CN1271471C - Heat-sensitive lithographic plate - Google Patents

Abstract

The present invention provides a radiation-sensitive lithographic printing plate which can be subjected to aqueous development or does not require any special treatment such as wet development and rubbing after image writing, in particular, a heat-sensitive lithographic printing plate which can be subjected to recording by a solid laser or semiconductor laser emitting infrared rays to allow direct plate making from digital data. Furthermore, the present invention also provides a masculine type heat-sensitive lithographic printing plate excellent in press life. The present invention comprises an image-forming layer containing a polymer which is capable of changing its hydrophilicity by heat and is crosslinked by crosslinking reaction.

Description

Heat-sensitive lithographic plate

The present invention relates to be used as the heat-sensitive lithographic plate of original edition for lithographic printing (the following PS version that also claims).Especially can utilize various laser such as visible light or infrared ray can directly to make a plate according to digital signal, and can water development or just can install to the heat-sensitive lithographic plate that prints on the printing machine without developing.Be particularly related to and be suitable for not having the heat-sensitive lithographic plate that galley is made in any processing.

When utilizing the PS version to make galley in the past, comprise following operation, promptly after exposure with remove supporting body surface image shape photographic layer (imaging layer) and utilize the wet development operation, wash the galley of development treatment with water water washing, perhaps use the rinsing liquid that contains surfactant, the insensitive lipoprotein liquid that contains gum arabic, starch derivative etc. to carry out postprocessing working procedures.

On the other hand, produce environmental problem in plate-making, printing industry owing to the alkalescence of development waste liquid in recent years.Along with the rationalization progress of plate-making industry, and wish to have a kind of wet development of above-mentioned such complexity that do not need to handle, and after exposure, can be directly used in the galley master of printing.

Open the spy and to have put down in writing the image forming material that is suitable for making positive type non-processor lithographic plate in the flat 7-186562 communique radiation-sensitive.Also put down in writing compound in this communique with specific carboxylic acid silicon structure.They contain the heating or acid effect under become hydrophilic functional group by hydrophobicity.Even though with such compound after exposure not development treatment also can print and printed article that can must meet the demands; But still expectation further improves its printability resistance.

The purpose of this invention is to provide a kind of energy water development, or need not the special lithographic plate of handling such as wet development or wiping after the image input radiation-sensitive; The heat-sensitive lithographic plate that can directly make a plate according to numerical data that utilizes particularly that the Solid State Laser of infra-red-emitting or semiconductor laser write down.

Another object of the present invention provides the outstanding positive type heat-sensitive lithographic plate of printability resistance.

Through studying intensively of present inventors, produce a kind of polymkeric substance imaging layer that causes the water wettability variation by heating that has, and pass through photo-crosslinking and crosslinked heat-sensitive lithographic plate, thereby reached above-mentioned purpose than polymkeric substance.

Heat-sensitive lithographic plate of the present invention by containing specific polymkeric substance in its imaging layer, thereby has improved the film strength of imaging layer.

Heat-sensitive lithographic plate of the present invention is in the acid that utilizes the hot of heater means generation or utilize sour generation means to produce, the image part water wettability of above-mentioned polymkeric substance is changed, do not need the imaging development treatment, can print, the printed article that the energy acquisition meets the demands, its printability resistance also is superior simultaneously.And the polymkeric substance crosslinked by photo-crosslinking is with different by the method for heat cross-linking, and be not crosslinked owing to do not pass through heating, protected the functional group that produces the water wettability variation because of heating effectively with regard to meaning.

The polymkeric substance that contains in the imaging layer of heat-sensitive lithographic plate of the present invention, Yin Re and water wettability is changed, because of photo-crosslinking crosslinked, but to this not special qualification.

Above-mentioned water wettability changes, and no matter is to change to water wettability from hydrophobicity, or change to hydrophobicity from water wettability, all can, preferably change from the hydrophobicity water wettability.

Above-mentioned water wettability changes, by hydrophobicity when water wettability changes, heat-sensitive lithographic plate of the present invention is formed with positive type; When changing, hydrophobicity just forming the negativity type by water wettability.

The water wettability of above-mentioned polymkeric substance changes, preferably have on the side chain by polymkeric substance be heated and gene that water wettability is changed is finished.

Gene as the water wettability variation that causes by heat; the gene that preferably is heated and is changed to water wettability by hydrophobicity is as concrete example, at first to from the sulfonic acid acyl group; the disulfonyl base, the instantiation of selecting at least a functional group in sulfimide base and the alkoxy alkane fat is elaborated.

Sulfonic acid fat base, disulfonyl base, sulfimide base be available following general expression (1), (2), (3) expression respectively.

[Chemical formula 1]

General expression (1)-L-SO ₂-O-R ¹

General expression (2)-L-SO ₂-SO ₂-R ²

General expression (3)

L represents functional group shown in general expression (1), (2), (3) is connected to the needed organic group that is made of the non-metallic atom of multivalence on the polymer backbone, R in the formula ¹, R ², R ³, R ⁴Expression displacement or do not have displacement aryl, replace or do not have the alkyl or the epimino base of displacement.

At R ¹, R ², R ³, R ⁴When representing the aryl of aryl or displacement, on aryl, contain isocyclic aryl and heterocyclic aryl.It is 6 to 19 compound that carbon numbers such as phenyl, naphthyl, anthryl, pyrenyl are arranged as isocyclic aryl, and two carbon numbers such as pyridine radicals, furyl and the quinolyl that is shortened into by phenyl ring, benzofuranyl, thioxanthene ketone group, carbazyl are arranged as heterocyclic aryl is 3 to 20 and to contain the heteroatoms number be 1 to 5 compound.R ¹, R ², R ³, R ⁴When the alkyl of expression displacement, it is 1 to 25 compound that this alkyl has straight chain shapes such as methyl, ethyl, isopropyl, the tert-butyl group, cyclohexyl, a chain or ring-type carbon number.

R ¹, R ², R ³, R ⁴Expression displacement aryl; the displacement heterocyclic aryl; during the displacement alkyl; can enumerate methoxyl as sub stituent; the carbon number of ethoxy etc. is 1 to 10 alkoxy; fluorine atom; the chlorine atom; halogen atoms such as bromine atoms; trifluoromethyl; the alkyl of halogens such as trichloromethyl displacement; methoxycarbonyl group; carbethoxyl group; tertbutyloxycarbonyl; right-carbon numbers such as chlorobenzene carbonyl are 2 to 15 alkoxy carbonyl group or fragrant oxygen carbonyl; hydroxyl; acetoxyl group; benzoyloxy group; right-acyloxy such as diphenylamino benzoyloxy group; the carbonate based of tertiary butyloxycarbonyl oxygen base etc.; the tertiary butyloxycarbonyl methoxyl; 2-gives a tongue-lashing ethers such as the oxygen base of muttering; amino; dimethylamino; diphenylamino; the morpholino base; displacements such as acetylamino; the amino of non-displacement; methyl mercapto; thioether groups such as thiophenyl; vinyl; alkenyls such as benzene thiazolinyl; nitro; cyano group; formoxyl; acetyl group; acyl groups such as benzoyl, phenyl; the aryl of naphthyl one class; heterocyclic aryl of pyridine radicals one class or the like.R is arranged again ¹～R ⁴When being displacement aryl, displacement heterocyclic aryl, except above-mentioned, can also use alkyl such as methyl, ethyl as sub stituent.

