydrous phthalic acid, anhydrous maleic acid, chlorine anhydrous maleic acid, x-benzene anhydrous maleic acid, anhydrous succinic acid, anhydrous pyromellitic acid etc.As phenols, bisphenol-A, P-nitrophenols, P-ethoxy phenol, 2,3 are for example arranged, 4-trihydroxybenzophenone, 4-dihydroxy benaophenonel, 2,4,4 '-trihydroxybenzophenone, 4,4,4 " tetrahydroxy-triphenylmethane, 4,4 '; 3 ", 4 " and four hydroxyls-3,5,3 ', 5 '-the tetramethyl triphenylmethane etc.

As organic acid, open clear 60-88942 communique, spy the spy and open and put down in writing in the flat 2-96755 communique.The sulfonic acid class is for example arranged, sulfinic acid class, alkyl sulfide acids, phosphonic acid based, phosphinic acids class, phosphoric acid ester, hydroxy acid class etc., P-toluenesulfonic acid, dodecylbenzene sulfonic acid, P-toluenesulfinic acid, ethyl sulfuric acid, phenyl-phosphonic acid, phenyl phosphinic acid, phosphoric acid benzene, phosphoric acid hexichol, benzoic acid, isophathalic acid, hexane diacid, P-toluic acid, 3 specifically can have been enumerated, 4-dimethoxy benzoic acid, phthalandione, terephalic acid, 1,4-cyclohexene-2, the 2-dihydroxy acid, sinapic acid, lauric acid, n-undecanoic acid, ascorbic acid etc.Above-mentioned ring-type acid anhydride class, phenols, organic acid occupy ratio in photosensitive composite, be preferably 0.05～15 weight %, more preferably 0.1～5 weight %.

In the photographic layer of photosensitive lithographic plate of the present invention, in order to enlarge the video picture scope, can add the picture spy and open the nonionic surfactant of putting down in writing in clear 62-251740 communique and the flat 2-181248 instructions of special hope, open the amphoteric surfactant of putting down in writing in clear 59-121044 communique, the flat 2-115992 instructions of special hope as the spy.As the instantiation of nonionic surfactant, sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, glyceryl monostearate, polyoxyethylene sorbitan monoleate, polyoxyethylene nonyl phenylate etc. are arranged.Instantiation as amphoteric surfactant, alkyl two (aminoethyl) aminoacetic acid, the poly-aminoethyl aminoacetic acid hydrochloride of alkyl are arranged, A Mugan restrains (ァ モ-グ Application K, trade name, first industry (strain) system, N-myristyl-N, the N-betaine type), 2-alkyl-N-hydroxyethyl-N-hydroxyethyl imidazole quinoline betaine, thunder collapse 15 (transliteration, レ Port Application 15 trade names, Sanyo change into (strain) system, alkyl imidazole system) etc.Above-mentioned nonionic surfactant, amphoteric surfactant shared ratio in photosensitive composite is preferably 0.05～15 weight %, more preferably 0.1～5 weight %.

In the photographic layer of photosensitive lithographic plate of the present invention, but, can add the oven dry agent, make other the filling material etc. of dye well of image colorant for the back of exposing directly obtains video.As spendable dyestuff among the present invention, for example have the spy to open to put down in writing in the flat 5-313359 communique by the kation with basic-dyeable fibre skeleton and have with sulfonic group as unique exchange base, have the basic-dyeable fibre that the salt of organic anion of 10 above carbon atoms of 1-3 hydroxyl forms.

