CN102582312A - Low chemical treatment violet laser photopolymerization type planographic printing plate - Google Patents

Abstract

A low chemical treatment violet laser photopolymerization type planographic printing plate comprises a photopolymerization type planographic printing plate body which comprises a supporter, a photopolymerization type photosensitive layer is arranged above the supporter, and an aqueous protective layer is attached on the photopolymerization type photosensitive layer. The planographic printing plate is characterized in that the photopolymerization type photosensitive layer contains nano-micron particles which are macromolecular polymerized particles existing in an emulsion scattered form. The printing plate has high press run and development performance, and a better low chemical treatment CTP (computer to print) plate precursor is provided.

Description

The purple laser photo-polymerization type lithographic printing plate of a kind of low chemical treatment

Technical field

The present invention relates to a kind of purple laser light aggretion type of low chemical treatment sensitive offset press version that on aluminum substrate, forms, relate to a kind of low chemical treatment photo-polymerization type lithographic printing plate that can use purple directly laser Graphic specifically.

Background technology

Along with the development of computer and semiconductor laser technique, the photosensitive polymer material is studied widely and is used as the laser imaging material in recent years.Lithography technique moves towards CTP technology (being called for short the CTP technology) from traditional laser photo film copy PS platemaking technology comprehensively, and the CTP plate is also popularized gradually.CTP plate kind is a lot, and the silver salt of relatively popularizing that comprises spreads CTP plate, UV-CTP version, purple laser polymerization CTP plate, thermal CTP plate material etc.

So-called photopolymerization is meant under the effect of light, makes the method for monomer generation polymerization.Light initiation polymerization divides two kinds of direct sunshine initiated polymerization and photosensitive polymerizations.The former, under the effect of light, light trigger generates active seed (free radical or cation), trigger monomer polymerization in excitation state; Latter's sensitising agent at first absorbing light produces the polymerization of active seed trigger monomer with the light trigger effect then; Thereby can realize required sensitive volume for example infrared light 830nm, green glow 532nm, blue light 488nm and orchid light 405nm according to the absorption spectrum of sensitising agent.

But photo-polymerization type lithographic printing plate for laser imaging; During exposure; Sensitizing dye in the photosensitive layer (sensitising agent) absorbs energy; Molecule to excitation state, makes decomposition of initiator produce free radical through energy transfer or electronics transfer from ground state transition, causes active material (the containing double bond compound) polymerization reaction take place in the photosensitive layer.Solidify through the regional polymerization reaction take place of laser explosure, in developer solution, become insolublely, form image areas by dissolving; Unexposed area is removed after the processing of developing, and forms the forme clear area.Usually in having the strong basicity developer solution of PH＞10, handle the forme through exposure, the developer solution alkalescence of PH＞10 is stronger, in use machine is had stronger corrosion, and the discharging of waste liquid after the use is also serious relatively to the pollution of environment.

Summary of the invention

The object of the invention just is to solve the above-mentioned technical problem that exists in the prior art; Provide a kind of low chemical treatment purple laser photo-polymerization type lithographic printing plate; Can make plate have the developing performance that higher press resistance rate is become reconciled, < 10 developer solution is handled the forme through exposure can to adopt PH.

For realizing the foregoing invention purpose, the technical scheme that the present invention adopts is following:

Low chemical treatment photo-polymerization type lithographic printing plate of the present invention; Include support in the said photo-polymerization type lithographic printing plate body; Be the photo-polymerization type photosensitive layer on support, on the photo-polymerization type photosensitive layer,, in the photo-polymerization type photosensitive layer, include a kind of micron particles of receiving with the water-based protective layer; It is a kind of high molecular polymerization particle that exists with the emulsion discrete form, and the described micron particles of receiving is the vinyl multiple copolymer that contains following construction unit:

A: styrol structural unit;

B: (methyl) acrylonitrile unit unit;

C: ammonia esterification polyethers self-emulsifying construction unit;

In the formula, R1 is hydrogen atom or methyl, and R2 is ester group, penylene base or carbon-carbon single bond, and r is the integer of 1-3; N is the integer of 9-140;

D: acrylamide hydrophilic derivant construction unit.

In the formula, R ³Be hydrogen atom or methyl, R ⁴Be hydroxyl or sulfoamido.

It is 20000-150000 that said vinyl multiple copolymer is received the weight average molecular weight of micron particles; Glass transition temperature is 30-260 ℃; Particle diameter is 15-300nm, and the weight percent content of styrene copolymerized unit A in copolymer is 30%-80%; The weight percent content of (methyl) acrylonitrile compolymer unit B in copolymer is 0.5%-40%; The weight percent content of ammonia esterification polyethers self-emulsifying construction unit C in copolymer is 0.5%-40%; The weight percent content of acrylamide hydrophilic derivant construction unit D in copolymer is 0.5%-40%.

Said vinyl multiple copolymer is received the weight average molecular weight of micron particles and is preferably 35000-120000; Glass transition temperature is preferably 40-220 ℃; Particle diameter is preferably 35-250nm, and the weight percent content of styrene copolymerized unit A in copolymer is preferably 40%-70%; The weight percent content of (methyl) acrylonitrile compolymer unit B in copolymer is preferably 5%-30%; The weight percent content of ammonia esterification polyethers self-emulsifying construction unit C in copolymer is preferably 5%-30%; The weight percent content of acrylamide hydrophilic derivant construction unit D in copolymer is preferably 5%-50%.

Said vinyl multiple copolymer is received the weight average molecular weight of micron particles and most preferably is 50000-100000; Glass transition temperature most preferably is 60-180 ℃; Particle diameter most preferably is 55-200nm, and the weight percent content of styrene copolymerized unit A in copolymer most preferably is 50%-60%; The weight percent content of (methyl) acrylonitrile compolymer unit B in copolymer most preferably is 10%-20%; The weight percent content of ammonia esterification polyethers self-emulsifying construction unit C in copolymer most preferably is 10%-20%; The weight percent content of acrylamide hydrophilic derivant construction unit D in copolymer most preferably is 10%-20%.

The vinyl multiple copolymer is received the method for synthetic employing random copolymerization of micron particles among the present invention; The initator of polymerization contains the peroxide thing at least; The copolymerization mode adopts emulsion polymerisation, and described peroxide is a kind of in benzoyl peroxide or persulfate such as potassium peroxydisulfate or azo-compound such as the azodiisobutyronitrile etc.The mode that feed way adopts part material to drip, thermoplasticity are received the size of micron particles through changing reaction system concentration and the control of dropping time, the mixture of reaction dissolvent employing alcohol and water, and reaction temperature is 60-90 ℃.

Described said vinyl multiple copolymer is received the percentage by weight of micron particles in the photo-polymerization type lithographic printing plate photosensitive layer between 1-30%, and best percentage by weight is between 1-20%.

Include support in the said photo-polymerization type lithographic printing plate body; Be the photo-polymerization type photosensitive layer on support, its photo-polymerization type photosensitive layer component comprises ethene property unsaturated group compound, one pack system or bi-component or the multicomponent initiator system and the colouring agent that can carry out photopolymerization reaction.

Described ethene property unsaturated group compound is simple function group or multi-functional monomer, simple function group or multi-functional oligomer; More than any one or more combination; The weight percent concentration of described ethene property unsaturated group compound in the photo-polymerization type photosensitive layer is 10-90%, is preferably 50-80%.

Described one pack system or bi-component or multicomponent initiator system comprise sensitizing dye, initator and aided initiating or join transfer agent that its weight percent concentration in the photo-polymerization type photosensitive layer is 5-30%, is preferably 5-20%.

Described colouring agent is dyestuff or pigment, and its weight percent concentration in the photo-polymerization type photosensitive layer is 0.5-20%.

Including support in the said photo-polymerization type lithographic printing plate body, is the photo-polymerization type photosensitive layer on support, and the dried coating weight of photo-polymerization type photosensitive layer is 0.1g/m ²-10g/m ², be preferably 0.3-5g/m ², further be preferably 0.5-3g/m ²

Include support in the said photo-polymerization type lithographic printing plate body; It on support the photo-polymerization type photosensitive layer; On the photo-polymerization type photosensitive layer, has the water-based protective layer; Its protective layer comprises water-soluble high-molecular compound, surfactant and antiseptic component, and the dried coating weight of water-based protective layer is for being 0.5-10g/m ², be preferably 1.0-5.0g/m ²

The present invention can make plate have the developing performance that higher press resistance rate is become reconciled owing to adopt the above-mentioned micron particles of receiving, thereby a kind of better low chemical treatment CTP plate precursor is provided.