R ¹, R ², R ³, R ⁴During expression ring-type imido grpup, can be 4 to 20 compound as cyclic imide with carbon numbers such as succinimide, BIDA, cyclohexyl dicarboxylic acid's imines, norbornene dicarboxylic acids imines.

Above-mentioned R ¹, R ², R ³, R ⁴What preferably adopt is the aryl of using electrophilic group displacements such as halogen, cyano group, nitro; Alkyl with electrophilic group displacements such as halogen, cyano group, nitros; Alkyl, naphthenic base and the epimino of 2 grades or 3 grades chains.

The multivalence of representing with L that is made of non-metallic atom links group, is to contain from 1 to 60 carbon atom, from 0 to 10 nitrogen-atoms, from 0 to 50 oxygen atom, from 1 to 100 hydrogen atom and from 0 to 20 compound that sulphur atom is formed.As linking group more specifically, can enumerate the compound that combines by following structural unit.

[changing 2]

-CH ₂- -O-

-S-

When multivalence binding group has sub stituent; can adopt the alkyl of carbon numbers from 1 to 20 such as methyl, ethyl as sub stituent; the aryl of carbon number such as phenyl, naphthyl from 6 to 16; the acyloxy of the carbon number from 1 to 6 of hydroxyl, carbonyl, sulfoamido, N-sulfoamido, acetoxyl group-class; the alkoxy of the carbon number from 1 to 6 of methoxyl, acetoxyl group one class; the halogen atom of chlorine, bromine one class; the carbon number of methoxycarbonyl group, carbethoxyl group, ring carbethoxyl group one class is 2 to 7 alkoxy carbonyl group, the carbonic acid acyl group of cyano group, tert-butyl group carbonic acid one class etc.

The alkoxy alkanoyl can be represented with following general expression (4).

[chemical formula 3]

General expression (4)

R in the formula ¹¹The expression hydrogen atom, R ¹²Expression hydrogen atom or carbon number are at the alkyl below 18, R ¹³The expression carbon number is at the alkyl below 18.Also has R ¹¹, R ¹²And R ¹³Also can be in inside in twos in conjunction with forming the space, particularly by R ¹²And R ¹³5 or 6 annulus are better in conjunction with forming.

Though enumerated above general expression (1)-(4) represented compound, be preferably the sulfonic acid acyl group of formula (1) expression and the alcoxyl alkanoyl of general expression (4) expression, good especially is the sulfonic acid acyl group of general expression (1) expression.Below list the object lesson of the functional group of general expression (1)-(4) expression.

[chemical formula 4]

[changing 5]

[changing 6]

Above-mentioned functional group heating or acid act on polymkeric substance the time, play the effect that changes to water wettability by hydrophobicity.Particularly these functional groups make preferably that the water droplet contact angle reduces more than 15 ° in the China ink of polymkeric substance, promptly, as the skyborne water droplet contact angle of polymkeric substance heated or acid effect can reduce more than 15 °, preferably be initially hydrophobicity and become hydrophilic polymers, and then as polymkeric substance, this aerial water droplet contact angle preferably reduces more than 40 °.As above-mentioned polymkeric substance specifically, aerial water droplet contact angle was the polymkeric substance more than 60 ° originally, but can reduce to below 20 ° after heating or acid effect.

The polymkeric substance that contains in the imaging layer of heat-sensitive lithographic plate of the present invention is that the water wettability of being heated changes, and can form crosslinked material with photo-crosslinking in addition.

Below be elaborated to utilizing photo-crosslinking to form cross-linked polymer.

Photo-crosslinking has the method for photodimerization, the polymerization of photoionization base.On polymkeric substance, embed the crosslinking active base, form crosslinked with himself or with monomer reaction.

Light dimerization reaction is to utilize the absorption of the functional group of self to light, or utilizes the photaesthesia agent to cause cross-linking reaction under rayed.

Photoionization base polymerization crosslinking is to utilize the Photoepolymerizationinitiater initiater of widely knowing, and causes cross-linking reaction under rayed.

The crosslinked polymkeric substance by photo-crosslinking is to contain photocrosslinking reaction functional group, and its another name is the monomer of hardening functional group and contains that monomer copolymerization of the group that produces the water wettability variation of being heated forms.

" photo-hardening functional group " is meant the functional group that is subjected to light and causes the hardening of resin reaction.

About the photo-hardening functional group, concrete adopts universe English husband, forever pine unit too youth's work " photosensitivity macromolecule (the talk .1977 of society publishes); " the color ultraviolet curable resin " of angle Tian Longhong work (publishing department of printing association published in 1981); G.E.Green and B.P.strak be published in enumerate in the introductions such as article that J.Macro.Sci.Reas.Chem.C21 (2) .187～273 (1981～82) and C.G.Rattey be published in " photopolymerization of surface coating " (A.Wiley Inter Science Pub.1982 publication) as ray hardening resin, be applied to the known functional group in the photoresist etc. already.

For example can list the aggretion type dimerization in conjunction with base, photo-crosslinking type dimerization in conjunction with base etc.

[chemical formula 7]

In conjunction with base, concrete can list following group as the aggretion type dimerization.CH ₂＝CH-，CH ₂＝CHCH ₂-，CH ₂＝CHCOO-，CH ₂＝C(CH ₃)COO-，C(CH ₃)H＝CHCOO-，CH ₂＝CHCONH-，CH ₂＝C(CH ₃)CONH-，C(CH ₃)H＝CHCONH-，CH ₂＝CHOCO-，CH ₂＝C(CH ₃)OCO-，CH ₂＝CHCH ₂OCO-，CH ₂＝CHNHCO-，CH ₂＝CHCH ₂NHCO-，CH ₂＝CHSO ₂-，CH ₂＝CHCO-，CH ₂＝CHO-，CH ₂＝CHS-。

As photo-crosslinking type dimerization in conjunction with base, particularly with the maleimide base shown in the following general expression (A) for well.

[chemical formula 8]

General expression (A)

[R in the formula (A) ²And R ³Represent hydrogen atom respectively, halogen atom and alkyl, R ²And R ³Also can be] in conjunction with forming 5 yuan or 6 yuan of rings

The R here ²And R ³The carbon number 1～4 of alkyl for well, good especially is methyl.R ²And R ³6 yuan of rings are also fine in conjunction with forming.Halogen atom with chlorine, bromine and iodine atom for well.

Object lesson with maleimide is opened (corresponding to United States Patent (USP) 4,079, No. 041) communique clear 52-988 number the spy, Deutsches Reichs-Patent 2,626, No. 769 instructionss, 21, No. 019 instructionss of European patent, European patent 3, No. 552 instructionss or Die AngewandteMackromolek ulare Chemi.115 volume (1983) 163～181 pages, the spy opens clear 49-128, No. 911～No. 128993, the spy opens clear 50-5376 number～No. 5380, and the spy opens clear 51-5298 number～No. 5300, the spy opens clear 50-50107 number, the spy opens clear 51-47940 number, and the spy opens clear 52-13907 number, and the spy opens clear 50-45076 number, the spy opens clear 52-121700 number, the spy opens clear 50-10844 number, and the spy opens clear 50-45087 number, and the spy opens clear 58-43951 number and waits each communique, Deutsches Reichs-Patent 2,349, No. 948,2, wait on the communique all on the books 616, No. 276.

