CN102582312B - A kind of low chemical treatment violet laser photopolymerization type planographic printing plate - Google Patents

Abstract

A kind of low chemical treatment violet laser photopolymerization type planographic printing plate; described Photopolymerization type lithographic plate main body includes support; it it is photo-polymerization type photosensitive layer on support; with aqueous protective layer on photo-polymerization type photosensitive layer; it is characterized in that: include one in photo-polymerization type photosensitive layer and receive micron particle, it is a kind of high molecular polymerization granule existed with emulsion discrete form.It can make plate have the developing performance that higher press resistance rate is become reconciled, thus providing a kind of better low chemical treatment CTP plate precursor.

Description

A kind of low chemical treatment violet laser photopolymerization type planographic printing plate

Technical field

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

Background technology

Recently as the development of computer and semiconductor laser technique, photosensitive polymer material is extensively studied as laser imaging material and applies.Lithography technique moves towards CTP technology (being called for short CTP technology) from traditional laser photo film copy PS platemaking technology comprehensively, and CTP plate is also popularized gradually.CTP plate kind is a lot, and relatively more universal includes Silver Salt Diffusion Transfer CTP Plate material, UV-CTP version, purple laser polymerization CTP plate, thermal CTP plate material etc..

So-called photopolymerization refers under the effect of light, makes the method that polymerization occurs monomer.Light initiation polymerization divides direct light initiation polymerization and photosensitive polymerization two kinds.The former, under the effect of light, light trigger generates activity seed (free radical or cation) in excited state, and trigger monomer is polymerized；Then the latter's photosensitizer first absorbing light produces activity seed trigger monomer and is polymerized with light trigger effect, thus can according to the absorption spectrum of photosensitizer, it is achieved required sensitive volume is infrared light 830nm, green glow 532nm, blue light 488nm and orchid light 405nm such as.

For can the photo-polymerization type lithographic printing plate of laser imaging, during exposure, sensitizing dye (photosensitizer) in photosensitive layer absorbs energy, molecule is from ground state transition to excited state, shifted by energy or electron transfer makes decomposition of initiator produce free radical, cause the active substance (containing double bond compound) in photosensitive layer that polyreaction occurs.Occur polyreaction to solidify through the region of laser explosure, become from dissolving insoluble in developer solution, form image areas；It is removed after the developed processing of unexposed area, forms forme clear area.In the strong basicity developer solution have PH > 10, generally process exposed forme, the developer solution alkalescence of PH > 10 is stronger, machine in use has stronger corrosion, and the discharging of waste liquid after using is also relatively serious to the pollution of environment.

Summary of the invention

The purpose of the present invention is that the above-mentioned technical problem solving exist in prior art, a kind of low chemical treatment violet laser photopolymerization type planographic printing plate is provided, plate can be made to have the developing performance that higher press resistance rate is become reconciled, the developer solution of PH < 10 can be adopted to process exposed forme.

For achieving the above object, the technical solution used in the present invention is as follows:

The low chemical treatment photo-polymerization type lithographic printing plate of the present invention; described Photopolymerization type lithographic plate main body includes support; it it is photo-polymerization type photosensitive layer on support; with aqueous protective layer on photo-polymerization type photosensitive layer; photo-polymerization type photosensitive layer includes one and receives micron particle; it is a kind of high molecular polymerization granule existed with emulsion discrete form, and described micron particle of receiving is the vinyl multiple copolymer containing, for example lower construction unit:

A: styrol structural unit；

B:(methyl) acrylonitrile unit unit；

C: ammonia Esterification polyether self emulsifying construction unit；

In 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 formula, R³For hydrogen atom or methyl, R⁴For hydroxyl or sulfoamido.

It is 20000-150000 that described vinyl multiple copolymer receives the weight average molecular weight of micron particle；Glass transition temperature is 30-260 DEG C；Particle diameter is 15-300nm, and styrenic interpolymerized units A weight percent content in the copolymer is 30%-80%；(methyl) acrylonitrile compolymer unit B weight percent content in the copolymer is 0.5%-40%；Ammonia Esterification polyether self emulsifying construction unit C weight percent content in the copolymer is 0.5%-40%；Acrylamide hydrophilic derivant construction unit D weight percent content in the copolymer is 0.5%-40%.

Described vinyl multiple copolymer is received the weight average molecular weight of micron particle and is preferably 35000-120000；Glass transition temperature is preferably 40-220 DEG C；Particle diameter is preferably 35-250nm, styrenic interpolymerized units A weight percent content in the copolymer and is preferably 40%-70%；(methyl) acrylonitrile compolymer unit B weight percent content in the copolymer is preferably 5%-30%；Ammonia Esterification polyether self emulsifying construction unit C weight percent content in the copolymer is preferably 5%-30%；Acrylamide hydrophilic derivant construction unit D weight percent content in the copolymer is preferably 5%-50%.

Described vinyl multiple copolymer is received the weight average molecular weight of micron particle and most preferably is 50000-100000；Glass transition temperature most preferably is 60-180 DEG C；Particle diameter most preferably is 55-200nm, styrenic interpolymerized units A weight percent content in the copolymer and most preferably is 50%-60%；(methyl) acrylonitrile compolymer unit B weight percent content in the copolymer most preferably is 10%-20%；Ammonia Esterification polyether self emulsifying construction unit C weight percent content in the copolymer most preferably is 10%-20%；Acrylamide hydrophilic derivant construction unit D weight percent content in the copolymer most preferably is 10%-20%.

Medium vinyl multiple copolymer of the present invention receive micron particle synthesis adopt random copolymerization method; the initiator of polymerization at least contains peroxide thing; copolymerization mode adopts emulsion to be polymerized, and described peroxide is the one in benzoyl peroxide or persulfate such as potassium peroxydisulfate or azo-compound such as azodiisobutyronitrile etc..Feed way adopts the mode of part material dropping, and the size of thermoplastic nano-micron particle controls by changing reaction system concentration and time for adding, and reaction dissolvent adopts the mixture of alcohol and water, and reaction temperature is 60-90 DEG C.

Described described vinyl multiple copolymer receives micron particle percentage by weight in photo-polymerization type lithographic printing plate photosensitive layer between 1-30%, and best percentage by weight is between 1-20%.