Addition is 0.2～5 weight % of total photosensitive composite.Can also add and to open the compound that the dyestuff interaction of putting down in writing in the flat 5-313359 communique produces the photolysis thing that changes tone with above-mentioned spy, for example there is the spy to open the O-naphthoquinones two nitrine-4-sulfamic acid halide of record in clear 50-36209 number (No. 3969118, United States Patent (USP)), the spy opens the trihalomethyl-2-pyrrone and trihalomethyl three azines of record in clear 53-36223 number (No. 4160671, United States Patent (USP)), the spy opens various O-naphthoquinones two triazo-compounds of record in clear 55-62444 number (No. 2038801, United States Patent (USP)), the spy opens the 2-trihalomethyl aryl 1 of record in clear 55-77742 number (No. 4279982, United States Patent (USP)), 3,4-oxidation azole compounds etc.These compounds can use separately, also can mix use.

As the image colorant, except above-mentioned spy opens the dyestuff of putting down in writing in the flat 5-313359 communique, also can use other dyestuff.As containing the best dyestuff that forms alkaline organic dyestuff, oil-soluble dyes and basic-dyeable fibre are arranged.

Specifically can enumerate oily edge BG, oily orchid-BOS, oily orchid-#603, (above product is Japan chemical industry Co., Ltd. system), Victoria orchid-BOH[hodogaya chemical (strain) system], rhodamine B (C145170B), malachite green (C142000), serge blue (C152015) etc.

When making photosensitive lithographic plate of the present invention, as its supporter, the aluminium sheet that hydrophilicity-imparting treatment is arranged, for example, silicate is handled the aluminium sheet of aluminium sheet, anodic oxidation aluminium sheet, formation graining, the aluminium sheet of plating silicate, also have other, handle the plastic foil and the paper of steel plate, hydrophilicity-imparting treatment as zine plate, corrosion resistant plate, chromium.

Wherein, best is aluminium sheet.Aluminium sheet comprises pure aluminum plate and aluminium alloy plate.As aluminium alloy, can use various, the alloy of metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel and aluminium for example.These compositions, any one all has can add iron and titanium, in addition, also can contain the impurity of negligible quantity.

Can carry out surface treatment to aluminium sheet as required.For example carry out the processing of sand milling order, silicate, fluoridize the dip treating of aqueous solution such as potassium silicate, phosphate, or surface treatment such as anodized.As putting down in writing in No. 2714066 instructions of United States Patent (USP).After forming graining, in sodium silicate aqueous solution, carry out the aluminium sheet of dip treating, during illustrating out for No. 3181461, United States Patent (USP) puts down in writing, after aluminium sheet is carried out anodized, in alkali metal silicate aqueous solution, carry out dip treating again.The most handy, above-mentioned anodized, can be by following enforcement, a kind of in the aqueous solution of organic acids such as mineral acids such as phosphoric acid, chromic acid sulfuric acid, boric acid or oxalic acid, sulfaminic acid or their salt or non-aqueous solution for example, or in the electrolytic solution of combination below two kinds, aluminium sheet as anode, is passed to electric current.

It also is effective that the silicate of putting down in writing in No. 3658662 instructions of United States Patent (USP) is electroplated.

These hydrophilicity-imparting treatment, except for supporting body surface is formed water wettability implements, the purpose of its enforcement is also for preventing and be provided with the reaction that the photosensitive composite on it is harmful to, also for improving the adherence with photographic layer.

Before aluminium sheet is formed graining, can remove the rolling oil on surface and, pre-treatment be implemented on its surface as required for presenting the aluminium surface of cleaning.Be the former, can use triclene equal solvent, surfactant etc., and be the latter, can use alkaline corrosion agent such as NaOH, potassium hydroxide.

As the method that forms graining, it all is effective adopting any method with in electrochemical method machinery, chemistry.As mechanical means,, spray sand-blast, will use the brushing method of nylon bruss wiping etc. as the water dispersion pulp liquid of pumice lapping compound as ball-milling method.As chemical method, open in the clear 54-31187 communique as the spy and to put down in writing, the method for in the full Heshui solution of the inorganic acid salt of aluminium, flooding.As electrochemical method, the best way is in the acidic electrolysis bath of hydrochloric acid, nitric acid or their acid mixture, passes to the method that alternating current carries out electrolysis.