The specific embodiment

Details are as follows with regard to the concrete manufacturing process of this kind photo-polymerization type lithographic printing plate below.

One, support

The support that uses among the present invention can use aluminium or its alloy alloy of silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel (for example with) of dimensionally stable.Usually can use the material known of in aluminium handbook the 4th edition (1990, light metal association distribution), putting down in writing in the past.Aluminium plate can be the aluminium sheet that adopts common semi-continuous casting method (DC method) to make, and also can be the aluminium plate that adopts the continuous casting rolling process to make in addition.As the method for continuous casting calendering, can use double roller therapy, tape casting method, piece material casting method etc.The content of xenogenesis element is below the 10 weight % in the alloy.The thickness of aluminium plate preferably is about about 0.1mm one 0.6 mm.In addition, the plastic foil or the paper of aluminium, aluminium alloy that also can use lamination or vapor deposition.

1, the surface treatment of support

When support is aluminium plate, according to purpose various processing are implemented on its surface usually.As general processing method, at first degreasing or electrolytic polishing are handled and crude removal is handled through aluminium sheet is carried out, and the aluminium surface is cleaned.Then, implement the mechanical surface roughened or/and the electrochemical surface roughened, give the aluminium plate surface fine concavo-convex.In addition, also increasing chemical etching processing and crude removal sometimes handles.Then,, implement anodized, as required hydrophilicity-imparting treatment is implemented or/and sealing of hole is handled in the aluminium surface then in order to improve the abrasion performance of surface of aluminum plate.

Between the reason, do not bring next into for the treatment fluid that makes previous processed and handle throughout, the liquid that preferably adopts nip rolls to carry out is removed and is adopted and the washing of carrying out such as sprays.In addition, can the overflow waste liquid of the electrolyte that uses in the electrochemical surface roughened be used as the crude removal treatment fluid, but the washing that can omit this moment after crude removal is handled is handled.

1. degreasing one electrolytic polishing is handled

The rolling oil that exists on the aluminium sheet, autoxidation epithelium, dirt etc. are removed; Turn to purpose to carry out electrochemical rough surface equably; In acidic aqueous solution, carry out the electrolytic polishing of aluminium sheet and handle, or in acid or aqueous alkali, carry out the chemical etching processing of aluminium sheet.Handle the meltage preferred dissolution 1--30g/m of the aluminium sheet that produces ²More preferably dissolve 1.5-20g/m ²

(a) electrolytic polishing is handled

Can use the known aqueous solution that is used for electrolytic polishing.The aqueous solution that preferably is the main body with sulfuric acid or phosphoric acid, preferred especially is the aqueous solution of main body with phosphoric acid.Can be from phosphoric acid 20-90 weight % (preferred 40-80 weight %), liquid temperature 10 1 90 ℃ of (preferred 50 1 80 ℃), current density 1-100A/dm ²(preferred 5-80A/dm ²), select in 180 seconds the scope of electrolysis time.Can in phosphate aqueous solution, add 50 weight % sulfuric acid, chromic acid, hydrogen peroxide, citric acid, hydrofluoric acid, phthalic anhydride etc.Electric current can use direct current, pulse direct current or exchange, but preferred direct current continuously.The device that electrolytic processing apparatus can use known electrolytic treatments such as flat type groove, star-like groove to use.Flow velocity is with respect to aluminium sheet, can for and stream, adverse current any, from the scope that 0.01--10000cm/ divides, choose.

The preferred 0.3--10cm of the distance of aluminium sheet and electrode, preferred especially 0.8-2cm.Can use for method for electrically and adopt the direct of conductive rollers, also can use the indirect electric mode (liquid is given electric mode) of giving that does not adopt conductive rollers to electric mode.The electrode material of using, structure can use known material, the structure that uses in the electrolytic treatments, the preferred carbon of negative electrode material, the preferred ferrite of anode material, indium oxide or paper tinsel.

(b) chemical etching in acid or aqueous alkali is handled

In acid or aqueous alkali, carry out the chemical etching processing of aluminium sheet and can use these known means.The liquid temperature is preferably 25-90 ℃, preferably carries out 1-120 and handles second.Preferred 0.5-25 weight % of the concentration of acidic aqueous solution, the aluminium that more preferably in acidic aqueous solution, dissolves is 0.5-5 weight %.Preferred 5-30 weight % of the concentration of aqueous alkali, the aluminium that more preferably in aqueous alkali, dissolves is 30 weight %.

2, crude removal is handled

After etch processes, when the aqueous solution that uses alkali has carried out chemical etching, owing to generate dirt, therefore general with phosphoric acid, nitric acid, sulfuric acid, chromic acid or contain these nitration mixture and handle (crude removal processing) in the interior acid more than 2 kinds on the surface of aluminium.The acidic aqueous solution that uses can dissolve 0-5 weight % aluminium, ℃ implements preferred 1-30 of processing time second down from normal temperature to 70 in the liquid temperature.In addition, as this acidic aqueous solution, can use the waste liquid of the electrolyte that in electrochemical surface roughened etc., uses, must be noted that not make aluminium sheet dry, the one-tenth in the crude removal liquid analyzes.After the crude removal processing finished, in order not bring treatment fluid into subsequent processing, the liquid that preferably adopts nip rolls to carry out was removed and is adopted and spray the washing of carrying out, but when next operation is the same aqueous solution, also can omit washing.

3, mechanical surface roughened

In order to obtain good aluminum support,, give fine concavo-convex normally to the surperficial graining of aluminium sheet.Mechanical surface roughened such as general known pelletization, brush granulation, wire granulation, sandblast granulation in this graining, but as a large amount of and continuous processing, the brush granulated processed is excellent.Specifically, the slurries at surface of aluminum plate injection silica sand, aluminium hydroxide etc. with the nylon brush roll rotation that 50-500rpm makes bristle footpath 0.2-0.9mm, carry out the mechanical surface roughened.The consumption electric power (removing the essence electric power of the mechanical loss of CD-ROM drive motor) of the rotation drive motor of the power that is pressed into of brush. preferred 0.2-15kw, more preferably 0.5-10kw.

4, electrochemical surface roughened

(a) use direct current the electrochemical surface roughened with hydrochloric acid or nitric acid the aqueous solution as main body; Can use the aqueous solution that in the electrochemical surface roughened of using common interchange, uses, can in the hydrochloric acid of 1-100g/L or aqueous solution of nitric acid, add 1g/L has the hydrochloric acid or the nitrate compound of salt acid ion to saturated aluminum nitrate, sodium nitrate, ammonium nitrate etc. use more than 1.The metal of in addition, can dissolved iron in the aqueous solution that is the main body with hydrochloric acid or nitric acid, containing in the aluminium alloy such as copper, manganese, titanium, magnesium, silica.The preferred use added aluminium chloride, aluminum nitrate so that aluminium ion reaches the liquid of 3-50g/L in the hydrochloric acid or nitric acid 0.5-2 weight % aqueous solution.Preferred 10 1 60 ℃ of temperature, more preferably 25-50 ℃.Use the treating apparatus that uses in the electrochemical surface roughening of direct current to make

With the device of known use direct current, use anode and the mutual devices of arranging of negative electrode a pair of or more than two pairs.It is the direct current below 20% that the direct current that uses in the electrochemical surface roughening preferably uses pulsation rate.Preferred 10-the 200A/dm of current density ², preferred 10 1 1000C/dm of the electric weight when aluminium sheet is anode ²Anode can be from ferrite, indium oxide, paper tinsel, known oxygen such as compound or plating paper tinsel is selected use taking place with electrode on valve metals such as titanium, niobium, zirconium.Negative electrode can be selected to use from carbon, paper tinsel, titanium, niobium, zirconium, stainless steel, the electrode that cathode for fuel cell, uses.