The present invention can use the monomer of for example representing with following general expression (B)～(D) in these compounds.

[chemical formula 9]

General expression (C)

[Chemical formula 1 0]

[the R in the formula (B)～(D) ²And R ³With the R in the general expression (A) ²And R ³Phasing is same, R ⁴Expression hydrogen atom or methyl, n ₁, n ₂And n ₃Be integer, with 1～6 for well]

Also having, as the monomer that uses in the photoionization base polymerization crosslinking, is to contain the compound of energy addition polymerization dimerization in conjunction with base.In detail, can have 1 at least, preferably have in the compound of 2 above unsaturated ethylene ethylene linkages and select arbitrarily from end.

For example have monomer, prepolymer is a dipolymer, the compound of trimer and oligomer or their potpourri and their chemical forms such as multipolymer.

As the example of monomer and multipolymer thereof, can enumerate acid amides as fat, unsaturated carboxylic acid and the aliphatics multivalence amines of unsaturated carboxylic acid (for example acrylic acid, methacrylic acid, furoate clothing, crotonic acid, iso-crotonic acid, maleic acid etc.) and aliphatics multivalence alcoholic compound etc.

The object lesson of the ester monomer that aliphatics multivalence alcoholic compound and unsaturated carboxylic acid generate, as acrylate diacrylate second diester, diacrylate three second diester, diacrylate-1 arranged, 3-fourth diester, diacrylate tetramethylene second diester, diacrylate propylene diester, new penta diester of diacrylate, propyl group three acrylic acid trimethyls, trihydroxy methyl propyl group three (acryloyl-oxy propyl group) ether, ethyl three acrylic acid trimethyls, the own mercapto ester of diacrylate, diacrylate-1,4-hexamethylene mercapto ester, diacrylate tetrem diester, diacrylate Ji Wusi ester, three acrylic acid Ji Wusi esters, tetrapropylene acid Ji Wusi ester, two seasons penta 4 of diacrylate ester, two seasons penta 4 of amyl group acrylic acid ester, two seasons penta 4 of hexyl acrylic acid ester, three acrylic acid sorbitol esters, tetrapropylene acid sorbitol ester, amyl group acrylic acid sorbitol ester, hexyl acrylic acid sorbitol ester, three (acrylyl oxy-ethyl) triisocyanate, methacrylic acid tetramethyl ester, polyacrylate oligomer etc.

As methacrylate dimethacrylate tetrem diester arranged, dimethacrylate three second diester, new penta diester of dimethacrylate, oxypropyl trimethyl acrylic acid trimethyl, ethyl-trimethyl acrylic acid trimethyl, dimethacrylate second diester, dimethacrylate-1,3-fourth diester, the own diester of dimethacrylate, dimethacrylate Ji Wusi ester, trimethyl acrylic acid Ji Wusi ester, tetramethyl acrylic acid Ji Wusi ester, two seasons penta 4 of dimethacrylate ester, two seasons penta 4 of hexyl methyl acrylic acid ester, two seasons penta 4 of amyl group methacrylic acid ester, the acrylic acid sorbitol ester of trimethyl, the acrylic acid pears alcohol ester of tetramethyl, two [right-(3-methacryloxypropyl-2-hydroxyl third oxygen) benzene] dimethylmethane, two [right-(methacryloxypropyl ethoxy) benzene] dimethylmethane etc.

As the two furoate clothing second diester that have of furoate clothing fat, two furoate clothing propylene diesters, two furoate clothings-1,3-fourth diester, two furoate clothings-1,4-fourth diester, two furoate clothing tetramethylene diester, two clothing chaff carbon Ji Wusi esters, the pears alcohol ester of four furoate clothings etc.

As the two crotonic acid second diester that have of crotons carbon ester, two crotonic acids, four methylene diester, two crotonic acid Ji Wusi esters, the pears alcohol ester of four crotonic acids etc.

As the two iso-crotonic acid second diester that have of iso-crotonic acid ester, two iso-crotonic acid Ji Wusi esters, the pears alcohol ester of four iso-crotonic acids etc.

As the two maleic acid second diester that have of maleate, two Malaysia triethylenetetraminehexaacetic acid diester, two maleic acid Ji Wusi esters, the pears alcohol ester of four maleic acids etc.

Can also list the potpourri of above-mentioned ester monomer.

Amide monomer as aliphatics multivalence amines and unsaturated carboxylic acid, concrete example has methylene-bisacrylamide, the di-2-ethylhexylphosphine oxide Methacrylamide, 1,6-hexylidene bisacrylamide, 1, the two Methacrylamides of 6-hexylidene, diethylene triamine three acrylamides, xylyl bisacrylamide, the two Methacrylamides of dimethyl benzene etc.

Other example also can be enumerated on the polyisocyanate acyl compound of putting down in writing in the special public clear 48-41708 communique that two above isocyanate group are arranged in a molecule and contain, in addition contain the vinyl urethane compound that two above polymerization of vinyl are arranged in the molecule of vinyl monomer of following formula (E) expression hydroxyl.

CH ₂＝C(R ₅)COOH ₂CH(R ₆)OH (E)

Can also enumerate as the spy and open the upward urethane acrylate class of record clear 51-37193 number, the spy opens clear 48-64183 number, the spy opens clear 49-43191 number, the spy opens clear 52-30490 number and waits the polyester acrylate class of putting down in writing on the communique, multi-functional acrylate or methacrylates such as epoxy acrylate class that epoxy resin and the reaction of (methyl) acrylic acid generate.Can also use the last compound of the Japan's bonding will Vol.20.No.7.300-308 of association page or leaf (1984) as photo-hardening type monomer and oligomer introduction.The use amount of these compounds be with respect to the 5-70 weight % (to call % in the following text) of total composition with 10-50 weight % for well.

As the Photoepolymerizationinitiater initiater that contains in the used photo-polymerization type imaging layer (composition) of the present invention, can according to the wavelength of employed light source suitably select to use various light triggers or the Photoepolymerizationinitiater initiater more than two kinds and with series (photopolymerization causes series).These are well-known in the report of patent, document.

For example during near the light source using 400nm, just be extensive use of benzyl, benzoin ether, the sweet ketone of rice, anthraquinone, thioxanthones, acridine, azophenlyene, benzophenone etc.

As the aforementioned lights sensitive agent, can use " the light reaction macromolecule " of EP 591786 and A.Reiser.Wiley Intersiciennce (1989) goes up the photodimerization type sensitizer of record.

It below is the example of the polymkeric substance of photo-crosslinking generation.

[Chemical formula 1 1]

[Chemical formula 1 2]

[Chemical formula 1 3]

Be the synthetic example of the used cross-linked polymer of the present invention below.

[polymkeric substance KP-3's is synthetic].