In the method for this surface roughening, it is best that the spy is opened the surface roughening process that the mechanically roughened and electrochemical rougheningization put down in writing in the clear 55-137993 communique makes up, and can make the bounding force of photoresist image and supporter very strong.

The graining that utilizes said method to carry out, preferably embodiment is in 0.3～1.0 the scope surfaceness (Ha) of surface of aluminum plate center line.

To having carried out the aluminium sheet of the processing of graining, the chemical corrosion that can wash as required like this.

Corrosion treatment liquid can from common can dissolved aluminum alkalescence or acidic aqueous solution choose.At this moment, on the surface of corrosion, must not form the covered film different with the aluminium of inducing by the corrosive liquid composition.Best mordant example as alkaline matter, has NaOH, potassium hydroxide, tertiary sodium phosphate, disodium hydrogen phosphate, tripotassium phosphate, dikalium phosphate etc.; As acidic materials, sulfuric acid, persulfuric acid, phosphoric acid, hydrochloric acid and salt thereof etc. are arranged; The metal that ionization tendency is lower than aluminium, the salt of zinc, chromium, cobalt, nickel, copper etc. for example, owing on corrosion surface, form unnecessary covered film, so very undesirable.

These mordant, at the working concentration of setting, under the temperature, the dissolution velocity of employed aluminium or alloy, preferably per 1 minute stain of dip time 0.3～40g/m ², higher or lowlyer also do not have much relations than this scope.

Corrosion is that aluminium sheet is flooded in above-mentioned corrosive liquid, or corrosive liquid is coated on the aluminium sheet corrodes, and etching extent is preferably handled 0.5～10g/m ²Scope.

As above-mentioned mordant, consider from the characteristics that corrosion speed is fast, preferably use the aqueous solution of alkalescence.At this moment, owing to generate dirt, handle so remove dirt usually.Remove the acid of using when dirt is handled and be nitric acid, sulfuric acid, phosphoric acid, chromic acid, fluoric acid, fluorine boronation hydracid etc.

The aluminium sheet of corrosion treatment is washed and anodic oxidation as required, and can utilizing in the art, customary way carries out anodic oxidation.Specifically,, or in the aqueous solution or non-aqueous solution that wherein make up more than two kinds, on aluminium sheet, pass to direct current or alternating current, on the aluminium support body surface, form the anodic oxidation covered film at sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfaminic acid, benzene sulfonic acid etc.

Anodised treatment conditions, owing to many variations is arranged according to the electrolytic solution that uses, thus generally can't determine, but say that generally suitable condition is, the 1-80 weight % of the concentration of electrolytic solution, the liquid temperature is 5～70 ℃, 0.5～60 ampere/dm of current density ², voltage 1～100V, electrolysis time 30 seconds～50 minutes.

The best way is put down in writing in BrP illustrates out for No. 1412768 in these anodized, in sulfuric acid, carry out anodised method with high current density, with put down in writing in No. 3511661 instructions of United States Patent (USP), be that electrolytic solution carries out anodised method with phosphoric acid.

As above-mentioned surface roughening, anodised aluminium sheet and then carry out hydrophilicity-imparting treatment as required, as the best way example is No. the 2714066th, United States Patent (USP) and No. 3181461 disclosed alkali silicate of using, as sodium silicate aqueous solution, or disclosed usefulness is fluoridized the disclosed method of handling with polyvinyl sulfonic acid in potassium zirconium and No. 4153461 instructions of United States Patent (USP) in the special public clear 36-22063 communique.