(b) use the electrochemical surface roughened that exchanges with hydrochloric acid or nitric acid the aqueous solution as main body; Can use the aqueous solution that in the electrochemical surface roughened that common use exchanges, uses; Can in the hydrochloric acid of 1--100g/L or aqueous solution of nitric acid, add lg/L and have nitrate ion to saturated aluminum nitrate, sodium nitrate, ammonium nitrate etc., aluminium chloride, sodium chloride, ammonium chloride etc. have at least 1 use of the hydrochloric acid or the nitrate compound of salt acid ion.The metal of in addition, can dissolved iron in the aqueous solution that is the main body with hydrochloric acid or nitric acid, containing in the aluminium alloy such as copper, manganese, nickel, titanium, magnesium, silica.

The preferred use added aluminium chloride, aluminum nitrate etc. so that aluminium ion reaches the liquid of 3-50g/L in the hydrochloric acid or nitric acid 0.5-2 weight % aqueous solution.Preferred 10-60 ℃ of temperature, more preferably 20-50 ℃.

(c) the AC power ripple that uses in the electrochemical surface roughening uses marking wave, square wave, platform shape ripple, triangular wave etc., but preferred square wave or platform shape ripple, preferred especially platform shape ripple.Electric current is from preferred 1-3msec of the time (TP) at 0 arrival peak.If littler than 1msec, it is inhomogeneous with the processing of the electric shock ripple of the vertical generation of direct of travel of aluminium sheet to be easy to generate what is called.If TP is bigger than 3msec, in the electrolyte that in the electrochemical surface roughening, uses with ammonium ion etc. as the electrolytic treatments in the nitric acid liquid of representative in, the influence that receives nature to produce the micro constitutent that increases easily is difficult for carrying out the generation sand holes of homogeneous.

(d) duty ratio of platform shape ripple interchange can use 1:2-2:1, in aluminium, does not use giving indirectly in the electric mode of conductive rollers, preferred duty ratio 1:l.The frequency that platform shape ripple exchanges can be used 0.1--120Hz, preferred 50 1 70Hz on the equipment.If lower than 50Hz, the carbon electrode of main pole dissolves easily, if bigger than 70Hz, receives the influence of the inductance composition on the electric power loop easily, the power supply cost up.But, when use contains the aluminium alloy greater than the Cu of 0.1wt%, the interchange of preferred frequency of utilization 0.1--10Hz.Preferred 10-the 200A/dm of the peak value of the current waveform of current density ²

(e) electrolytic cell that uses in the electrochemical surface roughening can use the electrolytic cell that uses in longitudinal type, platypelloid type, the known surface treatment such as star-like, and the electrolyte that in electrolytic cell, passes through can be parallel with advancing of aluminium net, also can drive in the wrong direction with it.

(f) in the AC power that can connect on the electrolytic cell more than 1.The anode that exchanges that on the aluminium sheet relative with main pole, adds and the current ratio of negative electrode are controlled,, made the part shunting of alternating current preventing impressed current anode preferably to be set aspect the carbon dissolution of main pole.Through rectifier cell or switch element; DC current on the impressed current anode that is provided with on the other groove outside the part shunting conduct that makes current value and 2 main electrodes can be controlled with the ratio of the current value of participating in anode reaction the participation cathode reaction current value that on the aluminium sheet relative with main pole, acts on.On the aluminium sheet relative, participate in ratio when anode (electric weight during negative electrode/electric weight) preferred 0.3-0.95 of the electric weight of anode reaction and cathode reaction with main pole.

(g) be in the aqueous solution of principal component with nitric acid or hydrochloric acid, using to exchange or direct current, with 10---1000C/dm ²Electric weight this aluminium sheet is carried out the electrochemical surface roughened, in acidic aqueous solution, use electric current to exchange as 1-3msec and frequency platform shape ripple from 0 to time of peaking as 50---70Hz.

5, (utilizing acid-alkaline liquid) handled in chemical etching

So that whole of the fine concavo-convex sand holes that form in mechanical surface roughened, the electrochemical surface roughened, dirt etc. are removed is purpose, carries out chemical etching and handles.The liquid temperature is preferably 25-90 ℃, preferably carries out 1-120 and handles second.Preferred 0.5-25 weight % of the concentration of acidic aqueous solution, the aluminium that more preferably in acidic aqueous solution, dissolves is 0.5-5 weight %.Preferred 5-30 weight % of the concentration of aqueous alkali, the aluminium that more preferably in aqueous alkali, dissolves is 1--30 weight %.In acid or aqueous alkali, carry out etch processes so that the meltage of aluminium sheet reaches 1g/m ²More than, 30g/m ²Below or the meltage of aluminium reach 0.1g/m ²More than, 3g/m ²Below.

In addition; When the aqueous solution of use alkali carries out chemical etching; Owing to generate dirt on the surface of aluminium, therefore in this case generally with phosphoric acid, nitric acid, sulfuric acid, chromic acid or contain these nitration mixture and carry out etch processes (required crude removal processing) in the interior acid more than 2 kinds.(identical) with above-mentioned crude removal record.

6, anodized

For water-retaining property, the abrasion performance that improves surface of aluminum plate, implement anodized.The electrolyte that uses in the anodized as aluminium sheet if form the porous oxide scale film, can use any electrolyte.Usually use sulfuric acid, phosphoric acid, oxalic acid, chromic acid or their mixed liquor.These electrolytical concentration are because of the suitably decision of electrolytical kind.Anodised treatment conditions become because of employed electrolyte, therefore cannot treat different things as the same, if electrolytical concentration is 1--80wt% usually, the liquid temperature is 5-70 ℃, and current density is 1--60A/dm ², voltage 1--100V, electrolysis time 5 seconds--be suitable in-300 seconds the scope.Sulfuric acid process is handled with DC current usually, but also can use interchange.The amount of anodic oxide coating is 0.5-10g/m ²Scope be suitable.The concentration of sulfuric acid uses 5-30%.In 20-60 ℃ temperature range, carry out 5-250 second electrolytic treatments.Preferably in this electrolyte, contain aluminium ion.The current density of this moment is 1--50A/dm more preferably ²Under the situation of phosphoric acid method, under the concentration 5-50%, 30-60 ℃ the temperature, 10-300 seconds, 1--15A/dm ²Current density under handle.The amount of anodic oxide coating is preferably 1.0g/m ²More than, more preferably 2.0-6.0g/m ²Scope.

7, hydrophilicity-imparting treatment

After having implemented anodized, as required hydrophilicity-imparting treatment is implemented on the aluminium surface.In the method, in sodium silicate aqueous solution,, or carry out electrolytic treatments with support impregnation.(other processing (washing, sealing of hole))

After reason finishes throughout,, adopt nip rolls liquid to remove and adopt and spray the washing of carrying out in order not bring treatment fluid into subsequent processing.Preferably after anodized, implementing sealing of hole handles.This sealing of hole is handled through dipping in the hydrothermal solution that contains hot water and inorganic salts or organic salt and is adopted water vapour to bathe and carry out.

Two, the formation of photosensitive layer

On priming coat, be coated with the coating of photo-polymerization type photosensitive composite and carry out drying, form photosensitive layer.

The photo-polymerization type photosensitive composite with the dissolving of the solid component concentration of 2-50 weight %, disperse, be applied on the support aluminum substrate and carry out drying.The coating weight of the layer (photosensitive layer) of the photo-polymerization type photosensitive composite that on the support aluminum substrate, is coated with is different because of purposes, and preferred dried weight is 0.3-4.0g/m usually ²Along with coating weight reduces, the light exposure that is used to obtain image get final product less, but the film-strength reduction.Along with coating weight increases, be essential with light exposure, but light-sensitive surface strengthen, for example, and when as galley, the galley of the number of pages many (high anti-brushes) that can obtain printing.In photosensitive composite, can add and be used to improve the surfactant of coated face matter, preferred especially fluorine class surfactant.

The photosensitive layer of the formation photosensitive lithographic plate that uses among the present invention with described receive a micron high molecular polymerization particle, can addition polymerization ethylenically unsaturated compounds, light trigger, macromolecule bond be must composition, as required can and with all cpds such as colouring agent, plasticizer, heat polymerization inhibitors.