With styrene sulfonic acid-1-methyl-2-methoxyl ethyl ester (0.4 mole), the N-[(3-methacryloxypropyl) propyl group]-2,3-dimethyl maleimide (0.1 mole) and MEK 203 grams are put into there-necked flask, 65 ℃ of nitrogen flow down and add 2.44 gram azo dimethyl Verelo nitriles (trade name, polypropylene nitrile synthetic cellulose).Keep this temperature and stir after 5 hours decompression and steam to contract and remove MEK, obtain solid.It according to fixed its mean molecular weight of GPC (polystyrene standard) 25,000 polymkeric substance.

[polymkeric substance KP-4,5 synthetic]

Except using the N-[(6-methacryloxypropyl) hexyl]-2,3-dimethyl maleimide or propenyl methacrylic acid are replaced the N-[(3-methacryloxypropyl) propyl group]-2, beyond the 3-dimethyl maleimide, all the other are synthetic identical with the polymkeric substance KP-3's of front.For the required styrene sulfonate of polymkeric substance KP-4, adopt the styrene sulfonic acid cyclohexyl.The mean molecular weight of polymkeric substance KP-4 is 56,000, and polymkeric substance KP-5 is 19,000.

[polymkeric substance KP-1's is synthetic]

Except 2-methylacryoyloxyethyl isocyanates is replaced the N-[(3-methacryloxypropyl) propyl group]-2, beyond the 3-dimethyl maleimide, all the other are synthetic identical with the polymkeric substance KP-3's of front.Then add acrylic acid (0.1 mole) in reactant liquor, further heated and stirred is 8 hours, and reaction finishes the back decompression distillation and removes the demethyl ethyl ketone, obtains solid.According to GPC (polystyrene standard) is that mean molecular weight is 23,000 polymkeric substance as can be known.

[polymkeric substance KP-2's is synthetic]

Except replacing the methacrylic acid with acrylic acid, all the other are identical with the synthetic method of the polymkeric substance KP-1 of front.Mean molecular weight is 23,000.

[polymkeric substance KP-9's is synthetic]

With [(3-acryloyl-oxy propane) sulphonic acid ester]-1-methyl-methoxy ethyl ester (0.4 mole), acrylic acid-2-[(6-chlorine third oxygen) ethyl] ester (0.1 mole) and 254 the gram methyl alcohol join in the there-necked flask, 64 ℃ of nitrogen flow down and add the two dimethyl verelo nitriles (trade name) of 2.44 gram azos, are cooled to room temperature after stirring 5 hours under this temperature.Triethylamine (0.1 mole) is added in the cooling back, stirs 6 hours, joins then in the excessive water, must solid.According to GPC (polystyrene standard) is that mean molecular weight is 25,000 polymkeric substance as can be known.

[KP-11's is synthetic for polymkeric substance KP-8, KP-10]

Except replacing corresponding monomer respectively, all the other synthesize with the same method of polymkeric substance KP-9.According to GPC (polystyrene standard) is mean molecular weight as can be known.KP-8 is 30,000, and KP-10 is 28,000, and KP-11 is 35,000 polymkeric substance.

[photo-thermal conversion agent]

When using the laser explosure imaging, in imaging layer, preferably contain the photo-thermal conversion agent for heat-sensitive lithographic plate of the present invention.Laser explosure with infrared ray for well.At this moment photo-thermal conversion agent is an infrared absorbent.

The optimal infrared absorbent of the present invention is ultrared dyestuff or the pigment of effective absorbing wavelength 760nm to the 1200nm scope, is more preferably the dyestuff or the pigment that wavelength 760～1200nm there are very big absorption.

Know dyestuff altogether as what dyestuff can use record in commercially available dyestuff or the document (for example " dyestuff brief guide ", Synthetic Organic Chemistry association compiles, and is clear and published in 45 years).Specifically can enumerate azo dyes, metal complex azo dyes, pyrazolone azo dyes, anthraquinone dye, phthalocyanine dye, carbonium dye, quinoneimine dye, methine dyes, cyanine dye, metal mercaptide salt complex etc.

Can list as the spy as desirable dyestuff and to open clear 58-125, No. 246, the spy opens clear 59-84356 number, the spy opens clear 59-202829 number, the spy opens the cyanine dye of putting down in writing in the clear 60-78787 grade, the spy opens clear 58-173696 number, the spy opens clear 58-181690 number, the spy opens the methine dyes of putting down in writing in the clear 58-194595 grade, the spy opens clear 58-112793 number, the spy opens clear 58-224793 number, the spy opens clear 59-48187 number, the spy opens clear 59-73996 number, the spy opens clear 60-52940 number, the spy opens the naphthoquinone dyestuff of putting down in writing in the clear 60-63744 grade, the spy opens the 30 carbon salt dyestuffs of putting down in writing in the clear 58-112792 grade, the cyanine dye of record etc. in No. 434875, the BrP.

United States Patent (USP) 5,156, be loaded with the sensitizer that is applicable near infrared absorption in 938, United States Patent (USP) 3,881, be loaded with aryl benzo (sulphur) pyralium salt in No. 924, the spy opens (United States Patent (USP) 4 clear 57-142645 number, 327, No. 169) in be loaded with the cyclonite pyralium salt, the spy opens clear 58-181051 number,-No. 220146, the spy opens clear 59-41363 number,-No. 84248,-No. 84249,-No. 146063, be loaded with pyran compounds in-No. 146061, the spy opens in clear 59-216146 number and is loaded with cyanine dye, be loaded with five methine sulphur pyralium salts in No. 4283475, the United States Patent (USP), the spy opens flat 5-13514 number, pyralium salt compound in-No. 19702 communiques.These all are good.

As dyestuff preferably, other example can be enumerated United States Patent (USP) 4,756, in No. 983 instructionss with formula (I), (II) hear-infrared absorption dye of being put down in writing.

In these dyestuffs, it is desirable to cyanine dye especially, 30 carbon salt dyestuffs, pyralium salt and nickelous sulfate complex compound.

As the used pigment of the present invention, can be with commercially available pigment or colored index brief guide, (Japanese pigment technology association compiles " up-to-date pigment brief guide ", issued a magazine in 1977), (CMC publishes " up-to-date pigment applications technology ", 1986 annuals), the pigment put down in writing in waiting of " printing-ink technology " (CMC publish, 1984 annuals).

Kind as pigment can list black, and yellow is orange, brown, and redness, purple, blue look, pigment and fluorescent pigments such as green, metal powder pigment and polymkeric substance are in conjunction with pigment.Specifically can use insoluble azo colour, azophloxine pigment, condensed azo pigment, chelating AZO pigments, the phthalocyanine AZO pigments, anthraquinone class pigment, perillene or purple perilla ketone pigment, thioindigo class pigment, quinoline a word used for translation ketone pigment ， dioxazines pigment, isoindoline-1-ketone pigment, Kui phthalein ketone pigment is sticky with red, azine pigment, nitroso pigments, nitropigments, natural pigment, fluorescent pigment, inorganic pigment, carbon black etc.It is desirable to carbon black in these pigment.

Can not carry out surface treatment to these pigment uses, use more superior after the surface treatment, the surface-treated method can be to resinize or wax, attaching surface activating agent in the surface, allow reactivity material (for example silane coupling agent or epoxide, polyisocyanate salt etc.) be combined in methods such as surface of pigments.Above-mentioned surface treatment method is recorded in " character of metallic soap alkali and application " (good fortune study), on " printing-ink technology " (CMC publishes 1984 annuals) and " up-to-date pigment applications technology " (CMC publishes 1986 annuals).