Described Photopolymerization type lithographic plate main body includes support, being photo-polymerization type photosensitive layer on support, its photo-polymerization type photosensitive layer component includes carrying out the ethylene unsaturated group compound of photopolymerization reaction, one pack system or bi-component or multicomponent initiator system and coloring agent.

Described ethylene unsaturated group compound is simple function group or multi-functional monomer, simple function group or multi-functional oligomer, any of the above or multiple combination, described ethylene unsaturated group compound weight percent concentration in photo-polymerization type photosensitive layer is 10-90%, it is preferred to 50-80%.

Described one pack system or bi-component or multicomponent initiator system, including sensitizing dye, initiator and aided initiating or connection transfer agent, its weight percent concentration in photo-polymerization type photosensitive layer is 5-30%, it is preferred to 5-20%.

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

Including support in described Photopolymerization type lithographic plate main body, be photo-polymerization type photosensitive layer on support, the dried coating weight of photo-polymerization type photosensitive layer is 0.1g/m²-10g/m², it is preferred to 0.3-5g/m², more preferably 0.5-3g/m²。

Described Photopolymerization type lithographic plate main body includes support; it it is photo-polymerization type photosensitive layer on support; with aqueous protective layer on photo-polymerization type photosensitive layer; its protective layer includes water-soluble high-molecular compound, surfactant and antimicrobial moiety, and the dried coating weight of aqueous protective layer is for for 0.5-10g/m², it is preferred to 1.0-5.0g/m²。

Due to the fact that the above-mentioned micron particle of receiving of employing, plate can be made to have the developing performance that higher press resistance rate is become reconciled, thus providing a kind of better low chemical treatment CTP plate precursor.

Detailed description of the invention

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

One, support

The support used in the present invention can use the aluminum of dimensionally stable or its alloy (such as with silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel alloy).Generally can be used in aluminum handbook the 4th edition (1990, light metal association distribution) the known material recorded.Aluminium plate can be the aluminium sheet adopting common semi-continuous casting method (DC method) to manufacture, and can also be adopt the aluminium plate that casting rolling process manufactures continuously in addition.Method as casting calendering continuously, it is possible to use double roller therapy, tape casting method, block casting method etc..In alloy, the content of xenogenesis element is below 10 weight %.The thickness of aluminium plate is preferably about 0.1mm mono-about 0.6mm.In addition it is also possible to use lamination or be deposited with aluminum, the plastic foil of aluminium alloy or paper.

1, the surface treatment of support

When support is aluminium plate, generally according to purpose, various process are implemented on its surface.As general processing method, first pass through and aluminium sheet is carried out defat or electrolytic polishing process and crude removal process, aluminum surface is cleaned.Then, implement mechanical surface roughening process or/and electrochemically grained process, give aluminium plate surface fine concavo-convex.Additionally, sometimes also increase chemical etching process and crude removal process.Then, in order to improve the abrasion performance of surface of aluminum plate, implement anodized, then as required hydrophilicity-imparting treatment is implemented or/and sealing pores in aluminum surface.

Throughout between reason, process to make the treatment fluid of previous processed not bring next into, it is preferable that the washing that injection etc. carries out is removed and adopted to the liquid carrying out adopting nip rolls to carry out.Furthermore, it is possible to the overflow waste liquid of the electrolyte used in electrochemically grained process to be used as crude removal treatment fluid, but now can omit the washing after crude removal processes and process.

1. defat one electrolytic polishing processes

The rolling oil existed on aluminium sheet, autoxidation epithelium, dirt etc. are removed, to carry out for the purpose of electrochemical surface roughening equably, the electrolytic polishing carrying out aluminium sheet in acidic aqueous solution processes, or the chemical etching carrying out aluminium sheet in acid or aqueous alkali processes.Process the meltage preferred dissolution 1--30g/m of the aluminium sheet produced².More preferably 1.5 20g/m are dissolved²。

A () electrolytic polishing processes

The known aqueous solution for electrolytic polishing can be used.Preferably based on the aqueous solution of sulphuric acid or phosphoric acid, it is particularly preferred to the aqueous solution based on phosphoric acid.Can from phosphoric acid 20 90 weight % (preferably 40 80 weight %), liquid temperature 10 1 90 DEG C (preferably 50 1 80 DEG C), electric current density 1-100A/dm²(preferably 5 80A/dm²), the electrolysis time scope of 180 seconds selects.50 weight % sulphuric acid, chromic acid, hydrogen peroxide, citric acid, Fluohydric acid., phthalic anhydride etc. can be added in phosphate aqueous solution.Electric current can use direct current, pulse direct current or exchange, but preferred direct current continuously.Electrolytic processing apparatus can use the device that the known electrolytic treatments such as flat type groove, star-like groove use.Flow velocity is relative to aluminium sheet, it is possible to for and flow, adverse current any, choose from the scope that 0.01--10000cm/ divides.

The preferred 0.3--10cm of distance of aluminium sheet and electrode, it is particularly preferred to 0.8 2cm.Can use to method for electrically adopt conductive rollers directly to electricity mode, it is possible to use do not adopt conductive rollers indirectly to electricity mode (liquid is to electricity mode).The electrode material, the structure that use can use the known material, the structure that use in electrolytic treatments, the preferred carbon of negative electrode material, the preferred ferrite of anode material, Indium sesquioxide. or paper tinsel.

B () chemical etching in acid or aqueous alkali processes

The chemical etching process carrying out aluminium sheet in acid or aqueous alkali can use these known means.Liquid temperature is preferably 25 90 DEG C, it is preferable that carry out 1-120 second processing.The concentration of acidic aqueous solution preferably 0.5 25 weight %, is 0.5 5 weight % more preferably in the aluminum dissolved in acidic aqueous solution.The concentration of aqueous alkali preferably 5 30 weight %, is 30 weight % more preferably in the aluminum dissolved in aqueous alkali.