Low chemical treatment photo-polymerization type lithographic printing plate of the present invention; In the photo-polymerization type photosensitive layer, include a kind of micron particles of receiving; It is a kind of high molecular polymerization particle that exists with the emulsion discrete form, and the described micron particles of receiving is the vinyl multiple copolymer that contains following construction unit:

A: styrol structural unit;

B: (methyl) acrylonitrile unit unit;

C: ammonia esterification polyethers self-emulsifying construction unit;

In the formula, R1 is hydrogen atom or methyl, and R2 is ester group, penylene base or carbon-carbon single bond, and r is the integer of 1-3; N is the integer of 9-140;

D: acrylamide hydrophilic derivant construction unit.

In the formula, R ³Be hydrogen atom or methyl, R ⁴Be hydroxyl or sulfoamido.

The micron particles of receiving of the present invention is a kind of high molecular polymerization particle that exists with the emulsion discrete form, and it comprises following dominance structure unit:

1, contains styrol structural unit A.As everyone knows, the styrol structural unit glass transition temperature is higher, and styrol copolymer can improve the hardness of coating, can increase the plate pressrun, and good ink affinity is arranged in addition;

2, contain cyanic acid side group hydrophobic group, have good drug resistance, pliability and hydrophobicity; Method that multiple copolymer of the present invention is introduced hydrophobic side chain radical nitrile is in the copolymerization component, to have designed the vinyl component structure unit B that side chain contains basic nitrile; It comprises itrile group methyl acrylate, itrile group ethyl acrylate, acrylonitrile or methacrylonitrile etc., preferred acrylonitrile or methacrylonitrile or their mixture.

3, contain ammonia esterification polyethers self-emulsifying construction unit, polymer can lean on the polyethers emulsification group of self to realize emulsification not adding under the condition that emulsifying agent exists, and synthetic emulsion particle is than outer emulsification emulsion particle homogeneous, mellow and full more, and stability is better; Simultaneously the ammonia ester bond of strong polarity exists, emulsion particle elasticity better, more wear-resisting; As everyone knows, polyurethane elastomer has very high wearability owing to contain the ammonia ester bond of strong polarity, is called as " wear-resisting king " resin.So we receive micron particles in thermoplasticity and introduce the ammonia ester bond of strong polarity simultaneously, introduce behind the ammonia ester bond of strong polarity emulsion particle elasticity better, more wear-resisting.Thermoplasticity of the present invention is received micron particles and in the copolymerization component, has been designed ammonia esterification polyethers self-emulsifying construction unit C, and its structure is following:

In the formula, R ¹Be hydrogen atom or methyl, R ²Be ester group, penylene base or valence link, r is the integer of 1-3; N is the 9-140 integer.

Typical example is stated structural formula as follows, but the present invention is not limited to the structural formula of following C1-C3.

C1

C2

C3

The existing industrialized product of C2 is sold.But C1, C3 laboratory are synthetic in batches.So in plate production, select for use as far as possible with industrialized products C 2.

4, contain acrylamide hydrophilic derivant construction unit, can provide good water development property or weak base to develop for receiving micron particles.

It is exactly the copolymerization units that in resin structure, directly contains hydrophilic group that the hydrophilic best approach of micron particles is received in realization.Hydrophilic group has carboxyl, hydroxyl, phosphate, sulfonic group, amino, amide groups, ether or the like.The micron particles of receiving of the present invention has designed acrylamide hydrophilic derivant construction unit D in the copolymerization component, its structure is following:

In the formula, R ³Be hydrogen atom or methyl, R ⁴Be hydroxyl or sulfoamido.

The typical example of typical case is stated structural formula as follows, but the present invention is not limited to the structural formula of following D1-D6.

D1

D2

D3

D4

D5

The amide groups of acrylamide hydrophilic derivant, phenolic hydroxyl group or sulfoamido can provide good hydrophilicity for receiving micron particles, and the amido link of simultaneously strong polarity also can provide good solvent resistance and wearability for the micron particles film of receiving that thermoplastic merges.

The synthetic micron particles of receiving of the present invention adopts the method for copolymerization, optional random copolymerization of copolyreaction or block copolymerization, preferred random copolymerization.The initator of polymerization comprises peroxide such as di-tert-butyl peroxide, benzoyl peroxide, persulfate such as potassium peroxydisulfate, Ammonium Persulfate 98.5, azo-compound such as azodiisobutyronitrile etc.The copolymerization mode adopts emulsion polymerisation.

Available reaction dissolvent has water, methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, butanols, acetone, MEK, cyclohexanone, ethyl acetate, butyl acetate, oxolane, 1; 4-dioxane, N; Dinethylformamide, dimethylacetylamide acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, toluene, EGME, ethylene glycol ethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, acetylacetone,2,4-pentanedione, DAA, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, glycol isopropyl ether, butyl glycol ether acetic acid esters, 3-methoxypropanol, methoxymethoxy ethanol, diethylene glycol dimethyl ether, diethylene glycol ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters,, methyl-sulfoxide, methyl lactate and ethyl lactate etc., or their mixture.Preferably adopt the mixture of alcohol and water, the mixture of preferred normal propyl alcohol-water or isopropyl alcohol-water.The preferred 40-100 of emulsion copolymerization reaction temperature ℃, optimum is 60-90 ℃.

So-called ethylenically unsaturated compounds is meant when the photo-polymerization type photosensitive composite is accepted the active ray irradiation, has the effect that utilizes Photoepolymerizationinitiater initiater and the compound of addition polymerization, crosslinked, the ethylenic unsaturated bond that solidifies.

The compound that contains the two keys of ethylenic that can addition polymerization can be from having 1, preferably having the compound of 2 above terminal olefinic link formula unsaturated bonds and select arbitrarily at least.

Can have for example monomer, prepolymer, i.e. 2 aggressiveness, 3 aggressiveness and oligomer, or the chemical form of their mixture and their copolymer etc.

Example as monomer and copolymer thereof; Can enumerate the ester of unsaturated carboxylic acid (for example acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid etc.) and aliphatic polyol compound, the acid amides of unsaturated carboxylic acid and aliphatic polyamine compound etc.

Concrete example as the monomer of the ester of aliphatic polyol compound and unsaturated carboxylic acid; Comprise: as glycol diacrylate, the triethylene glycol diacrylate, 1 of acrylic acid ester; 3--butanediol diacrylate, 1; 4--butanediol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloyl-oxy propyl group) ether, trimethylolethane trimethacrylate acrylic acid ester, hexanediyl ester, 1,4--cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol five acrylic acid ester, dipentaerythritol acrylate, sorbierite triacrylate, sorbierite tetraacrylate, sorbierite five acrylic acid ester, sorbierite six acrylic acid ester, three (acrylyl oxy-ethyl) isocyanuric acid ester, polyester acrylic ester oligomer etc.

As methacrylate; Comprise 1; 4--butanediol dimethylacrylate, triethylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylol-propane trimethacrylate, trimethylolethane trimethacrylate methacrylate, ethylene glycol dimethacrylate, 1,3--butanediol dimethylacrylate, hexanediol dimethacrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl acrylic acid ester, dipentaerythritol dimethylacrylate, dipentaerythritol hexamethyl acrylic acid ester, dipentaerythritol pentamethyl acrylic acid ester, sorbierite trimethyl acrylic ester, sorbierite tetramethyl acrylic acid ester, two [right--(3--methacryloxy-2--hydroxyl propoxyl group) phenyl] dimethylmethane, two [right--(methacryloxy ethyoxyl) phenyl] dimethylmethane etc.As itaconate; Comprise ethylene glycol bisthioglycolate itaconate, propane diols diitaconate, 1; 3--butanediol diitaconate, 1,4--butanediol diitaconate, 1,4--butanediol diitaconate, pentaerythrite diitaconate, sorbierite four itaconates etc.

As crotonates, comprise ethylene glycol bisthioglycolate crotonates, l, 4--butanediol two crotonates, pentaerythrite two crotonates, sorbierite four crotonates etc.

As the iso-crotonic acid ester, comprise ethylene glycol bisthioglycolate iso-crotonic acid ester, pentaerythrite two iso-crotonic acid esters, sorbierite four iso-crotonic acid esters etc.

As maleate, comprise ethylene glycol bisthioglycolate maleate, triethylene glycol dimaleate, pentaerythrite dimaleate, sorbierite four maleates etc.

In addition, can also enumerate the mixture of above-mentioned ester monomer.