As above-mentioned surface roughening, anodic oxidation, and then need carry out on the aluminium sheet of hydrophilicity-imparting treatment the following coating that is formed by water soluble compound being set.As the example of this water soluble compound, as disclosed in the public clear 57-16349 communique of spy.The combination of water-soluble metal salt and hydrophilic cellulose (for example zinc chloride and carboxymethyl cellulose, magnesium chloride and hydroxyethyl cellulose etc.), disclosed polyacrylic acid amide in No. 3511661 instructions of United States Patent (USP), disclosed polyvinyl sulfonic acid in the special public clear 46-35685 communique, the spy opens disclosed amino acid and basic salt Na salt in the clear 60-149491 communique, alkali metal layers salt such as K salt, ammonium salt, hydrochloride, oxalates, acetate, phosphate etc.), the spy opens disclosed amine and salt thereof with hydroxyl in the clear 60-232998 communique, the amine of best hydroxyl and salt thereof.The following coating of this water soluble compound preferably is set in 1-80mg/m with solid component meter ²In the scope.

The present invention is dissolved in the solvent by the composition with above-mentioned each photosensitive composite, is coated on the supporter, obtains photosensitive lithographic plate.As the solvent that uses herein, the r-butyrolactone is arranged, ethylene dichloride, cyclohexanone, methyl ethyl ketone, the ethylene glycol monomethyl ether, ethylene glycol list ethylether, 2-methoxyethyl acetate ether, 1-methoxy-2-propyl alcohol, 1-methoxy-2-propyl-acetic acid ester, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide (DMSO), dimethylformamide, dimethyl formamide, water, the N-methylpyrrole ketone of washing, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methyl alcohol, ethanol, isopropyl alcohol, divinyl ethylene glycol dimethyl ether etc., these solvents can use separately also can mix use.Concentration (solid constituent) in the same mentioned component is that 2～50 weight % are suitable.According to purposes, the coating weight difference for example, for photosensitive lithographic plate, as solid constituent, is preferably 0.5～30g/m ²Along with the minimizing of coating weight, though photonasty increases, the rerum natura of light-sensitive surface decreases.

In the photographic layer of photosensitive lithographic plate of the present invention, good in order to make coating, can add surfactant, it is for example special that to open the fluorine of putting down in writing in the clear 62-170950 communique be surfactant.Optimum addition is 0.01～1 weight % of total photosensitive composite, more preferably 0.050.5 weight %.As the photographic layer surface of above-mentioned setting,, be preferably formed as the protection surface layer in order to shorten the time that vacuumizes when the sealing of using the vacuum saggar exposes and to prevent to burn.Concrete grammar has the spy to open the method for putting down in writing in clear 50-125805 number, special public clear 57-6582 number, special public clear 61-28986 number each communique that the protection surface layer is set, the method for putting down in writing in the special public clear 62-62337 communique that the pressed powder hot melt is adhered to etc.

Imaging liquid for photosensitive lithographic plate of the present invention, the preferably actual alkaline aqueous solution that does not contain organic solvent, specifically there are sodium silicate, potassium silicate, hydrogen-oxygen to criticize aqueous solution such as sodium, potassium hydroxide, lithium hydroxide, sodium phosphate, phosphoric acid-hydrogen sodium, ammonium phosphate, phosphoric acid-hydrogen ammonium, sodium metasilicate, sodium carbonate, sodium bicarbonate, sal tartari, potassium bicarbonate, ammoniacal liquor, their concentration is 0.1～10 weight %, is preferably 0.5～5 weight %.In these, contain the imaging liquid of alkaline silicates such as potassium silicate, lithium metasilicate, sodium silicate, when printing, be difficult to produce and pollute, so the composition of ideal alkaline silicate is [SiO with mol ratio ₂]/[M]=0.5～2.5 [SiO wherein ₂], [M] represent SiO respectively ₂Mole degree, the most handy 0.8～8 weight %SiO that contains of former volumetric molar concentration and total alkaline metal ₂Former imaging liquid.Now look like for example can add water-soluble sulfites such as sodium sulphite, potassium sulfite, magnesium sulfite, resorcinol, methylresorcinol, p-dihydroxy-benzene, Acid Thiosalicylique etc. in the liquid at this.The optimum content of these compounds in imaging liquid is 0.002～4 weight %, is preferably 0.01～1 weight %.