2, crude removal processes

After etch processes, when the aqueous solution using alkali has carried out chemical etching, due to the Surface Creation dirt at aluminum, therefore general phosphoric acid, nitric acid, sulphuric acid, chromic acid or carry out processing (crude removal process) at the nitration mixture of interior acid of more than two kinds containing these.The acidic aqueous solution used can dissolve 05 weight % aluminum, implements liquid temperature is from room temperature to 70 DEG C, processes the time preferred 1-30 second.Additionally, as this acidic aqueous solution, it is possible to use at the waste liquid of the middle electrolyte used such as electrochemically grained process, it has to be noted that not making aluminium sheet dry, the one-tenth in crude removal liquid analyzes.After crude removal process terminates, in order to not bring treatment fluid into subsequent processing, it is preferable that the washing that injection carries out is removed and adopted to the liquid carrying out adopting nip rolls to carry out, but when subsequent processing is same aqueous solution, it is also possible to omit washing.

3, mechanical surface roughening process

In order to obtain good aluminum support, it is common that the surface frosted order to aluminium sheet, give fine concavo-convex.The mechanical surface roughening process such as commonly known pelletization, brush granulation, tinsel granulation, sandblasting granulation in this graining, but process as a large amount of and continuous print, brush granulated processed is excellent.Specifically, spray the serosity of silica sand, aluminium hydroxide etc. in surface of aluminum plate, make with 50 500rpm the nylon brush roll of bristle footpath 0.2 0.9mm rotate, carry out mechanical surface roughening process.The consumption electric power (removing the essence electric power of the mechanical loss driving motor) of the rotation drive motor of the pressing-in force of brush. preferably 0.2 15kw, more preferably 0.5 10kw.

4, electrochemically grained process

(a) use the electrochemically grained process of direct current based on the aqueous solution of hydrochloric acid or nitric acid, can be used in using the aqueous solution used in the electrochemically grained process of common exchange, it is possible in the hydrochloric acid or aqueous solution of nitric acid of 1-100g/L, add 1g/L used above to 1 with the hydrochloric acid of salt acid ion or nitrate compound such as saturated aluminum nitrate, sodium nitrate, ammonium nitrate.Additionally, the metal that can contain in the aluminium alloy such as dissolved iron, copper, manganese, titanium, magnesium, silicon dioxide in the aqueous solution based on hydrochloric acid or nitric acid.It is preferably used in hydrochloric acid or nitric acid 0.5 2 weight % aqueous solution and adds aluminum chloride, aluminum nitrate so that aluminium ion reaches the liquid of 3 50g/L.Temperature preferably 10 1 60 DEG C, more preferably 25 50 DEG C.The process device using the electrochemically grained middle use of direct current can make

With the device of known use direct current, use the device anode of a pair or more than two pairs and negative electrode arranged alternately.The direct current of electrochemically grained middle use is preferably used the direct current that pulsation rate is less than 20%.Electric current density is 10 200A/dm preferably², aluminium sheet is preferably 10 1 1000C/dm of electricity during anode².Anode can from ferrite, Indium sesquioxide., paper tinsel, selection use in the known oxygen generation electrode such as compound or plating paper tinsel on the valve metals such as titanium, niobium, zirconium.Negative electrode can from carbon, paper tinsel, titanium, niobium, zirconium, rustless steel, selection use in the electrode of use cathode for fuel cell.

(b) use the electrochemically grained process of exchange based on the aqueous solution of hydrochloric acid or nitric acid, the aqueous solution used can be used in the common electrochemically grained process using exchange, can adding lg/L in the hydrochloric acid of 1--100g/L or aqueous solution of nitric acid and have nitrate ion to saturated aluminum nitrate, sodium nitrate, ammonium nitrate etc., aluminum chloride, sodium chloride, ammonium chloride etc. have the hydrochloric acid of salt acid ion or at least 1 use of nitrate compound.Additionally, the metal that can contain in the aluminium alloy such as dissolved iron, copper, manganese, nickel, titanium, magnesium, silicon dioxide in the aqueous solution based on hydrochloric acid or nitric acid.

It is preferably used in hydrochloric acid or nitric acid 0.5 2 weight % aqueous solution and adds aluminum chloride, aluminum nitrate etc. so that aluminium ion reaches the liquid of 3 50g/L.Temperature preferably 10 60 DEG C, more preferably 20 50 DEG C.

Alternating current power supply ripple use marking wave, square wave, platform shape ripple, the triangular wave etc. of (c) electrochemically grained middle use, but preferred square wave or platform shape ripple, it is particularly preferred to platform shape ripple.Electric current is from 0 time (TP) the preferably 1-3msec arriving peak.If it is less than 1msec, it is easy to the process producing the so-called electric shock ripple that produce vertical with the direct of travel of aluminium sheet is uneven.If TP is bigger than 3msec, in the electrolyte of electrochemically grained middle use with ammonium ion etc. for the electrolytic treatments in the nitric acid liquid of representative, it is easy to by the impact naturally producing the micro constitutent increased, not easily carry out homogeneous generation sand holes.

D the duty ratio of () platform shape ripple exchange can use 1:2 2:1, do not use the indirect in electricity mode of conductive rollers, it is preferable that duty ratio 1:l in aluminum.The frequency of platform shape ripple exchange can use 0.1--120Hz, preferred 50 1 70Hz on equipment.If lower than 50Hz, the carbon electrode of main pole easily dissolves, if bigger than 70Hz, it is easy to by the impact of the inductance composition on electric power loop, power supply cost up.But, when using containing during more than the aluminium alloy of the Cu of 0.1wt%, it is preferred to use the exchange of frequency 0.1--10Hz.The peak value of the current waveform of electric current density preferably 10 200A/dm²。

E the electrolysis bath of () electrochemically grained middle use can use the electrolysis bath used in longitudinal type, platypelloid type, the known surface treatment such as star-like, the electrolyte passed through in electrolysis bath can be parallel with the traveling of aluminum net, it is also possible to drives in the wrong direction with it.

F () can connect the alternating current power supply of more than 1 on electrolysis bath.The anode of exchange additional on the aluminium sheet relative with main pole and the current ratio of negative electrode are controlled, in the carbon dissolution preventing main pole, it is preferable that impressed current anode is set, make the part shunting of alternating current.By rectifier cell or switch element, make the part shunting of current value as with 2 main electrodes outside other groove on DC current on the impressed current anode that arranges, it is possible to the ratio of the current value participating in cathode reaction current value and participation anode reaction of effect on the aluminium sheet relative with main pole is controlled.On the aluminium sheet relative with main pole, participate in the ratio (during negative electrode electricity during electricity/anode) preferably 0.3 0.95 of the electricity of anode reaction and cathode reaction.