In addition; Concrete example as the monomer of the acid amides of aliphatic polyamine compound and unsaturated carboxylic acid; Comprise di-2-ethylhexylphosphine oxide-acrylamide, di-2-ethylhexylphosphine oxide--Methacrylamide, 1; The 6--hexa-methylene is two--acrylamide, 1, and the 6--hexa-methylene is two--Methacrylamide, diethylenetriamines three acrylamides, xylylene bisacrylamide, the two Methacrylamides of xylylene etc.

In addition, the use amount of these ethylenically unsaturated compounds is with 5-80 weight % of the full composition of photosensitive layer, and the scope of preferred 30 1 70 weight % is used.

In addition; The purple laser light polymerization initiator that contains in the photosensitive layer as photosensitive lithographic plate of the present invention; Wavelength according to the light source that uses can suitably be selected known various light triggers in patent, the document etc., or the paralled system of the light trigger more than 2 kinds (light initiation system) uses.Below enumerate concrete example, but be not limited to these.

For example, can enumerate cation pigment/borate-based, the luxuriant titanium of merocyanine pigment/two system, the luxuriant titanium of carbazole type pigment/two system etc.

In the present invention, especially preferably use two cyclopentadiene titanium compounds.

As two cyclopentadiene titanium compounds, can use various these materials, more particularly, can enumerate dicyclopentadienyl-Ti--dichloride, dicyclopentadienyl-Ti--diphenyl, dicyclopentadienyl-Ti--two--2; 3,4,5,6--phenyl-pentafluoride--1-base, dicyclopentadienyl-Ti--two--2; 3,5,6--phenyl tetrafluoride--1--base, dicyclopentadienyl-Ti--two--2,4; 6--trifluoro-benzene-1--base, dicyclopentadienyl-Ti--two--2,6--two fluorobenzene--1--base, dicyclopentadienyl-Ti--two--2,4--two fluorobenzene--1--base, two--methyl cyclopentadienyl-Ti--two--2; 3,4,5; The 6--phenyl-pentafluoride--1--base, two--methyl cyclopentadienyl-Ti--two--2,6--two fluorobenzene--1--base, dicyclopentadienyl-Ti--two--2, the 6--difluoro--3--(pyrroles--the 1--yl)--benzene--1--base etc.

In addition; Known as required through in above-mentioned light trigger, adding thiol moiety such as 2--mercaptobenzothiazoler, 2--mercaptobenzimidazole, 2--mercaptobenzoxazole; N--phenylglycine, N; Hydrogen donating compounds such as amines such as N--dialkyl amido aromatic series Arrcostab can further improve light-initiated ability.

The use amount of these Photoepolymerizationinitiater initiaters (being) is with respect to ethylenically unsaturated compounds 100 weight portions, in 0.05-100 weight portions, preferred 0.1--70 weight portion, more preferably use in the scope of 0.2-50 weight portions.

The macromolecule bond that uses in the photosensitive layer as photosensitive lithographic plate of the present invention; Because not only the epithelium as said composition forms agent; And must be dissolved in the alkaline developer, therefore use the organic high molecular polymer of in buck solubility or swellability.As such organic high molecular polymer, comprise that side chain has carboxylic acid group's addition polymer, i.e. methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid, partial esterification maleic acid etc.

Comprise the acid cellulose derivative that has the carboxylic acid group equally at side chain in addition.Polymer that this is external to have addition cyclic acid anhydride on the addition polymer of hydroxyl etc. is useful.Wherein preferred especially [(methyl) benzyl acrylate/(methyl) acrylic acid/as required other addition polymerization sex ethylene base monomers] copolymer and [(methyl) allyl acrylate/(methyl) acrylic acid/as required other addition polymerization sex ethylene base monomers] copolymer.In addition, as water soluble organic polymer, PVP, PEO etc. is useful.In addition, in order to improve the intensity of cured film, pure soluble polyamide, 2, polyethers of 2--two--(4--hydroxyphenyl)--propane and chloropropylene oxide etc. also is useful.

These high molecular polymers can improve the intensity of cured film through importing radical reaction property group at side chain.As functional group that can polyaddition reaction; Can enumerate ethylenic unsaturated bond base, amino, epoxy radicals, in addition, as the functional group that can become free radical through illumination; Can enumerate sulfydryl, mercapto, halogen atom, triazine structure, salt structure etc.; In addition, as polar group, can enumerate carboxyl, imino group etc.As above-mentioned functional group that can polyaddition reaction; Ethylenic unsaturated bond bases such as preferred especially acryloyl group, methacryl, pi-allyl, styryl; In addition; From amino, hydroxyl, phosphonate group, phosphate, carbamoyl, NCO, urea groups, l, the functional group that 3-urylene, sulfonic group, ammonium are selected also is useful.

In order to keep the development property of composition, macromolecule bond of the present invention preferably has appropriate molecular amount, acid number, uses effectively that weight average molecular weight is 5000-30 ten thousand, acid number is 10-200 high molecular polymer.

These organic high molecular polymers can all mix amount arbitrarily in the composition.But, when surpassing 90 weight %, produce not preferred result at the aspects such as image intensity that form.Be preferably 10-90%, more preferably 30-80%.In addition, can photopolymerisable ethylenically unsaturated compounds and organic high molecular polymer represent with weight ratio, be preferably the scope of l/9-9/l.Preferred scope is 2/8-8/2, further is preferably 3/7-7/3.

In addition, in the present invention, except above basis, in the manufacturing of photosensitive composite or in preserving,, preferably add a spot of heat polymerization inhibitors in order to stop the unnecessary thermal polymerization of polymerisable ethylenically unsaturated compounds.As suitable heat polymerization inhibitors; Can enumerate quinhydrones, p methoxy phenol, BHT, burnt tangerine phenol, tert-butyl catechol, benzoquinones, 4; 4 '-sulfo-two (3 methy 6 tert butyl phenol), 2,2 '-methylene two (4-methyl-6-tert butyl phenol), the inferior cerium salt of N-nitroso phenyl hydroxylamine, N-nitroso phenyl hydroxylamine aluminium salt etc.The addition of heat polymerization inhibitors is with respect to the weight of whole compositions, preferably about 0.01%-about 5%.

In addition, the resistance that produces for anti-block gathers, and can add the such advanced higher fatty acid derivative of mountain lush acid, mountain lush acid acid amides etc. as required, and its surface of being partial to photosensitive layer is existed.The addition of advanced higher fatty acid derivative is preferably the 0.5%-10% of whole compositions.

In addition, with the purpose that is colored as of photosensitive layer, can add colouring agent.As colouring agent, comprise for example pigment such as phthualocyanine pigment, azo pigment, carbon black, titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone based dye, cyanine based dye.The addition of dyestuff and pigment is preferably the 0.5%-20% of whole compositions.

In addition, in order to improve the rerum natura of cured film, can add additives such as plasticizer such as inorganic filler or dioctyl phthalate, repefral, tricresyl phosphate.Their addition is preferably below 10% of whole compositions.

On the support aluminium plate during photosensitive coated layer composition, be dissolved in and supply in the various organic solvents to use.As solvent used herein; Comprise acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethylene, oxolane, toluene, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, acetylacetone,2,4-pentanedione, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, glycol monomethyl isopropyl ether, ethylene glycol monomethyl ether acetate, 3 one methoxypropanol, methoxymethoxy ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate one 3 one methoxy propyl yl acetates, N, N dimethyl formamide, dimethyl sulfoxide (DMSO), Y one butyrolactone, methyl lactate, ethyl lactate etc.These solvents can separately or mix and use.In addition, the concentration of the solid constituent in the coating solution is that 50 weight % are suitable.

In order to improve coated face matter, in the optical polymerism composition of the photosensitive layer of photosensitive lithographic plate of the present invention, can add surfactant.Its amount of coating is in dried weight, about 0.1g/m ²-10g/m ²Scope be suitable.0.3-5g/m more preferably ²Further be preferably 0.5-3g/m ²

(coating process)

As the coating process of photosensitive composite, can use the method for coating scraper (coating rod), the method for extrusion type coating machine, the method for ball coating machine (slide beald coater) etc., but be not limited to these.