The particle diameter of pigment with 0.01 micron～10 microns scope for well, better 0.05 micron～1 micron scope, particularly 0.1 micron～1 micron scope is best.When the particle diameter of pigment during less than 0.01 micron, the stability that is dispersed in heat-sensitive composition in the coating fluid is just bad, and during greater than 10 microns, the homogeneity of coating back imaging layer is just bad.

As the method for dispersed color, can take to be used for the known dispersion technology of printing ink manufacturing or toner manufacturing.Can list ultrasonic decollator, sand mill, masher, micro grinder, super grinding machine, bowl mill, turbine grinding machine, dispersion machine, KD grinding machine, get body mill, dynatron, tri-roll press machine, homogenizer etc. as the device that disperses, detailed see " up-to-date pigment applications technology " (CMC publishes, 1988 annuals).

Total solid component ratio in the imaging layer composition of these dyestuffs or pigment relatively hot susceptibility lithographic plate is 0.01～50 weight %, be preferably 0.1～10 weight %, in the occasion of dyestuff, be 0.5～10 weight %, be 1.0～10 weight % in the occasion of pigment.The addition of pigment or dyestuff is during less than 0.01 weight %, and light sensitivity reduces, and when surpassing 50 weight %, just causes the pollution at non-image position in the printing easily.

[other composition]

Though use mentioned component among the present invention as required,, also can add various other compounds as required.

For example can use and have the coloring agent of the dyestuff of bigger absorption in the visible region as image.The concrete oil yellow enumerated 101#, oil yellow 103#, oil product 321#, glossy dark green BG, oily blue BOS, oil blue 603#, glossy black BY, glossy black BS, glossy black T-505 (above is that east chemical industry dwarf formula commercial firm makes), the pure orchid of Victoria, crystal violet (CI42535), ethyl violet, rhodamine B (CI145170B), peacock green (CI42000), methylene blue (CI52015) etc., or the spy opens clear 62-293247 communique, special dyestuff of being willing to record in flat 7-335145 number.

Its addition is to be the ratio of 0.01～10 weight % with respect to the total solid composition in the heat-sensitive lithographic plate imaging layer.

In the imaging layer of radioinduction lithographic plate of the present invention, can also be added to the surfactant that enlarges stability with respect to printing condition.Have the spy to open clear 62-251740 number or special open the non-ionics of putting down in writing in the flat 3-208514 communique, the spy opens clear 59-121044 communique, the spy opens the amphoteric surfactant of putting down in writing in the flat 4-13149 communique.

Examples of nonionic surfactants has sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, glyceryl monostearate, polyoxyethylene nonyl phenylate etc.

The object lesson of amphoteric surfactant has alkyl two (amino-ethyl) glycocoll, the poly-amino-ethyl glycine hydrochloride of alkane, second-alkyl-N-carboxyethyl-N-hydroxyethyl imidazole betaine salt or N-four decyls-N, N-betaines (for example trade name Ah rubbing wants K, and first Industrial Co., Ltd makes).

In addition as required, in heat-sensitive lithographic plate imaging layer of the present invention, can also add the plastifier of paying pliability etc. to filming.For example can use polyethylene glycol, tributyl citrate, diethyl phthalate, Dibutyl phthalate, phthalandione dihexyl, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, oleic acid tetrahydrofurfuryl, the oligomer of acrylic or methacrylic acid or superpolymer etc.

The imaging layer manufacturing of heat-sensitive lithographic plate of the present invention normally is dissolved in above-mentioned each composition in the solvent, is coated on the suitable supporter.Solvent used herein, though dichloroethylene, thiacyclohexane, MEK, methyl alcohol, ethanol, propyl alcohol, glycol monoethyl ether, 1-methoxy-2-propyl alcohol, acetate-2-methoxy ethyl ester, acetate-1-methoxy-2-propyl ester, dimethoxy ethane, methyl lactate, ethyl lactate, N are arranged, the N-dimethyl acetamide, N, dinethylformamide, tetramethylurea, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), sulfolane, r-butyrolactone, toluene and water etc., but be not limited in these compounds.

These solvents can be used alone or as a mixture.The concentration of mentioned component in the solvent (the total solid composition that comprises adjuvant) is preferably in 1～50 weight % scope.After the coating drying, the coating weight on the supporter (solid very much) is generally with at 0.5～5.0 gram/rice ²For good.The method of coating has multiple, for example bar type coating, and rotary coating, spraying, curtain coating, dip-coating, airblade coating, blade coating, roller are coated with etc.

Can also add the surfactant that improves coating in the heat-sensitive lithographic plate imaging layer of the present invention.The for example special fluorochemical surfactant of putting down in writing in the clear 62-170950 communique of opening.Desirable addition is to be 0.01～1 weight % with respect to total solid composition in the imaging layer, preferably 0.05～0.5 weight %.

Employed supporter (substrate) when the present invention is coated with the image forming material of above-mentioned imaging layer on original edition for lithographic printing plate is the plate object of dimensionally stable, as the supporter of galley, comprises still can using of using now.As such supporter, can use paper, the paper of laminated plastic (for example tygon, polypropylene, polystyrene etc.), aluminium (comprising aluminium alloy), sheet metals such as zinc, iron, copper, cellulose diacetate, Triafol T, cellulose propionate, butyric acid cellulose, butyric acid vinegar carbon cellulose, plastic foils such as nitre ester fiber element, polyvinyl terephthalic ester, tygon, polypropylene, polycarbonate, polyvinyl acetal, the paper of above-mentioned metal laminate or evaporation or plastic foil etc., but good especially be aluminium sheet.Aluminium sheet comprises pure aluminum plate and aluminium alloy plate.Can use as aluminium alloy various, the alloy of metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel and aluminium for example.These compositions contain the impurity that some iron and titanium maybe can the ignorance amounts.

The supporter that uses in the original edition for lithographic printing plate of the present invention (substrate) is the plate object of dimensionally stable, as the supporter of galley, comprises that use so far and still spendable.Though comprise paper as such support, laminated plastic (for example tygon, polypropylene, polystyrene etc.) paper, aluminium (comprising aluminium alloy), plastic foils such as sheet metals such as zinc, iron, copper, cellulose diacetate, Triafol T, third carbon cellulose, butyric acid cellulose, butyric acid cellulose acetate, cellulose nitrate, polyvinyl terephthalic ester, tygon, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, above-mentioned metal laminate or the paper of evaporation or plastic foil etc., but aluminium sheet best.Aluminium sheet comprises pure aluminum plate and aluminium alloy plate.Aluminium alloy has multiple the use, for example the alloy of metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel and aluminium.Contain the impurity that some iron and titanium or other can the ignorance amounts in these compositions.

Supporter is carried out surface treatment as required, for example water wettability is carried out on the surface of supporter and handle.