G (), with nitric acid or hydrochloric acid for the aqueous solution of main constituent, uses exchange or direct current, with 10---1000C/dm²Electricity this aluminium sheet is carried out electrochemically grained process, in acidic aqueous solution, using electric current is 1-3msec and platform shape ripple exchange that frequency is 50---70Hz from 0 to time of peaking.

5, chemical etching processes (utilizing acid-alkaline liquid)

By will mechanical surface roughening process, electrochemically grained process be formed whole of fine concavo-convex sand holes, for the purpose of dirt etc. removes, carry out chemical etching process.Liquid temperature is preferably 25 90 DEG C, it is preferable that carry out 1-120 second processing.The concentration of acidic aqueous solution preferably 0.5 25 weight %, is 0.5 5 weight % more preferably in the aluminum dissolved in acidic aqueous solution.The concentration of aqueous alkali preferably 5 30 weight %, is 1--30 weight % more preferably in the aluminum dissolved in aqueous alkali.Acid or aqueous alkali are etched process so that the meltage of aluminium sheet reaches 1g/m²Above, 30g/m²Below or the meltage of aluminum reach 0.1g/m²Above, 3g/m²Below.

In addition, when the aqueous solution using alkali carries out chemical etching, due to the Surface Creation dirt at aluminum, therefore general phosphoric acid, nitric acid, sulphuric acid, chromic acid or be etched processing (required crude removal processes) at the nitration mixture of interior acid of more than two kinds containing these in this case.(identical with above-mentioned crude removal record).

6, anodized

In order to improve the water-retaining property of surface of aluminum plate, abrasion performance, implement anodized.As the electrolyte used in the anodized of aluminium sheet, if forming porous oxidation epithelium, it is possible to use any electrolyte.Generally use sulphuric acid, phosphoric acid, oxalic acid, chromic acid or their mixed liquor.These electrolytical concentration suitably determine because of electrolytical kind.Anodised treatment conditions become because of the electrolyte that uses, therefore cannot treat different things as the same, if generally electrolytical concentration is 1--80wt%, liquid temperature is 5 70 DEG C, and electric current density is 1--60A/dm², voltage 1--100V, electrolysis time 5 seconds---be suitable in the scope of 300 seconds.Sulfuric acid process processes typically by DC current but it also may use exchange.The amount of anodic oxide coating is 0.5 10g/m²Scope be suitable.The concentration of sulphuric acid uses 5 30%.5 250 seconds electrolytic treatments are carried out in the temperature range of 20 60 DEG C.Preferably in this electrolyte contains aluminium ion.The more preferably 1--50A/dm of electric current density now².When phosphoric acid method, at the concentration 5 50%, the temperature of 30 60 DEG C, 10 300 seconds, 1--15A/dm²Electric current density under process.The amount of anodic oxide coating is preferably 1.0g/m²Above, more preferably 2.0 6.0g/m²Scope.

7, hydrophilicity-imparting treatment

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

After reason terminates throughout, in order to not bring treatment fluid into subsequent processing, carry out adopting nip rolls liquid to remove and adopt the washing that injection carries out.Preferably in implementing sealing pores after anodized.This sealing pores is by dipping in the hydrothermal solution containing hot water and inorganic salt or organic salt and adopts water vapour bath to carry out.

Two, the formation of photosensitive layer

Priming coat it is coated with the coating of photo-polymerization type photosensitive composite and is dried, forming photosensitive layer.

Photo-polymerization type photosensitive composite dissolves with the solid component concentration of 2 50 weight %, disperses, and is applied on support aluminum substrate and is dried.On support aluminum substrate, the coating weight of the layer (photosensitive layer) of the photo-polymerization type photosensitive composite of coating is different because of purposes, it is usually preferred to dried weight is 0.3 4.0g/m².Along with coating weight reduces, for obtaining the light exposure of image less, but film-strength reduction.Along with coating weight increases, with light exposure for required, but light-sensitive surface strengthens, for instance, when as galley, it is possible to the galley of the number of pages many (high resistance to brush) obtaining printing.Photosensitive composite can add for improving the surfactant of coated face matter, particularly preferably fluorine class surfactant.

The photosensitive layer constituting photosensitive lithographic plate used in the present invention with described receive a micron high molecular polymerization granule, can the ethylenically unsaturated compounds of addition polymerization, light trigger, macromolecule bonding agent for essential component, the various compounds such as coloring agent, plasticizer, heat polymerization inhibitors be can be used together as required.

The low chemical treatment photo-polymerization type lithographic printing plate of the present invention, photo-polymerization type photosensitive layer includes one and receives micron particle, it is a kind of high molecular polymerization granule existed with emulsion discrete form, and described micron particle of receiving is the vinyl multiple copolymer containing, for example lower construction unit:

A: styrol structural unit；

B:(methyl) acrylonitrile unit unit；

C: ammonia Esterification polyether self emulsifying construction unit；

In 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 formula, R³For hydrogen atom or methyl, R⁴For hydroxyl or sulfoamido.

The micron particle of receiving of the present invention is a kind of high molecular polymerization granule existed with emulsion discrete form, and it includes following dominance structure unit:

1, containing styrol structural unit A.It is known that styrol structural unit glass transition temperature is higher, styrol copolymer can improve the hardness of coating, can increase plate pressrun, the ink affinity additionally having had；

2, containing cyano group side base hydrophobic group, there is good drug resistance, pliability and hydrophobicity；It is the vinyl component construction unit B devising side chain in copolymerization component containing base nitrile that the multiple copolymer of the present invention introduces the method for hydrophobic side chain radical nitrile, it includes itrile group acrylic acid methyl ester., itrile group ethyl acrylate, acrylonitrile or methacrylonitrile etc., it is preferable that acrylonitrile or methacrylonitrile or their mixture.