Three, the formation of protective finish

As the water soluble polymer that contains hydrogen associativity group that is contained in the protective finish, can enumerate polyvinyl alcohol and part ester, ether and acetal, or contain and make them have its copolymer of the not substituted ethylene alcohol unit of essential water miscible real mass.As polyvinyl alcohol, can enumerate 71-100% hydrolysis, the degree of polymerization polyvinyl alcohol in 300-2400 scopes.Specifically can enumerate PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203; PVA-204; PVA-205, PVA-2107, PVA-2177, PVA-220, PVA-224, PVA-217EE, PVA-220, PVA-224 7 PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA-420, PVA-613, L-8 etc.As above-mentioned copolymer, can enumerate 88-100% hydrolysed polyvinyl acetate chloracetate or propionic ester, polyvinyl formal and Pioloform, polyvinyl acetal and their copolymer.As other useful polymer, can enumerate PVP, gelatin and gum arabic, these can use separately or and use.These water soluble polymers contain 30-99% ratio with respect to all solids composition of protective finish, preferred 50-99% ratio.

In protective finish, can also add the surfactant that is used to improve coating, the known additives such as water miscible plasticizer that are used to improve the epithelium rerum natura.As water miscible plasticizer, comprise for example propionamide, cyclohexanediol, glycerine, sorbierite etc.In addition, can add water miscible (methyl) acrylic acid series polymeric compounds etc.Its amount of coating is in dried weight, about 0.1g/m ²-Yue 15g/m ²Scope be suitable.1.0g/m more preferably ²---5.0g/m ²Drying coated weight as protective finish is generally 0.5-10g/m ², be preferably 1.0-5.0g/m ²

Synthesizing of emulsion particle

Emulsion particle P01's is synthetic

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 500 g isopropyl alcohols, 150g deionized water, 10g (10 weight %) example compound C2 (n is about 9～10), 10 g (10 weight %) example compound D1; Heated and stirred is even; 60 ℃ drip 60g (60 weight %) SM (styrene), 20g (20 weight %) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile) down; 2.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 13.3%, and the GPC molecular weight is 20000, and particle diameter is 15nm.

Emulsion particle P02's is synthetic

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 400 g isopropyl alcohols, 125g deionized water, 15g (15 weight %) example compound C2 (n is about 13～14), 15 g (15 weight %) example compound D2; Heated and stirred is even; 90 ℃ of following Dropwise 5 5g (55 weight %) SM (styrene), 15g (15 weight %) MAN (methacrylonitrile), 0.7g BPO (benzoyl peroxide); 2.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 16.0%, and the GPC molecular weight is 35000, and particle diameter is 35nm.

Emulsion particle P03's is synthetic

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 350 g isopropyl alcohols, 100g deionized water, 10g (10 weight %) example compound C2 (n is about 22～23), 10 g (10 weight %) example compound D3; Heated and stirred is even; 80 ℃ drip 60g (60 weight %) SM (styrene), 20g (20 weight %) AN (acrylonitrile), 0.7g potassium peroxydisulfate down; 2.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 18.2%, and the GPC molecular weight is 50000, and particle diameter is 55nm.

Emulsion particle P04's is synthetic

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g isopropyl alcohols, 75g deionized water, 15g (15 weight %) example compound C2 (n is about 34～35), 15 g (15 weight %) example compound D4; Heated and stirred is even; 80 ℃ of following Dropwise 5 5g (55 weight %) SM (styrene), 15g (15 weight %) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile); 2.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 85000, and particle diameter is 135nm.

Emulsion particle P05's is synthetic

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 230 g isopropyl alcohols, 70g deionized water, 10g (10 weight %) example compound C2 (n is about 43～44), 20 g (20 weight %) example compound D5; Heated and stirred is even; 80 ℃ of following Dropwise 5 5g (55 weight %) SM (styrene), 15g (15 weight %) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile); 2.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 25.%, and the GPC molecular weight is 100000, and particle diameter is 200nm.

Emulsion particle P06's is synthetic

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g isopropyl alcohols, 75g deionized water, 5g (5 weight %) example compound C2 (n is about 54～55), 14.5 g (14.5 weight %) example compound D1; Heated and stirred is even; 80 ℃ drip 80g (80 weight %) SM (styrene), 0.5g (0.5 weight %) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile) down; 2.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 90000, and particle diameter is 140nm.

Emulsion particle P07's is synthetic

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g isopropyl alcohols, 75g deionized water, 0.5g (0.5 weight %) example compound C2 (n is about 65～66), 24.5g (24.5 weight %) example compound D2; Heated and stirred is even; 80 ℃ drip 70g (70 weight %) SM (styrene), 50g (50 weight %) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile) down; 2.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 95000, and particle diameter is 150nm.

Emulsion particle P08's is synthetic

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g isopropyl alcohols, 75g deionized water, 19.5g (19.5 weight %) example compound C2 (n is about 80～81), 0.5 g (0.5 weight %) example compound D3; Heated and stirred is even; 80 ℃ of following Dropwise 5 0g (50 weight %) SM (styrene), 30g (30 weight %) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile); 2.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 110000, and particle diameter is 170 nm.

Emulsion particle P09's is synthetic

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g isopropyl alcohols, 75g deionized water, 10g (10 weight %) example compound C2 (n is about 90～91), 40 g (40 weight %) example compound D4; Heated and stirred is even; 80 ℃ drip 40g (40 weight %) SM (styrene), 10g (10 weight %) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile) down; 2.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 125000, and particle diameter is 190nm.

Emulsion particle P10's is synthetic

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g isopropyl alcohols, 75g deionized water, 30g (30 weight %) example compound C2 (n is about 113～114), 30 g (30 weight %) example compound D5; Heated and stirred is even; 80 ℃ drip 30g (30 weight %) SM (styrene), 10g (10 weight %) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile) down; 2.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 135000, and particle diameter is 250nm.

Emulsion particle P11's is synthetic

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g isopropyl alcohols, 75g deionized water, 40g (40 weight %) example compound C2 (n is about 138～140), 5 g (5 weight %) example compound D1; Heated and stirred is even; 80 ℃ drip 25g (25 weight %) SM (styrene), 30g (30 weight %) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile) down; 2.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 150000, and particle diameter is 300nm.

Emulsion particle P12's is synthetic

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g isopropyl alcohols, 75g deionized water, 10g (10 weight %) example compound C2 (n is about 43～44), 10 g (10 weight %) example compound D1; Heated and stirred is even; 80 ℃ drip 60g (60 weight %) SM (styrene), 20g (20 weight %) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile) down; 2.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 85000, and particle diameter is 145nm.

Emulsion particle P13's is synthetic

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g isopropyl alcohols, 75g deionized water, 10g (10 weight %) example compound C2 (n is about 43～44), 10 g (10 weight %) example compound D1; Heated and stirred is even; 80 ℃ drip 60g (60 weight %) SM (styrene), 20g (20 weight %) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile) down; 1.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 105000, and particle diameter is 190nm.

Emulsion particle P14's is synthetic

Emulsion particle P14

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g isopropyl alcohols, 75g deionized water, 15g (15 weight %) example compound C2 (n is about 43～44), 20 g (20 weight %) example compound D4; Heated and stirred is even; 80 ℃ of following Dropwise 5 5g (55 weight %) SM (styrene), 10g (10 weight %) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile); 2 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 90000, and particle diameter is 170nm.

Emulsion particle P15's is synthetic

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g isopropyl alcohols, 75g deionized water, 10g (10 weight %) example compound C2 (n is about 54～55), 10 g (10 weight %) example compound D3; Heated and stirred is even; 80 ℃ drip 60g (60 weight %) SM (styrene), 20g (20 weight %) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile) down; 1.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 110000, and particle diameter is 195nm.

Emulsion particle P16's is synthetic

The first step: synthon C1: in the flask that condenser pipe, nitrogen protection, thermometer, dropping funel and agitator are arranged, add hydroxyl value through the PEG (n is about 22～23) of the fusion of demarcation and the X1 compound of equivalent; 60 ℃ of bulk reactions under laurate diisobutyl tin DBTDL catalysis; Reacted reaction complement mark: disappear about 1 hour through peak, infrared spectrum detection of active NCO 2275 place.

The structural formula of X1 compound is:

Second step: in the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g isopropyl alcohols, 75g deionized water, 20g (20 weight %) example compound C1 (n is about 22～23), 10 g (10 weight %) example compound D1; Heated and stirred is even; 70 ℃ of following Dropwise 5 5g (55 weight %) SM (styrene), 15g (15 weight %) AN (acrylonitrile), 0.7g potassium peroxydisulfate; 1.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 85000, and particle diameter is 235nm.