Can contain following a kind of surfactant at least in this imaging liquid, the spy opens that clear 50-51324 communique, spy are opened the anionic surfactant that puts down in writing in the clear 59-84241 communique, and amphoteric surfactant, spy are opened clear 59-75255 communique, the spy opens the nonionic surfactant of putting down in writing in clear 60-111246 communique and the clear 60-213943 communique of Te Kai.Contain perhaps that the spy opens clear 55-95946 communique, the spy opens the polyelectrolyte of putting down in writing in the clear 56-142528 communique, improve wetting state, and can improve the stability (now looking like scope) of video picture photosensitive composite, ideal.The addition of these surfactants is preferably 0.001～2 weight %, more preferably 0.003～0.5 weight %.As the alkaline metal of alkaline silicate, in total alkaline metal, contain the above potassium of 20 moles of %, in these imaging liquids,, preferably contain 90 moles more than the % because generation insolubles seldom is ideal, good especially situation is the potassium that contains 100 moles of %.

And then in the imaging liquid that uses in the present invention, also can add organic solvent and special slaine, the organosilane chemical combination top grade defoamers of putting down in writing in the sequestrant of putting down in writing in the clear 58-190952 communique, the special fair 1-30139 communique of opening such as some alcohol.

Light source as exposure is used has carbon arc lamp, mercury vapor lamp, xenon lamp, tungsten lamp, metal halide lamp etc.

Needless to say more, the also available spy of above-mentioned photosensitive lithographic plate opens the method for putting down in writing in clear 54-8002 number, 55-115045 number, 59-58431 number each communique processing of making a plate.That is, after video picture is handled,, or contain the processing of aqueous acid, or contain the resin not sensitizationization processing after aqueous acid is handled because of the processing of washed resin not sensitizationization.And then, in the videograph process of this photosensitive lithographic plate, because according to treatment capacity, aqueous alkali consumption, alkali concn reduces, perhaps, because the long-play of automatic developing liquid, air has reduced alkali concn, cause processing power to reduce, at this moment, as the spy opens clear 54-62004 number record, use and replenish liquid recovery processing power.This situation preferably uses the method for record in No. the 4882246th, the United States Patent (USP) to replenish.The plate-making of informing is handled, and preferably uses the special automatic developing device of opening record in flat 2-7054 2-32357 number to carry out.

After photosensitive lithographic plate of the present invention being carried out image exposure, video picture, washing or flushing, when eliminating unnecessary image section, preferably use the elimination liquid of putting down in writing in the special fair 2-13293 communique.And then in the final operation of plate-making, resin not sensitizationization rubber as desired coating, put down in writing in the preferably following document, that is, special public clear 62-16834 number, 62-25118 number, 63-52600 number, spy are opened clear 62-7595 number, 62-11693 number, 62-83194 number etc.Photonasty lithographic plate of the present invention carried out image exposure, video picture, washing or flushing, carry out cancel job according to hope, after the washing, when carrying out printing down, before printing down, preferably utilize special public clear 61-2518 number,, 55-28062 number, spy open whole the liquid of putting down in writing in clear 62-31859 number, 61-159655 communique and handle.

Followingly illustrate in greater detail the present invention, but these do not limit content of the present invention according to synthesis example, embodiment.