3, containing ammonia Esterification polyether self emulsifying construction unit, polymer can lean on the polyethers emulsifying group of self to realize emulsifying under not having additional emulsifying agent existent condition, and the emulsion particle of synthesis is more homogeneous, mellow and full than outer emulsifying emulsion particle, and stability is better；Simultaneously highly polar ammonia ester bond exists, emulsion particle elastic better, more resistant to mill；It is known that polyurethane elastomer is owing to having significantly high wearability containing highly polar ammonia ester bond, it is referred to as " wear-resisting king " resin.So, we are simultaneously introduced highly polar ammonia ester bond at thermoplastic nano-micron particle, introduce emulsion particle after highly polar ammonia ester bond elastic better, more resistant to mill.The thermoplastic nano-micron particle of the present invention devises ammonia Esterification polyether self emulsifying construction unit C in copolymerization component, and its structure is as follows:

In formula, R¹For hydrogen atom or methyl, R²For ester group, penylene base or valence link, r is the integer of 1-3；N is 9-140 integer.

Typical example sees below structural formula, but the invention is not limited in the structural formula of following C1-C3.

C1

C2

C3

C2 has industrialized product and sells.C1, C3 can laboratory batch synthesis.So select with industrialized products C 2 in plate produces as far as possible.

4, containing acrylamide hydrophilic derivant construction unit, it is possible to for receiving the micron particle good water development of offer or weak base development.

The hydrophilic best approach of micron particle that realizes receiving is exactly direct copolymerization units containing hydrophilic group in resin structure.Hydrophilic group has carboxyl, hydroxyl, phosphate, sulfonic group, amino, amide groups, ether etc..The micron particle of receiving of the present invention devises acrylamide hydrophilic derivant construction unit D in copolymerization component, and its structure is as follows:

In formula, R³For hydrogen atom or methyl, R⁴For hydroxyl or sulfoamido.

The typical example of typical case sees below structural formula, but the invention is not limited in 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 hydrophilic for receiving micron particle, and simultaneously highly polar amido link also can provide good solvent resistance and wearability for the micron particle film of receiving that thermoplastic merges.

Synthesize the method that micron particle adopts copolymerization of receiving of the present invention, the optional random copolymerization of copolyreaction or block copolymerization, it is preferable that random copolymerization.The initiator of polymerization includes peroxide such as di-tert-butyl peroxide, benzoyl peroxide, and persulfate is potassium peroxydisulfate, Ammonium Persulfate 98.5 such as, azo-compound such as azodiisobutyronitrile etc..Copolymerization mode adopts emulsion to be polymerized.

Available reaction dissolvent has water, methanol, ethanol, normal propyl alcohol, isopropanol, butanol, acetone, butanone, Ketohexamethylene, ethyl acetate, butyl acetate, oxolane, 1, 4-dioxane, N, dinethylformamide, dimethyl acetylamide acetone, methyl ethyl ketone, hexamethylene, ethylene dichloride, toluene, ethylene glycol monomethyl ether, ethylene glycol, 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 acetas, 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 acetas, , dimethyl sulfoxide, methyl lactate and ethyl lactate etc., or their mixture.Mixture preferably with alcohol and water, it is preferable that the mixture of normal propyl alcohol-water or isopropanol-water.Preferred 40-100 DEG C of emulsion copolymerization reaction temperature, optimum is 60-90 DEG C.

So-called ethylenically unsaturated compounds, refers to that photo-polymerization type photosensitive composite accepts active ray when irradiating, there is the effect utilizing Photoepolymerizationinitiater initiater and addition polymerization, crosslinking, solidification the compound of ethylenic unsaturated bond.

Containing can the compound of ethylenic double bond of addition polymerization, it is possible to from least having 1, preferably have the compound of more than 2 terminal ethylenic unsaturated bonds and arbitrarily select.

Can have such as 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, the ester of unsaturated carboxylic acid (such as acrylic acid, methacrylic acid, itaconic acid .beta.-methylacrylic acid, iso-crotonic acid, maleic acid etc.) and aliphatic polybasic alcoholic compound, the amide etc. of unsaturated carboxylic acid and aliphatic polybasic amines can be enumerated.

Concrete example as aliphatic polybasic alcoholic compound and the monomer of the ester of unsaturated carboxylic acid, including: as the glycol diacrylate of acrylate, triethylene glycol diacrylate, 1, 3--butanediol diacrylate, 1, 4--butanediol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tris (acryloxypropyl) ether, methylolethane triacrylate, hexanediyl ester, 1, 4--cyclohexanediol diacrylate, Aronix M 240, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol diacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol five acrylate, sorbitol six acrylate, three (acrylyl oxy-ethyl) isocyanuric acid ester, polyester acrylate oligomers etc..

As methacrylate, including 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, pentaerythritol tetramethylacrylate, dipentaerythritol dimethylacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylates, sorbitol trimethyl acrylic ester, sorbitol tetramethyl acrylate, two [p--(3--methacryloxy 2--hydroxy propyloxy group) phenyl] dimethylmethane, two [p--(methacroyloxyethoxy) phenyl] dimethylmethane etc..As itaconate, including ethylene glycol bisthioglycolate itaconate, propylene glycol diitaconate, 1,3--butanediol diitaconate, Isosorbide-5-Nitrae--butanediol diitaconate, Isosorbide-5-Nitrae--butanediol diitaconate, tetramethylolmethane diitaconate, sorbitol four itaconate etc..

As crotonates, including ethylene glycol bisthioglycolate crotonates, l, 4--butanediol two crotonates, tetramethylolmethane two crotonates, sorbitol four crotonates etc..

As iso-crotonic acid ester, including ethylene glycol bisthioglycolate iso-crotonic acid ester, tetramethylolmethane two iso-crotonic acid ester, sorbitol four iso-crotonic acid ester etc..

As maleate, including ethylene glycol bisthioglycolate maleate, 2,2'-ethylenedioxybis(ethanol). dimaleate, tetramethylolmethane dimaleate, sorbitol four maleate etc..

Further, it is also possible to enumerate the mixture of above-mentioned ester monomer.

In addition, concrete example as aliphatic polybasic amines and the monomer of the amide of unsaturated carboxylic acid, including methylene-bis-acrylamide, di-2-ethylhexylphosphine oxide--Methacrylamide, 1,6--hexa-methylene pair--acrylamide, 1,6--hexa-methylene are double; two--the double; two Methacrylamides of Methacrylamide, diethylenetriamines three acrylamide, xylylene bisacrylamide, xylylene etc..