Emulsion particle P17's is synthetic

The first step: synthon C1: in the flask that condenser pipe, nitrogen protection, thermometer, dropping funel and agitator are arranged, add hydroxyl value through the PEG (n is about 43～44) of the fusion of demarcation and the X1 compound of equivalent; 60 ℃ of bulk reactions under laurate diisobutyl tin DBTDL catalysis; Reacted reaction complement mark: disappear about 1 hour through peak, infrared spectrum detection of active NCO 2275 place.

The structural formula of X1 compound is:

Second step: in the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g isopropyl alcohols, 75g deionized water, 10g (10 weight %) example compound C1 (n is about 43～44), 10 g (10 weight %) example compound D3; Heated and stirred is even; 80 ℃ drip 60g (60 weight %) SM (styrene), 20g (20 weight %) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile) down; 1.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 110000, and particle diameter is 175nm.

Emulsion particle P18's is synthetic

The first step: synthon C3: in the flask that condenser pipe, nitrogen protection, thermometer, dropping funel and agitator are arranged, add hydroxyl value through the PEG (n is about 34～35) of the fusion of demarcation and the X3 compound of equivalent; 60 ℃ of bulk reactions under laurate diisobutyl tin DBTDL catalysis; Reacted reaction complement mark: disappear about 1 hour through peak, infrared spectrum detection of active NCO 2275 place.

The structural formula of X3 compound is:

Second step: in the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g isopropyl alcohols, 75g deionized water, 15g (15 weight %) example compound C1 (n is about 34～35), 10 g (10 weight %) example compound D2; Heated and stirred is even; 80 ℃ of following Dropwise 5 5g (55 weight %) SM (styrene), 15g (15 weight %) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile); 1.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 91000, and particle diameter is 255nm.

Emulsion particle P19's is synthetic

The first step: synthon C3: in the flask that condenser pipe, nitrogen protection, thermometer, dropping funel and agitator are arranged, add hydroxyl value through the PEG (n is about 80～81) of the fusion of demarcation and the X3 compound of equivalent; 60 ℃ of bulk reactions under laurate diisobutyl tin DBTDL catalysis; Reacted reaction complement mark: disappear about 1 hour through peak, infrared spectrum detection of active NCO 2275 place.

The structural formula of X3 compound is:

Second step: in the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g isopropyl alcohols, 75g deionized water, 10g (10 weight %) example compound C3 (n is about 80～81), 20 g (20 weight %) example compound D4; Heated and stirred is even; 90 ℃ of following Dropwise 5 0g (50 weight %) SM (styrene), 20g (20 weight %) AN (acrylonitrile), 0.7g BPO (benzoyl peroxide); 1.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 105000, and particle diameter is 195nm.

Comparative example B01

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g normal propyl alcohols, 75g deionized water, 5g lauryl sodium sulfate; 80 ℃ drip 60g (60 weight %) SM (styrene), 40g (40 weight %) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile) down; 1.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 85000, and particle diameter is 165nm.

Comparative example B02

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g normal propyl alcohols, 75g deionized water; 80 ℃ drip 60g (60 weight %) SM (styrene), 20g (20 weight %) AN (acrylonitrile), 20g (20 weight %) PEGMA (polyethoxy methacrylate n is about 43～44), 0.7gAIBN (azodiisobutyronitrile) down; 1.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 95000, and particle diameter is 180nm.

Comparative example B03

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add 250 g normal propyl alcohols, 75g deionized water, 5g lauryl sodium sulfate; 80 ℃ of following Dropwise 5 0g (50 weight %) SM (styrene), 30g (30 weight %) AN (acrylonitrile), 20g (20 weight %) example compound D4; 0.7g AIBN (azodiisobutyronitrile); 1.5 hours dropping time; React again and add 0.3g AIBN (azodiisobutyronitrile) after 7.5 hours, continue to react again after 12 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 80000, and particle diameter is 170nm.

Comparative example B04

In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device, add the 325g butanone; 15g (15 weight %) example compound C2 (n is about 43～44), 15 g (15 weight %) example compound D4; 55g (55 weight %) SM (styrene), 15g (15 weight %) AN (acrylonitrile), 0.7g AIBN (azodiisobutyronitrile); After the back flow reaction 7 hours, add 0.3g AIBN (azodiisobutyronitrile), continue to react again after 5 hours and finish.

Solid content is 23.5%, and the GPC molecular weight is 80000.

The present invention will be described below in conjunction with embodiment, but the present invention does not receive the qualification of these embodiment.

Embodiment 1

[making of photopolymerizable lithographic plate]

The curling aluminium volume for web-like (shape curls) of aluminium sheet (support) of thick 0.30mm is fixed on the machine of seeing off.Surface treatment with 10% NaOH, down will see the aluminium sheet that machine sees off continuously off at 70 ℃ and flood for 60 seconds from this, carry out etching after, after washing with flowing water, use 20%HN0 ₃Washing, washing neutralize.Under the condition of VA=12.7V, use sinusoidal wave alternately waveform electric current, in 1% aqueous solution of nitric acid with 300 coulombs/dm ²Anode the time electric weight it is carried out the electrolytic surface roughened.Measure its surface roughness, it is 0.6u m (Ra representes).

Then impregnated in 30% H ₂SO ₄In the aqueous solution, after carrying out 2 minutes crude removals under 55 ℃, at 33 ℃, 20%H ₂SO ₄In the aqueous solution, on the face of graining, dispose negative electrode, at current density 5A/dm ²Down, carry out anodic oxidation in 50 seconds, thickness is 2.7g/m ²In addition, the anodic oxide coating at the back side is about 0.5g/m at the central portion of aluminium sheet at this moment ², be about 1.0g/m in the end ²

Following hydrophilic layer coating composition is mixed, stir down at 30 ℃.After about 5 minutes, find heating, react after 60 minutes, content is transferred in the other container that through adding 10000 weight portion methyl alcohol again, coating is used in the modulation primary coat.

(liquid composition is used in primary coat)

Methyl alcohol 100 weight portions

Water 120 weight portions

Phosphoric acid (85% aqueous solution) 10 weight portions

3～methacryloxypropyl triethoxysilane, 25 weight portions

This aqueous coating is applied on the aluminium sheet of above-mentioned processing and reaches 0.1g/m ², carry out drying and reach 70 ℃ until the aluminium temperature, cool off then until the aluminium temperature and reach below 50 ℃.

On the priming coat that obtains like this, be coated with the high sensitivity optical polymerism composition of following composition, make drying coated weight reach 1.6g/m ², carry out drying and reach 100 ℃ until the aluminium temperature, cool off then until the aluminium temperature and reach below 50 ℃.

(photosensitive layer coating liquid composition)

Polyurethane acrylic acid ester (SARTOMER company, CN970A60) 2.0 weight portions

Emulsion particle P01 1.0 weight portions

Acrylic ester oligomer (SARTOMER company, CN549) 2.0 weight portions

Multifunctional monomer (SARTOMER company, SR531) 1.5 weight portions

Sensitizer (second photographic film plant, SDV-2) 0.2 weight portion

Photoepolymerizationinitiater initiater (CIBA, titanocene compound) 0.2 weight portion

Phthalocyanine color dispersion ((second photographic film plant, 15:1 CuPc) 0.02 weight portion

Fluorine is non-ionic surface active agent (3M company, FC-4431) 0.03 weight portion

Methyl ethyl ketone 40 weight portions

Propylene glycol monomethyl ether acetate 40 weight portions

Be coated on this photosensitive layer coating by the following protective finish that constitutes of forming with protective finish, making drying coated weight is 2.0g/m ², at drying section, blowed 120 ℃ of dry wind temperature second 5 minutes with wind speed 8m/, carry out drying and make polyvinyl alcohol dry, cool off then until the aluminium temperature and reach below 50 ℃.