Synthesis example 1

To have stirring machine, cooling tube, in the 200ml there-necked flask of the funnel that drips, add 3.60g (0.015 mole) N-(P-aminosulfonyl benzene) methacrylic acid acid amides, 1.13g (0.01 mole) N-iso-propyl group acrylic acid amides, 1.50g (0.015 mole) methyl methacrylate, 3.18g (0.06 mole) vinyl cyanide and 20gN, the N-dimethyl acetamide.Utilize hot bath to be heated to 65 ℃ on one side, stir on one side, in this potpourri, adding 0.25gV-65 (with the pure medicine of light (strain) system), the limit keeps 65 ℃, and the limit flows down at nitrogen and stirred 2 hours.In 2 hours, pass through addition funnel, in this reaction mixture, drip 3.60gN-(P-aminosulfonyl benzene) methacrylic acid acid amides 1.13gN-iso-propyl group acrylic acid amides-1.50g methyl methacrylate 3.18g vinyl cyanide and 20gN again, the potpourri of N-dimethyl acetamide and 0.25gV-56.After dripping end, stirred 2 hours down at 65 ℃ again.Reaction finishes the back and adds 40g methyl alcohol, cools off, and stirs to add 2L water down, stirs after 30 minutes, and filtration drying obtains 18g white solid [macromolecular compound (a)].The weight average molecular weight (polystyrene standard) of utilizing silica gel to soak into this macromolecular compound of chromatography determination is 45000.

Synthesis example 2～6

The same with synthesis example 1, macromolecular compound (b)～(f) shown in the synthetic table 1.

Below be described more specifically the present invention with embodiment.[%] among the embodiment do not have representing with [weight %] of special appointment.

Embodiment 1～9 and comparative example 1～3

With nylon bruss and 400 purpose float stone aqueous suspensions, the surface of aluminum plate that 0.30mm is thick washes after forming graining.After dipping corroded in 60 seconds in 10% sodium hydrate aqueous solution under 70 ℃, with circulating water flushing, 20%HNO again ₃Neutralization is cleaned, washing.At V _AUnder the condition of=12.7V, with sinusoidal wave exchange current, in 1% aqueous solution of nitric acid, with 160 coulombs/dm ²The anode electric weight, base is carried out the electrolytic surface roughened.Measuring its surfaceness is 0.6 μ (Ra represents).Then, at 55 ℃, 30% H ₂SO ₄After dipping removed protective surface in 2 minutes in the aqueous solution, at 20%H ₂SO ₄In the aqueous solution, with current density 2A/dm ²Modulation substrate carries out anodic oxidation, forms 2.7g/m ²Thickness.

The following masking liquid (A) of the following composition of coating on the substrate surface of handling like this, in 80 ℃ of following dry 30 seconds, dried is 300mg/m by complexor ²

Following masking liquid (A)

Amino-ethyl sulfonic acid 0.01g

Benzene sulfonic acid 0.15g

Triethanolamine 0.05g

Beta-alanine 0.10g

Methyl alcohol 40g

Pure water 60g

Operation makes substrate (I) like this.

Then, upward be coated with 25ml/m at this substrate (I) with the bar type coating process ²Following sensitization liquid (B), (C), 100 ℃ dry 1 minute down, obtain photosensitive lithographic plate [B]-1～[B]-8, [C]-1～[C]-4 of positive type.Dried coating weight is about 1.7g/m ²

In sensitization liquid [B]-1～[B]-8, [C]-1～[C]-4, use the producing high-molecular of compound of the present invention moistening in some tables 1 or comparison to contain thing and be shown in table 1.

[sensitization liquid (B)]

2,3,4-three oxybenzene ketone and naphthoquinones-1,2, the carboxylate (esterification yield of-two nitrine-5-sulfonyl chloride; 90 moles of %) 0.45g

Cresols one formaldehyde phenolic resin (, the contrast; 6 pairs 4, weight average molecular weight 3000, number mean molecular weight 1100 contains 0.7% unreacted cresols) 0.2g

M-cresols-formaldehyde phenolic resin (weight average molecular weight 1700, number mean molecular weight 600 contain 1% unreacted cresols) 0.3g

The condensation product of burnt Chinese parasol tree phenol and acetone (weight average molecular weight 2200, number mean molecular weight 700) 0.1g

Macromolecular compound of the present invention (or comparing macromolecular compound) 1.1g

Positive octyl phenol-the formaldehyde resin of P-(putting down in writing in No. 4123279 instructions of United States Patent (USP)) 0.02g