To having metal, particularly having the supporter on aluminium surface, preferably advance graining and handle, at sodium silicate, fluoridize the dip treating in the aqueous solution such as potassium zirconium, phosphate, or surface treatment such as anodic oxidation.Also has the aluminium sheet of putting down in writing in 2,714, No. 066 instructions of picture United States Patent (USP) in graining processing back dip treating in sodium silicate aqueous solution, United States Patent (USP) 3, in 181, No. 461 explanations record to after the aluminium sheet anodized, dip treating in the aqueous solution of alkali silicate again.Supporter after handling like this is very suitable.For above-mentioned anodization, for example use mineral acid or organic acid or these sour brine solution or non-aqueous solution such as oxalic acid, sulfaminic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid, in the electrolytic solution of independent or two or more combinations, as anode, energising is handled with aluminium sheet.

The silicate electro-deposition of putting down in writing in the United States Patent (USP) 3,658, No. 682 instructionss also is effective.These water wettabilities are handled, and except that for supporting body surface is formed the water wettability, also for preventing that going up the recording layer of setting with it produces adverse reaction, also are the adherence of raising and recording layer.Before aluminium sheet being carried out the graining processing, preferably implement surperficial pre-treatment as required, remove the rolling oil on surface and the aluminium surface of exposing cleaning.Can use triclene equal solvent, surfactant for pre-treatment.Can use the method for the alkaline corrosion such as NaOH, potassium hydroxide of extensive employing for aftertreatment.

About the method that graining is handled, no matter machinery, chemistry or electrochemical method all is effective.Ball-milling method, abrasive blasting method are arranged and resemble the brushing method etc. of the lapping compound aqueous dispersion mud of float stone one class with the nylon bruss wiping as the method for machinery.Method as chemistry has the spy to open the method for putting down in writing in the clear 54-31187 communique of flooding in the saturated aqueous solution of mineral acid aluminium salt.As electrochemical method, it is desirable to method at hydrochloric acid, nitric acid or their acid mixture alternating current electrolysis in acidic electrolysis bath.The combined asperities method of the mechanical asperitiesization put down in writing in the clear 55-137993 communique and electrochemical asperitiesization of particularly opening with the spy in such asperities method is for well.Owing to strengthened the adhesion of susceptibility image and supporter, so ideal.

Preferably implement graining according to top method and handle the scope that the mean roughness (Ra) that makes the surface of aluminum plate center line reaches the 0.3-1.0 micron.

This aluminium sheet of handling through graining is washed and chemical corrosion as required.

Usually select the alkali or the aqueous acid of dissolved aluminum about corrosion treatment liquid.At this moment on the surface that is corroded, must not contain because of the corrosive liquid composition and induce the covered film different that forms with aluminium.Desirable mordant for example, as alkaline matter NaOH, potassium hydroxide, tertiary sodium phosphate, disodium hydrogen phosphate, tripotassium phosphate, dikalium phosphate etc. are arranged, as acidic materials sulfuric acid, persulfuric acid, phosphoric acid, hydrochloric acid and salt thereof etc. are arranged.But than the low metal of aluminium ion tendency, for example the salt of zinc, chromium, cobalt, nickel, copper etc. forms unnecessary covered film owing to understand on the corrosion surface, so inapplicable.

The concentration that these mordant use, the setting of temperature, the dissolution velocity of used aluminium or alloy, preferably with every dipping formed in one minute the 0.3-40 gram/square metre mode carry out.More also can in this scope.

Desirable processing is that aluminium sheet is impregnated in the corrosive liquid, or corrosive liquid is applied on the aluminium sheet, etching extent 0.5-10 gram/square metre scope.

As above-mentioned mordant, consider preferably to use aqueous alkali from the characteristics that said corrosion speed is fast.But at this moment can generate dirt, will carry out crude removal usually and handle.The acid that is used for the crude removal processing has nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluorite, boron hydrofluorite etc.The aluminium sheet of corrosion treatment is washed and anodic oxidation as required.Anodic oxidation can be undertaken by the method that use in this field always.Specifically can perhaps in their composition solutions or non-aqueous solution more than two kinds,, on the aluminium support body surface, form anode oxide film at sulfuric acid, phosphoric acid, chromic acid, hydrobromic acid, sulfaminic acid, benzene sulfonic acid etc. to perfectly straight stream of aluminium sheet or alternating current.

Anodised treatment conditions, though various variations are arranged according to the difference of using electrolytic solution, cannot treat different things as the same, but the concentration of general electrolytic solution is at 1-30 weight %, 5-70 ℃ of liquid temperature, current density 0.5-60 ampere/square decimeter, voltage 1-100 volt, 30 seconds-50 minutes scope of electrolysis time is suitable.

In these anode oxidative treatment methods, particularly BrP 1,412, put down in writing in No. 768 instructionss, in sulfuric acid, carry out anodised method and United States Patent (USP) 3,511 with high current density, put down in writing in No. 611 instructionss, carry out anodised method for well as electrolytic solution with phosphoric acid.

Above-mentioned through surperficial asperities processing and further anodised aluminium sheet, preferably carry out water wettability as required and handle, its desirable example is a United States Patent (USP) 2,714, No. 066 and 3, the alkali silicate that discloses in 181, No. 461, for example clear 36-22 of sodium silicate aqueous solution facture and Te Kai, that points out in No. 063 communique fluoridizes potassium zirconium, and the disposal route of the polyvinylsulfonic acid of pointing out in 4,153, No. 461 instructionss of United States Patent (USP).

Organic underlayer:

Heat sensitivity lithographic plate of the present invention will be coated with organic bottom before the coating imaging layer, to reduce residual non-image part in the imaging layer.The organic compound that this organic underlayer is used, for example can select carboxymethyl cellulose for use, dextrin, Arabic gum, contain sulfonic acid just like second-tarine etc., also can select for use and contain substituent benzene sulfonic acid, naphthalene sulfonic acids, alkyl sulfonic acid, glyceryl sulfonic acid, the organic sulfonic acid of methylene-disulfonic acid and ethylidene sulfonic acid etc., also can select for use and contain substituent phosphenylic acid, naphthyl phosphoric acid, organic phosphoric acid such as alkyl phosphoric acid and phosphoglycerol, can also select for use and contain substituent phenyl-phosphonic acid, the naphthyl phosphonic acids, the organic phospho acid of alkyl phosphonic acid and glycerine phosphonic acids etc. also has the hydrochloride that contains hydramine of amino acids such as glycocoll or Beta-alanine and triethanolamine hydrochloric acid etc.Except these chemical substances of independent use, also can use potpourri more than two kinds.

Can be with the macromolecular compound that other polymerization (right-the vinyl benzoic acid) structural unit is arranged.

This organic underlayer can be provided with as follows.Be about to above-mentioned organic compound solvent in organic solvents such as water or methyl alcohol, ethanol, MEK or their mixed solvent, coat on the supporter, then Gan Zao method; Perhaps supporter has been dissolved in organic solvent such as water or methyl alcohol, ethanol, methyl ethyl ketone or their mixed solvent in the solution of above-mentioned organic compound and flooded, be adsorbed with organic compounds, washed then, dry method.The organic concentration of former approach is the solution of 0.005-10 weight %, and various coating process coatings are arranged.For example with bar type coating, rotary coating, spraying, curtain coating etc., any method all has passable.And the solution concentration of latter's method is 0.01-20 weight %, is preferably 0.05-5 weight %, and dipping temperature is 20-90 ℃, is preferably 25-50 ℃, and dip time is 0.1 second-20 minutes, is preferably 2 seconds-1 minute.