Additionally, these ethylenically unsaturated compounds make consumption with 5 80 weight % of photosensitive layer whole part, it is preferable that the scope of 30 1 70 weight % uses.

In addition, as the purple laser light polymerization initiator contained in the photosensitive layer of the photosensitive lithographic plate of the present invention, wavelength according to the light source used can suitably select known various light triggers in patent, document etc., or the paralled system of light trigger of more than two kinds (light initiation system) uses.It is exemplified below concrete example, but is not limited to these.

For example, it is possible to enumerate cation pigment/borate-based, merocyanine pigment/titanocenes system, carbazole type pigment/titanocenes system etc..

In the present invention, it is particularly preferred to use titanocenes compound.

As titanocenes compound, this material various can be used, more specifically, dicyclopentadienyl Ti--dichloride can be enumerated, dicyclopentadienyl Ti--diphenyl, dicyclopentadienyl Ti--bis---2, 3, 4, 5, 6--phenyl-pentafluoride--1-base, dicyclopentadienyl Ti--bis---2, 3, 5, 6--phenyl tetrafluoride--1--base, dicyclopentadienyl Ti--bis---2, 4, 6--trifluoro-benzene-1--base, dicyclopentadienyl Ti--bis---2, 6--difluorobenzene--1--base, dicyclopentadienyl Ti--bis---2, 4--difluorobenzene--1--base, two--methyl cyclopentadienyl Ti--bis---2, 3, 4, 5, 6--phenyl-pentafluoride--1--base, two--methyl cyclopentadienyl Ti--bis---2, 6--difluorobenzene--1--base, dicyclopentadienyl Ti--bis---2, 6--difluoro--3--(pyrroles--1--yl)--benzene--1--base etc..

In addition, known to adding the thiol moiety such as 2--mercaptobenzothiazoler, 2--mercaptobenzimidazole, 2--mercaptobenzooxazole in above-mentioned light trigger, N--phenylglycine, N, hydrogen the giving property compounds such as amines such as N--dialkyl amido aromatic alkyl ester, it is possible to improve light-initiated ability further.

What these Photoepolymerizationinitiater initiaters (were) makes consumption relative to ethylenically unsaturated compounds 100 weight portion, at 0.05 100 weight portions, preferably 0.1---use in the scope of 70 weight portions, more preferably 0.2 50 weight portions.

As the macromolecule bonding agent used in the photosensitive layer of the photosensitive lithographic plate of the present invention, owing to serving not only as the peel-forming agent of said composition, and must be dissolved in alkaline developer, the organic high molecular polymer being therefore used in aqueous alkali solubility or swellability.As such organic high molecular polymer, there is including side chain the addition polymer of carboxylic acid group, i.e. methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid-copolymers, maleic acid, partial esterification maleic acid etc..

In addition the same acid cellulose derivant at side chain with carboxylic acid group is included.On this external addition polymer with hydroxyl, the polymer of addition cyclic acid anhydride etc. are useful.Wherein particularly preferably [(methyl) benzyl acrylate/(methyl) acrylic acid/other addition polymerization sex ethylene base monomers] as required copolymer and [(methyl) allyl acrylate/(methyl) acrylic acid/other addition polymerization sex ethylene base monomers] as required copolymer.Additionally, as water soluble organic polymer, polyvinyl pyrrolidone, poly(ethylene oxide) etc. are useful.Additionally, for the intensity improving cured film, alcohol soluble polyamide, the polyethers etc. of propane and chloropropylene oxide is also useful to 2,2--bis---(4--hydroxyphenyl)--.

These high molecular polymers are by importing free-radical reactive group at side chain, it is possible to improve the intensity of cured film.As can the functional group of polyaddition reaction, ethylenic unsaturated bond base, amino, epoxy radicals can be enumerated, in addition, as the functional group that can be become free radical by illumination, sulfydryl, mercapto, halogen atom, triazine structure, salt structure etc. can be enumerated, additionally, as polar group, it is possible to enumerate carboxyl, imino group etc..As above-mentioned can the functional group of polyaddition reaction; the particularly preferably ethylenic unsaturated bond base such as acryloyl group, methylacryloyl, pi-allyl, styryl; in addition; the functional group selected from amino, hydroxyl, phosphonate group, phosphate, carbamoyl, NCO, urea groups, l, 3-urylene, sulfonic group, ammonium is also useful.

In order to maintain the developability of compositions, the macromolecule bonding agent of the present invention preferably has suitable molecular weight, acid number, and effectively to use weight average molecular weight be 5,000 30 ten thousand, acid number is the high molecular polymer of 10 200.

These organic high molecular polymers can mix arbitrary amount in all compositions.But, when more than 90 weight %, in the image intensity etc. formed, produce preferred result.It is preferably 10 90%, more preferably 30 80%.Furthermore, it is possible to photopolymerisable ethylenically unsaturated compounds and organic high molecular polymer represent with weight ratio, it is preferred to the scope of l/9 9/l.Preferred range for 2/8 8/2, more preferably 3/7 7/3.

Additionally, in the present invention, except above basis, in the manufacture of photosensitive composite or in preserving, in order to stop the unnecessary thermal polymerization of polymerisable ethylenically unsaturated compounds, it is preferable that add a small amount of heat polymerization inhibitors.As suitable heat polymerization inhibitors, can enumerate hydroquinone, p methoxy phenol, ditertbutylparacresol, burnt Fructus Citri tangerinae phenol, tert-butyl catechol, benzoquinone, 4,4 '-sulfo-two (3 methy 6 tert butyl phenol), 2,2 '-methylene two (4-methyl-6-tert-butylphenol), N-nitroso-group phenylhydroxylamine Asia cerium salt, N-nitroso-group phenylhydroxylamine aluminium salt etc..The addition of heat polymerization inhibitors is relative to the weight of all compositions, it is preferable that about 0.01%-about 5%.

Additionally, the inhibition produced for anti-block, mountain lush acid, the mountain lush acid such advanced higher fatty acid derivative of amide etc. can be added as required, dry run after coating make it be partial to the surface of photosensitive layer and exist.The addition of advanced higher fatty acid derivative is preferably the 0.5%-10% of all compositions.