Naphthoquinones two nitrine-1,2-two nitrine-4-sulfonic acid chloride 0.01g

Tetrahydrochysene anhydrous phthalic acid 0.01g

Benzoic acid 0.02g

4-[P-N-(P-acrinyl) aminophenyl]-2, two (the trichloromethyl)-S-three azine 0.02g of 6-

N-(1,2 naphthoquinones-2-two nitrine-4-sulphonyl oxygen-cyclohexane-1, the inferior acid amides 0.01g of 2-dicarboxylic acid

With the pure blue BOH[hodogaya chemical of Victoria (strain) system] negative ion is become the dyestuff of 1-naphthalene sulfonic aicd

0.05g

Curcumin 0.005g

1-(Alpha-Methyl-α-(4-hydroxyl-3,5-xylenediol) ethyl)-4-[α, α-two (4-hydroxyl-3,5-xylenediol) ethyl] benzene (spy opens (X) of the chemical combination in the flat 6-282067 instructions) 0.04g

U.S. loud, high-pitched sound method time storehouse F-176 (transliteration, メ ガ Off ァ ッ Network F-176

Big Japanese ink chemical industry (strain) system, fluorine are surfactant) 0.01g

Methyl ethyl ketone 10g

Υ-butyrolactone 5g

1-methoxy-2-propyl alcohol 5g

[sensitization liquid (C)]

2,3,4-three oxybenzene ketone and naphthoquinones-1, the carboxylate of 2-two nitrine-5-sulfonyl chloride (esterification yield, 90 moles of %) 0.45g

Macromolecular compound of the present invention (or comparing macromolecular compound) 1.7g

Naphthoquinones two nitrine-1,2-two nitrine-4-sulfonic acid chloride 0.01g

Tetrahydrochysene anhydrous phthalic acid 0.02g

Benzoic acid 0.02g

4-[P-N-(P-acrinyl) aminobenzene]-2, two (the trichloromethyl)-S-three azine 0.02g of 6-

N-(1,2-naphthoquinones-2-two nitrine-4-sulphonyl oxygen) cyclohexane-1, the inferior acid amides 0.01g of 2-dicarboxylic acid

With the pure blue BOH[hodogaya chemical of Victoria (strain) system] negative ion is become the dyestuff 0.05g of 1-naphthalene sulfonic aicd

Curcumin 0.005g

1-[Alpha-Methyl-α-(4-hydroxyl-3,5-xylenediol) ethyl]-4-(α, α-two (4-hydroxyl-3,5-xylenediol) ethylbenzene (spy opens the compound (X) in the flat 6-282067 instructions) 0.04g

U.S. loud, high-pitched sound method time storehouse F-176 (transliteration, メ ガ Off ァ ッ Network F-176

Big Japanese ink chemical industry (strain) system fluorine is a surfactant) 0.01g

Methyl ethyl ketone 10g

Υ-butyrolactone 5g

1-methoxy-2-propyl alcohol 5g

On the photographic layer of photosensitive lithographic plate [B]-1～8 and [C]-1～4, paste the positive transparent original painting of stick figure and site picture, expose from 70cm with the carbon arc lamp of 30A.

With the photosensitive lithographic plate [B]-1～8 and [C]-1～4 of exposure, in DP-4 (trade name; Fuji description (strain) system) in 8 times of dilute aqueous solutions, under 25 ℃, 60 seconds of dipping video picture.

With the high skill industry system KOR of society type printing machine, with commercially available common prepared Chinese ink and UV prepared Chinese ink, print on good quality paper lithographic plate that use obtains [B]-1～8 and [C]-1～4.Flat those galleys [B]-1～8 of research and the final printing number of [C]-1～4 and the pollution situation of printed article are shown in table 2.

As seen in Table 2, use the lithographic plate [B]-1～8 and [C]-1～3 (embodiment 1～9) of macromolecular compound of the present invention to compare with [B]-7,8, [C]-4 (comparative example 1～3), using common prepared Chinese ink, when UV prepared Chinese ink is any, the printing number is all a lot, printability resistance is very good, and stain resistance is also very good.