Solution used herein utilizes alkaline matters such as ammonia, triethylamine, potassium hydroxide, or acidic materials such as hydrochloric acid, phosphoric acid regulate pH values all can, be adjusted in the 1-12 scope and use.In order to improve the tone rendering of heat-sensitive lithographic plate, also can add weld.

Organic underlayer dried by complexor with 2-200 milligram/square metre for suitable, be preferably the 5-100 milligram/square metre.Less than 2 milligrams/square metre or printability resistance can be all insufficient during greater than 200 milligrams/square metre.

In order to improve the adherence of organic underlayer and imaging layer, can coat at least a silane coupling agent that contains addition polymerization functional group on the surface of aluminium support body, it is under the catalytic action of organic sulfonic acid shown in the following general expression (F), add water decomposition and polycondensation reaction, the compound that obtains is coated with and is located on the aluminium support body surface.

RSO ₃H (F)

(R represents the organic group of carbon number 2-50)

Silane coupling agent adds the compound that water decomposition and polycondensation reaction form under the catalytic action of above-mentioned organic sulfonic acid, be containing-inorganic polymer of Si-O-si-key on fixing addition reactivity functional group's organic mineral complex.

On supporting body surface, be coated with adhesive linkage among the present invention, can use this organic mineral complex, adopt so-called sol-gel process (to call the SG method in the following text).About SG method visible " state-of-the-art technology of organosilicon polymer ", chapter 6, (the refined husband of modern well is outstanding for sol-gel process and " research trend of polymeric silicon ", CMC publishes, distribution in 1996), and " science of sol-gel process " (makes flower Ji husband work, AGUNE holds wind society and publishes, and issues a magazine in 1988).But the present invention not only is defined in these methods.

This organic mineral complex is applied on the supporter as adhesive linkage, a drying, the inorganic polymer part is just with the supporter adherence, and the addition active function groups just intactly remains on the supporting body surface.

Make silane coupling agent in the presence of catalyzer according to the SG method, in containing the solution such as alcohol of low amounts of water, add the reaction of water decomposition and condensation polymerization, this is contained the fluid composition of inorganic polymer, be applied to as adhesive linkage on the surface of supporter, according to circumstances carry out drying, so just the addition reaction active function groups can be applied on the supporter.

Because complexing is fixed on the distribution of the addition active function groups on the supporting body surface, the seldom distribution of chemical property such as left and right supporting surface acid point or alkali point is so the SG method is a kind of good method.

As the used silane coupling agent of the present invention, can enumerate the compound shown in following general expression (G).

R _a(R _b)SiR _c(R _d) (G)

(R _a-R _dHave at least two to represent that carbon numbers are the alkyl below 10, or-OCOR ' base, other expression addition polymerization base, R ' represents alkyl).

The alkyl of R ' expression has methyl, ethyl, propyl group etc. in the general expression (G), and the addition polymerization active group has alkenyl, alkynyl etc., between silicon atom and these addition polymerization active groups, and also can be in conjunction with various concatenating groups.As alkenyl vinyl, propenyl, butenyl group, dialkyl group maleimide base etc. are arranged, as alkynyl ethinyl, alkyl ethinyl etc. are arranged.

Can enumerate the compound of record among " silane coupling agent " (Edwin P.Plued demaunPlemum Press 1982) as silane coupling agent.

Specifically can list compounds such as tetramethoxy-silicane, tetraethoxysilane, tetraisopropoxysilan, four (just-propoxyl group) silane, four (just-butoxy) silane, four (2-ethyl butoxy) silane, four (2-ethyl hexyl oxy) silane, four (2-methoxy ethoxy) silane, tetraphenoxy-silicane alkane, tetrem acyloxy silane.Especially with tetraethoxysilane for well.

Silane coupling agent as the ethene dimerization association reaction base of tool addition polymerization specifically has: CH ₂=CH-Si (OCOCH ₃) ₃,

CH ₂＝CH-Si(OC ₂H ₅) ₃、

CH ₂＝CH-Si(OCH ₃) ₃、

CH ₂＝CHCH ₂-Si(OC ₂H ₅) ₃、

CH ₂＝CHCH ₂NH(CH ₂) ₃-Si(OCH ₃) ₃、

CH ₂＝CHCOO-(CH ₂) ₃-Si(OCH ₃) ₃、

CH ₂＝CHCOO-(CH ₂) ₃-Si(OC ₂H ₅) ₃、

CH ₂＝CHCOO-(CH ₂) ₄-Si(OCH ₃) ₃、

CH ₂＝C(CH ₃)COO-(CH ₂) ₃-Si(OCH ₃) ₃、

CH ₂＝C(CH ₃)COO-(CH ₂) ₃-Si(OC ₂H ₅) ₃、

CH ₂＝C(CH ₃)COO-(CH ₂) ₄-Si(OCH ₃) ₃、

CH ₂＝C(CH ₃)COO-(CH ₂) ₅-Si(OCH ₃) ₃、

(CH ₂＝C(CH ₃)COO-(CH ₂) ₃) ₂-Si(OCH ₃) ₂、

CH ₂＝C(CH＝CH ₂)-Si(OCH ₃) ₃、

CH ₂＝CH-SO ₂NH-(CH ₂) ₃-Si(OCH ₃) ₃、

CH ₂＝CH-ph-O-Si(OCH ₃) ₃、

(ph represents phenyl ring)

CH ₂＝CH-ph-CONH-(CH ₂) ₃-Si(OCH ₃) ₃、

CH ₂＝CH-ph-CH ₂NH-(CH ₂) ₃-Si(OCH ₃) ₃、

CH ₂＝CH-ph-CH ₂NH-C ₂H ₄NH(CH ₂) ₃-Si(OCH ₃) ₃·HCl

HC≡C-Si(OC ₂H ₅) ₃、

CH ₃C≡C-Si(OC ₂H ₅) ₃、

DMI-(CH ₂)m-CONH-(CH ₂) ₃-Si(OCH ₃) ₃、

(DMI: expression dimethyl maleimide, m=1～20)

CH ₂＝CHCH ₂O-Si(OCH ₃) ₃、

(CH ₂＝CHCH ₂O) ₄Si、

HO-CH ₂-C≡C-Si(OC ₂H ₅) ₃、

CH ₃CH ₂CO-C≡C-Si(OC ₂H ₅) ₃、

CH ₂＝CHS-(CH ₂) ₃-Si(OCH ₃) ₃、

CH ₂＝CHCH ₂O-(CH ₂) ₂-SCH ₂-Si(OCH ₃) ₃、

CH ₂＝CHCH ₂S-(CH ₂) ₃-S-Si(OCH ₃) ₃、

(CH ₃) ₃CCO-C≡C-Si(OC ₂H ₅) ₃、

(CH ₂＝CH) ₂N-(CH ₂) ₂-SCH ₂-Si(OCH ₃) ₃、

CH ₃COCH＝C(CH ₃)-O-Si(OCH ₃) ₃

But be not limited to these compounds.

Silane coupling agent also can be so that ratio and several compound are used arbitrarily.