Additionally, be colored as purpose with photosensitive layer, it is possible to add coloring agent.As coloring agent, the pigment such as including such as phthualocyanine pigment, azo pigment, white carbon black, titanium oxide, ethyl violet, crystal violet, azo dye, anthraquinone based dye, cyanine based dye.The addition of dyestuff and pigment is preferably the 0.5%-20% of all compositions.

Additionally, for the physical property improving cured film, it is possible to add the additives such as plasticizer such as inorganic filler or dioctyl phthalate, dimethyl phthalate, tricresyl phosphate.Their addition is preferably less than the 10% of all compositions.

On support aluminium plate during photosensitive coated layer compositions, be dissolved in various organic solvent for.As solvent used herein, including acetone, methyl ethyl ketone, hexamethylene, 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, Ketohexamethylene, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, ethyleneglycol monopropylether, 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 1 Methoxypropylacetate, N, N dimethyl formamide, dimethyl sulfoxide, Y mono-butyrolactone, methyl lactate, ethyl lactate etc..These solvents can be used alone or as a mixture.Additionally, the concentration of the solid constituent in coating solution is 50 weight % is suitable.

In order to improve coated face matter, the optical polymerism composition of the photosensitive layer of the photosensitive lithographic plate of the present invention can add surfactant.Its amount of coating with dried weighing scale, about 0.1g/m²-10g/m²Scope be suitable.It is more preferably 0.3-5g/m².More preferably 0.5-3g/m²。

(coating process)

Coating process as photosensitive composite, it is possible to use be coated with the method etc. of the method for scraper (coatingrod), the method for extrusion type coating machine, ball coating machine (slidebealdcoater), but be not limited to these.

Three, the formation of coating is protected

As the water soluble polymer containing hydrogen associativity group contained in protection coating, it is possible to enumerate polyvinyl alcohol and part ester, ether and acetal, or containing making them have its copolymer of the unsubstituted vinyl alcohol units of required water miscible real mass.As polyvinyl alcohol, it is possible to enumerate 71 100% hydrolysis, the degree of polymerization at the polyvinyl alcohol of 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-2247PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA-420, PVA-613, L-8 etc..As above-mentioned copolymer, it is possible to enumerate 88 100% hydrolysed polyvinyl acetate chloracetates or propionic ester, polyvinyl formal and Pioloform, polyvinyl acetal and their copolymer.As the polymer that other are useful, it is possible to enumerate polyvinyl pyrrolidone, gelatin and Radix Acaciae senegalis, these can be used alone or and use.These water soluble polymers are relative to all solids composition of protection coating, containing the ratio of 30 99%, it is preferable that the ratio of 50 99%.

Protection coating can also add the surfactant for improving coating, for improving the known additives such as the water miscible plasticizer of epithelium physical property.As water miscible plasticizer, including such as propionic acid amide., cyclohexanediol, glycerol, sorbitol etc..Furthermore, it is possible to add water miscible (methyl) acrylic acid series polymeric compounds etc..Its amount of coating with dried weighing scale, about 0.1g/m²-Yue 15g/m²Scope be suitable.It is more preferably 1.0g/m²---5.0g/m².As the drying coated weight of protection coating, it is generally 0.5-10g/m², it is preferred to 1.0-5.0g/m²。

The synthesis of emulsion particle

The synthesis of emulsion particle P01

At 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 500g isopropanol, 150g deionized water, 10g(10 weight %) example compound C2 (n is about 9～10), 10g(10 weight %) example compound D1, heated and stirred is uniform, 60g(60 weight % is dripped at 60 DEG C) SM (styrene), 20g (20 weight %) AN (acrylonitrile), 0.7gAIBN (azodiisobutyronitrile), time for adding 2.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P02

At 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 400g isopropanol, 125g deionized water, 15g(15 weight %) example compound C2 (n is about 13～14), 15g(15 weight %) example compound D2, heated and stirred is uniform, 55g(55 weight % is dripped at 90 DEG C) SM (styrene), 15g (15 weight %) MAN (methacrylonitrile), 0.7gBPO (benzoyl peroxide), time for adding 2.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P03

At 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 350g isopropanol, 100g deionized water, 10g(10 weight %) example compound C2 (n is about 22～23), 10g(10 weight %) example compound D3, heated and stirred is uniform, 60g(60 weight % is dripped at 80 DEG C) SM (styrene), 20g (20 weight %) AN (acrylonitrile), 0.7g potassium peroxydisulfate, time for adding 2.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P04

At 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 250g isopropanol, 75g deionized water, 15g(15 weight %) example compound C2 (n is about 34～35), 15g(15 weight %) example compound D4, heated and stirred is uniform, 55g(55 weight % is dripped at 80 DEG C) SM (styrene), 15g (15 weight %) AN (acrylonitrile), 0.7gAIBN (azodiisobutyronitrile), time for adding 2.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P05

At 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 230g isopropanol, 70g deionized water, 10g(10 weight %) example compound C2 (n is about 43～44), 20g(20 weight %) example compound D5, heated and stirred is uniform, 55g(55 weight % is dripped at 80 DEG C) SM (styrene), 15g (15 weight %) AN (acrylonitrile), 0.7gAIBN (azodiisobutyronitrile), time for adding 2.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P06

At 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 250g isopropanol, 75g deionized water, 5g(5 weight %) example compound C2 (n is about 54～55), 14.5g(14.5 weight %) example compound D1, heated and stirred is uniform, 80g(80 weight % is dripped at 80 DEG C) SM (styrene), 0.5g (0.5 weight %) AN (acrylonitrile), 0.7gAIBN (azodiisobutyronitrile), time for adding 2.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P07

At 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 250g isopropanol, 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 uniform, 70g(70 weight % is dripped at 80 DEG C) SM (styrene), 50g (50 weight %) AN (acrylonitrile), 0.7gAIBN (azodiisobutyronitrile), time for adding 2.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P08

At 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 250g isopropanol, 75g deionized water, 19.5g(19.5 weight %) example compound C2 (n is about 80～81), 0.5g(0.5 weight %) example compound D3, heated and stirred is uniform, 50g(50 weight % is dripped at 80 DEG C) SM (styrene), 30g (30 weight %) AN (acrylonitrile), 0.7gAIBN (azodiisobutyronitrile), time for adding 2.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P09