Lithographic plate	The macromolecular compound that uses	Printing number when using common prepared Chinese ink	Printing number when using UV prepared Chinese ink	Pollution situation
					[B]-1 embodiment 1	Macromolecular compound (a)	65,000	40,000	○
[B]-2 embodiment 2	Macromolecular compound (b)	65,000	40,000	○
					[B]-3 embodiment 3	Macromolecular compound (c)	60,000	30,000	○
[B]-4 embodiment 4	Macromolecular compound (d)	65,000	40,000	○
					[B]-5 embodiment 5	Macromolecular compound (e)	60,000	35,000	○
[B]-6 embodiment 6	Macromolecular compound (f)	58,000	28,000	○
					[B]-7 comparative example 1	Macromolecular compound (g)	36,000	18,000	×
[B]-8 comparative example 2	Macromolecular compound (b)	32,000	8,000	○
					[C]-1 embodiment 7	Macromolecular compound (a)	82,000	60,000	○
[C]-2 embodiment 8	Macromolecular compound (b)	78,000	58,000	○
					[C]-3 embodiment 9	Macromolecular compound (d)	80,000	62,000	○
[C]-4 comparative example 3	Macromolecular compound (b)	41,000	16,000	×

* visual valuation zero: good, *: excess contamination

As above explanation, photosensitive lithographic plate of the present invention contains the multipolymer of the monomer component that has above-mentioned (A) and (B) represent in photographic layer, this photographic layer is good to the adherence of substrate, pay soft epithelium, because organic solvent dissolution is good, so the coating when being coated with on supporter might as well, behind coating, drying, the image exposure, the video picture of exposed portion in the alkaline aqueous solution imaging liquid is good, a shape image that obtains, mar proof, good with the adherence of supporter during as galley, can obtain the good printed article of a lot of numbers.

Drug resistance is good, needn't carry out printing down and handle, and when using the printing of UV prepared Chinese ink, still can obtain the good printed article of a lot of numbers, and it is good that the final effect that obtains has provided printability resistance, do not produce the lithographic plate of pollution during printing.

Claims (2)

1, a kind of sensitive offset press version, feature be have moisture insoluble and in alkaline aqueous solution soluble vinyl polymerization be in the photosensitive lithographic plate of photographic layer of macromolecular compound and O-naphthoquinones two triazo-compounds, this vinyl polymerization is that macromolecular compound is to contain following (A) and (B) multipolymer of expression monomer component:

(A) have the basic compound of the alkalescence of solubility shown in the following formula (I):

X in the formula ¹Expression-O-or-NR ³-, R ¹Expression-H or-CH ₃, R ²Expression singly-bound, alkylidene or have the alkylidene of ester concatenating group, acid amides concatenating group, inferior acid amides concatenating group, ether concatenating group, carbamate concatenating group or urea concatenating group, Y ¹The expression arylene, Z ¹Expression-SO ₂NHR ⁴Base, n represent 0 or 1, R ²When singly-bound, and Z ¹During for-OH, n is 1, and m represents the integer more than 1, R ³Alkyl, naphthenic base, the aryl or aralkyl of expression hydrogen atom, a 1-12 carbon atom, R ⁴Expression hydrogen atom, C ₁-C ₃Alkyl or phenylene;

(B) with following formula (II) expression acrylic acid amides or methacrylic acid amide compound:

In the formula, R ¹⁶Expression-H or CH ₃, R ¹⁷, R ¹⁸Represent hydrogen atom or C respectively ₁-C ₆Alkyl; Described A content of monomer is the 1-40 mole % with respect to the interpolymer mole, and the B content of monomer is the 1-50 mole % with respect to the interpolymer mole.

2, a kind of sensitive offset press version according to claim 1, feature is described R ¹⁷, R ¹⁸In a side or both sides be hydrogen atom.