Above-mentioned when containing the adhesive linkage that makes silane coupling agent can carry out the compound of SG reaction and being coated on the support, this compound can use separately also can mix use.Also can use with appropriate solvent dilution back.As solvent can be methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, ethylene glycol, hexene ethylene glycol, THF, DMF etc., though alcohols is good especially, also organic solvent can be mixed and use.

Solvent load is generally 0.2-500 doubly according to the total weight of using silane coupling agent, is preferably 0.5-100 doubly, and more preferably 1-20 doubly.When being less than 0.2 times, reactant liquor is easy to gelation and instability after after a while; And during greater than 500 times, the time of reaction is wanted several days, and is also bad.

In the present invention in order to promote hydrolysis reaction can add water.The amount of water that adds the water decomposition silane coupling agent, generally each mole compound is the 0.1-1000 mole, is preferably the 0.5-200 mole, more preferably the 5-100 mole.When per 1 mole compound of the water yield is less than 0.1 grammol, will postpone the polycondensation reaction that adds water decomposition and follow, finishing stable surface treatment then needs several days time; When per 1 mole compound of the water yield is more than 1000 moles on the other hand, can cause that adherence is bad when the composition that metal surface coating generates, or composition stability in time degenerates, gelation immediately usually is difficult to stably be coated with operation.

Allotment is suitable for the temperature of composition of SG method, can be in the scope of room temperature～100 ℃.Also can under the temperature higher, react, at this moment can in reactor, install back flow condenser as required than solvent boiling point.

Back side coating:

Can carry out back side coating as required at the back side of supporter.As back side coating, that puts down in writing in organic high molecular compound that can adopt the spy to open to put down in writing in the flat 5-45885 communique and the flat 6-35174 communique of Te Kai adds the coating that metal oxide that water decomposition and polycondensation form forms by the organic or inorganic metallic compound.

In the middle of these coatings, Si (OCH ₃) ₄, Si (OC ₂H ₅) ₄, Si (OC ₃H ₇) ₄, Si (OC ₄H ₉) ₄Deng the alkyl oxide low price of silicon, obtain easily.The coating of metal oxides water wettability that is made by these compounds is good, and is good especially.

Just can be made into heat-sensitive lithographic plate of the present invention by above step.Can directly implement thermal photography to image by hot record-header; Also can carry out image exposure by ultrared Solid State Laser or the semiconductor laser of emission wavelength 760nm～1200nm.The present invention carries out water development after thermal photography or laser are taken pictures.If be necessary then to carry out again plastic resin treatment, version installed on the printing machine print then; Also can after take pictures, thermal photography or laser version be installed on the printing machine print immediately.Carrying out heat treated after thermal photography or laser are taken pictures can be better.Be divided in 80 ℃～150 ℃ scopes, to carry out 10 seconds～5 as heat treated condition.By this heat treated, during thermal photography or laser just can reduce needed heat or laser energy when taking pictures.

According to the lithographic plate of such processing acquisition, or carry out water development, or intactly install on the offset press like this, can print many times.

Following examples are to detailed explanation of the present invention, but the present invention is not limited to these embodiment.

[embodiment 1-4]

[manufacture method] with support of solution-gel

With nylon bruss and 400 order float stone aqueous suspensions the aluminium sheet of 0.30 millimeters thick is carried out graining and handle, wash.70 ℃ flood 60 seconds down to corrode in the sodium hydrate aqueous solution of 10 weight %, then with the nitric acid neutralization of circulating water washing back with 20 weight %, wash again.Then at V _AUse sine wave alternating current under the condition of=12.7 shapes, in the aqueous solution of nitric acid of 1 weight % with 160 moles/square decimeter.Hour the anode electric weight carry out the processing of electrolysis asperities.Measure 0.6 micron of surface roughness (expression Ra).Then in 30% aqueous sulfuric acid, carry out 55 ℃ of dipping decontamination in 2 minutes processing down, and then the current density with the 2A/ square decimeter is carried out anodized in the aqueous sulfuric acid of 20 weight %, 2 minutes time, the thickness of anode oxide film reach 2.7 the gram/square metre.

Adjust the liquid composition (colloidal sol) of SG method according to following order

Sol solutions

Methyl alcohol 130 grams

Water 20 grams

85 weight % phosphatase 11s, 6 grams

Tetraethoxysilane 50 grams

3-metering system oxygen propyl group trimethoxy silane 60 grams

The sol solutions of above-listed component mixed stirs, confirm its heating after 5 minutes, react and after 60 minutes content is moved on in another container, adding methyl alcohol 3000 restrain sol solutions.Dilute this solution with methyl alcohol/ethylene glycol=9/1 (weight ratio), be 3 milligrams/square metre by the weight of silicon on the substrate and be coated with, 100 ℃ of dryings 1 minute.

[modulation of imaging layer coating fluid]

As the coating fluid of imaging layer, by the modulation of composition shown in following solution

Embodiment	Use polymkeric substance	Add monomer	Sensitizer (polymerization initiator)	The photo-thermal coversion material	Coating solvent
						1 2 3 4 5 6	KP-3 0.4 gram KP-5 0.4 gram KP-1 10.4 gram KP-4 40.4 gram KP-9 0.4 gram KP-11 0.4 gram	Not having no ATMMT 0.2 gram ATMMT 0.2 gram does not have	Following formula (I) the 0.04 following formula of gram (I) 0.04 gram DMAB 0.04 gram DMAB 0.04 gram DMAB 0.04 gram DMAB 0.04 gram	IR125 0.04 gram IR125 0.04 gram IR125 0.04 gram IR125 0.04 gram IR125 0.04 gram IR125 0.04 gram	MEK 1.6 gram MEK 1.6 gram MEK 1.6 gram MEK 1.6 gram MEK 1.6 gram MEK 1.6 grams

(notes) MEK: methyl ethyl ketone

ATMMT: tetrapropylene acid Ji Wusi ester

DMAB:4 ' 4 dimethylamino benzophenone

IR125:(Japan and the pure medicine system of light)

[changing 14]

(formula I)

With above-mentioned solution coat to the supporter of making by aforementioned operation, 80 ℃ of dryings one minute.

Then this coating thing is carried out the original edition for lithographic printing that ultraviolet exposure (metal halide lamp, 1000 readings) obtains to have the photo-crosslinking imaging layer.

[printing test]

To the original edition for lithographic printing that makes, carry out image exposure with the ultrared semiconductor laser of emission 830nm, the original edition for lithographic printing after the exposure is intactly printed test on extra large Dare SOR-M machine, resistance to soiling is assessed.

Even the result prints 20,000 printed matters not pollute.

As mentioned above, can provide the heat-sensitive lithographic plates that needn't carry out special processing such as wet development processing or wiping after energy water development or the image input according to the present invention.Particularly can provide with emission infrared solid laser or semiconductor laser etc., carry out record, the heat-sensitive lithographic plate that can directly make a plate from digitalized data according to the present invention.

And can provide anti-brush good positive type heat-sensitive lithographic plate according to the present invention.

Claims (1)

1. heat-sensitive lithographic plate, its feature is being, contain the polymkeric substance imaging layer that the back that is heated is changed to water wettability by hydrophobicity, and the back that is heated is positioned on the side chain of polymkeric substance to the group that water wettability changes by hydrophobicity, and is that polymkeric substance passes through photo-crosslinking and crosslinked.