(protective layer coating solution composition)

Polyvinyl alcohol (kuraray company, PVA-117) 20 weight portions

PVP (Shanghai reagent company of traditional Chinese medicines group) 2 weight portions

Surfactant (Shanghai reagent company of traditional Chinese medicines group, OP-15) 0.5 weight portion

Distilled water 300 weight portions

Embodiment 2-16

In embodiment 2-5, difference is that emulsion particle P01 changes respectively and is emulsion particle P02-P16 in the photosensitive layer coating liquid composition of embodiment 1, and all the other adopt with embodiment 1 same method and make photo-polymerization type lithographic printing plate.

Comparative example 1-4

In comparative example 1-4, with the difference of embodiment 1 be that emulsion particle P01 changes respectively to outside B01, B02, B03, the B04 in the photosensitive layer coating liquid composition of embodiment 1, adopt with embodiment 1 same method and make photo-polymerization type lithographic printing plate.

The photo-polymerization type lithographic printing plate sample is estimated

The photosensitive layer developing performance is estimated (drop)

Get above-mentioned plate batten, the flush away protective layer dries, and on the placement platform, whenever drips developer solution at a distance from 5 seconds with dropper, drips 6 altogether, drips off after last and waits 5 seconds.Rinsing well with deionized water at once, measure the version base density of blank space with reflection densitometer, do contrast with the white version base density of uncoated sensitization liquid, is the clean time with first of equal densities, and the time is short more, and developing powder is fast more.The present invention uses developer solution to be alkalescent, and its pH value is lower than 10, and PH is the developer solution of 8.5-9.5.

Pressrun is estimated

The photopolymerization flat stamping version that makes with said method through 405 or the purple laser of 410nm with suitable light exposure photosensitive layer is carried out image exposure, make and see that light is partly solidified.Through development treatment, that removes photopolymerization layer does not see the light part, can on aluminium sheet support surface, form image.The present invention uses developer solution to be alkalescent, and its pH value is lower than 10, and PH is the developer solution of 8.5-9.5.

To between developing, be purpose behind the image exposure, can be arranged on the heating process of carrying out 1 second-5 minutes clock times under 50 ℃-150 ℃ the temperature with the curing degree that improves the photo-polymerization type photosensitive layer.

In addition, as stated, the known protective finish that on the photosensitive layer of photosensitive lithographic plate of the present invention, is provided with oxygen barrier performance, the present invention uses developer solution to carry out the method for removal of removal and the photosensitive layer unexposed portion of protective finish simultaneously.

Carried out the photosensitive lithographic plate of development treatment like this, water wash water, the leacheate that contains surfactant etc., the lipoprotein liquid of not feeling that contains gum arabic or starch derivatives etc. carry out post processing.Lithographic plate through this Processing of Preparation is installed on the offset press, is used for the printing of multipage.

Can find out from subordinate list 1, contain the present invention and receive the purple laser light polymerization of the low chemical treatment version of micron particles that the ammonia ester bond of strong polarity exists in the micron particles owing to receive, flat stamping version coating press resistance rate is higher; Simultaneously because to receive the permeability of micron particles better, and wherein contain acrylamide hydrophilic derivant construction unit, so plate has good developing performance.

Table 1 plate application performance table

Claims (9)

1. the purple laser photo-polymerization type lithographic printing plate of one kind low chemical treatment; Include support in the said photo-polymerization type lithographic printing plate body; Be the photo-polymerization type photosensitive layer on support, on the photo-polymerization type photosensitive layer,, it is characterized in that: in the photo-polymerization type photosensitive layer, include a kind of micron particles of receiving with the water-based protective layer; It is a kind of high molecular polymerization particle that exists with the emulsion discrete form, and the described micron particles of receiving is the vinyl multiple copolymer that contains following construction unit:

A: styrol structural unit;

B: (methyl) acrylonitrile unit unit;

C: ammonia esterification polyethers self-emulsifying construction unit;

In the formula, R ¹Be hydrogen atom or methyl, R ²Be ester group, penylene base or carbon-carbon single bond, r is the integer of 1-3; N is the integer of 9-140;

D: acrylamide hydrophilic derivant construction unit;

In the formula, R ³Be hydrogen atom or methyl, R ⁴Be hydroxyl or sulfoamido.

2. low chemical treatment photo-polymerization type lithographic printing plate according to claim 1 is characterized in that: it is 20000-150000 that said vinyl multiple copolymer is received the weight average molecular weight of micron particles; Glass transition temperature is 30-260 ℃; Particle diameter is 15-300nm, and the weight percent content of styrene copolymerized unit A in copolymer is 30%-80%; The weight percent content of (methyl) acrylonitrile compolymer unit B in copolymer is 0.5%-40%; The weight percent content of ammonia esterification polyethers self-emulsifying construction unit C in copolymer is 0.5%-40%; The weight percent content of acrylamide hydrophilic derivant construction unit D in copolymer is 0.5%-40%.

3. low chemical treatment photo-polymerization type lithographic printing plate according to claim 2 is characterized in that: it is 35000-120000 that said vinyl multiple copolymer is received the weight average molecular weight of micron particles; Glass transition temperature is 40-220 ℃; Particle diameter is 35-250nm, and the weight percent content of styrene copolymerized unit A in copolymer is 40%-70%; The weight percent content of (methyl) acrylonitrile compolymer unit B in copolymer is 5%-30%; The weight percent content of ammonia esterification polyethers self-emulsifying construction unit C in copolymer is 5%-30%; The weight percent content of acrylamide hydrophilic derivant construction unit D in copolymer is 5%-50%.

4. low chemical treatment photo-polymerization type lithographic printing plate according to claim 3 is characterized in that: it is 50000-100000 that said vinyl multiple copolymer is received the weight average molecular weight of micron particles; Glass transition temperature is 60-180 ℃; Particle diameter is 55-200nm, and the weight percent content of styrene copolymerized unit A in copolymer is 50%-60%; The weight percent content of (methyl) acrylonitrile compolymer unit B in copolymer is 10%-20%; The weight percent content of ammonia esterification polyethers self-emulsifying construction unit C in copolymer is 10%-20%; The weight percent content of acrylamide hydrophilic derivant construction unit D in copolymer is 10%-20%.

5. want 1 or 2 or 3 or 4 said described photo-polymerization type lithographic printing plates according to right; It is characterized in that: described said vinyl multiple copolymer is received the percentage by weight of micron particles in the photo-polymerization type lithographic printing plate photosensitive layer between 1-30%, and best percentage by weight is between 1-20%.

6. photo-polymerization type lithographic printing plate according to claim 1; It is characterized in that: include support in the said photo-polymerization type lithographic printing plate body; Be the photo-polymerization type photosensitive layer on support, its photo-polymerization type photosensitive layer component comprises ethene property unsaturated group compound, one pack system or bi-component or the multicomponent initiator system and the colouring agent that can carry out photopolymerization reaction.

7. photo-polymerization type lithographic printing plate according to claim 6; It is characterized in that: described ethene property unsaturated group compound is simple function group or multi-functional monomer, simple function group or multi-functional oligomer; More than any one or more combination; The weight percent concentration of described ethene property unsaturated group compound in the photo-polymerization type photosensitive layer is 10-90%, is preferably 50-80%.

8. photo-polymerization type lithographic printing plate according to claim 6; It is characterized in that: described one pack system or bi-component or multicomponent initiator system; Comprise sensitizing dye, initator and aided initiating or join transfer agent; Its weight percent concentration in the photo-polymerization type photosensitive layer is 5-30%, is preferably 5-20%.

9. photo-polymerization type lithographic printing plate according to claim 6 is characterized in that: described colouring agent is dyestuff or pigment, and its weight percent concentration in the photo-polymerization type photosensitive layer is 0.5-20%;

According to claim 1 or 6 described photo-polymerization type lithographic printing plates; It is characterized in that: include support in the said photo-polymerization type lithographic printing plate body; Be the photo-polymerization type photosensitive layer on support, the dried coating weight of photo-polymerization type photosensitive layer is 0.1g/m ²-10g/m ², be preferably 0.3-5g/m ², further be preferably 0.5-3g/m ²Include support in the said photo-polymerization type lithographic printing plate body; It on support the photo-polymerization type photosensitive layer; On the photo-polymerization type photosensitive layer, has the water-based protective layer; Its protective layer comprises water-soluble high-molecular compound, surfactant and antiseptic component, and the dried coating weight of water-based protective layer is for being 0.5-10g/m ², be preferably 1.0-5.0g/m ²