At 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 250g isopropanol, 75g deionized water, 10g(10 weight %) example compound C2 (n is about 90～91), 40g(40 weight %) example compound D4, heated and stirred is uniform, 40g(40 weight % is dripped at 80 DEG C) SM (styrene), 10g (10 weight %) AN (acrylonitrile), 0.7gAIBN (azodiisobutyronitrile), time for adding 2.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P10

At 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 250g isopropanol, 75g deionized water, 30g(30 weight %) example compound C2 (n is about 113～114), 30g(30 weight %) example compound D5, heated and stirred is uniform, 30g(30 weight % is dripped at 80 DEG C) SM (styrene), 10g (10 weight %) AN (acrylonitrile), 0.7gAIBN (azodiisobutyronitrile), time for adding 2.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P11

At 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 250g isopropanol, 75g deionized water, 40g(40 weight %) example compound C2 (n is about 138～140), 5g(5 weight %) example compound D1, heated and stirred is uniform, 25g(25 weight % is dripped at 80 DEG C) SM (styrene), 30g (30 weight %) AN (acrylonitrile), 0.7gAIBN (azodiisobutyronitrile), time for adding 2.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P12

At 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 250g isopropanol, 75g deionized water, 10g(10 weight %) example compound C2 (n is about 43～44), 10g(10 weight %) example compound D1, heated and stirred is uniform, 60g(60 weight % is dripped at 80 DEG C) SM (styrene), 20g (20 weight %) AN (acrylonitrile), 0.7gAIBN (azodiisobutyronitrile), time for adding 2.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P13

At 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 250g isopropanol, 75g deionized water, 10g(10 weight %) example compound C2 (n is about 43～44), 10g(10 weight %) example compound D1, heated and stirred is uniform, 60g(60 weight % is dripped at 80 DEG C) SM (styrene), 20g (20 weight %) AN (acrylonitrile), 0.7gAIBN (azodiisobutyronitrile), time for adding 1.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P14

Emulsion particle P14

At 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 250g isopropanol, 75g deionized water, 15g(15 weight %) example compound C2 (n is about 43～44), 20g(20 weight %) example compound D4, heated and stirred is uniform, 55g(55 weight % is dripped at 80 DEG C) SM (styrene), 10g (10 weight %) AN (acrylonitrile), 0.7gAIBN (azodiisobutyronitrile), time for adding 2 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P15

At 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 250g isopropanol, 75g deionized water, 10g(10 weight %) example compound C2 (n is about 54～55), 10g(10 weight %) example compound D3, heated and stirred is uniform, 60g(60 weight % is dripped at 80 DEG C) SM (styrene), 20g (20 weight %) AN (acrylonitrile), 0.7gAIBN (azodiisobutyronitrile), time for adding 1.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P16

The first step: synthon C1: add the hydroxyl value X1 compound through the melted PEG (n is about 22～23) demarcated and equivalent in the flask having condensing tube, nitrogen protection, thermometer, Dropping funnel and agitator; 60 DEG C of bulk reactions under lauric acid diisobutyl stannum DBTDL catalysis; react about 1 hour, react complement mark: detect peak, active isocyanate base 2275 place by infrared spectrum and disappear.

The structural formula of X1 compound is:

Second step: at 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 250g isopropanol, 75g deionized water, 20g(20 weight %) example compound C1 (n is about 22～23), 10g(10 weight %) example compound D1, heated and stirred is uniform, 55g(55 weight % is dripped at 70 DEG C) SM (styrene), 15g (15 weight %) AN (acrylonitrile), 0.7g potassium peroxydisulfate, time for adding 1.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P17

The first step: synthon C1: add the hydroxyl value X1 compound through the melted PEG (n is about 43～44) demarcated and equivalent in the flask having condensing tube, nitrogen protection, thermometer, Dropping funnel and agitator; 60 DEG C of bulk reactions under lauric acid diisobutyl stannum DBTDL catalysis; react about 1 hour, react complement mark: detect peak, active isocyanate base 2275 place by infrared spectrum and disappear.

The structural formula of X1 compound is:

Second step: at 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 250g isopropanol, 75g deionized water, 10g(10 weight %) example compound C1 (n is about 43～44), 10g(10 weight %) example compound D3, heated and stirred is uniform, 60g(60 weight % is dripped at 80 DEG C) SM (styrene), 20g (20 weight %) AN (acrylonitrile), 0.7gAIBN (azodiisobutyronitrile), time for adding 1.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P18

The first step: synthon C3: add the hydroxyl value X3 compound through the melted PEG (n is about 34～35) demarcated and equivalent in the flask having condensing tube, nitrogen protection, thermometer, Dropping funnel and agitator; 60 DEG C of bulk reactions under lauric acid diisobutyl stannum DBTDL catalysis; react about 1 hour, react complement mark: detect peak, active isocyanate base 2275 place by infrared spectrum and disappear.

The structural formula of X3 compound is:

Second step: at 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 250g isopropanol, 75g deionized water, 15g(15 weight %) example compound C1 (n is about 34～35), 10g(10 weight %) example compound D2, heated and stirred is uniform, 55g(55 weight % is dripped at 80 DEG C) SM (styrene), 15g (15 weight %) AN (acrylonitrile), 0.7gAIBN (azodiisobutyronitrile), time for adding 1.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

The synthesis of emulsion particle P19

The first step: synthon C3: add the hydroxyl value X3 compound through the melted PEG (n is about 80～81) demarcated and equivalent in the flask having condensing tube, nitrogen protection, thermometer, Dropping funnel and agitator; 60 DEG C of bulk reactions under lauric acid diisobutyl stannum DBTDL catalysis; react about 1 hour, react complement mark: detect peak, active isocyanate base 2275 place by infrared spectrum and disappear.

The structural formula of X3 compound is:

Second step: at 1000ml band temperature control heating, mechanical agitation, the four-hole boiling flask of condensing reflux and nitrogen protection device adds 250g isopropanol, 75g deionized water, 10g(10 weight %) example compound C3 (n is about 80～81), 20g(20 weight %) example compound D4, heated and stirred is uniform, 50g(50 weight % is dripped at 90 DEG C) SM (styrene), 20g (20 weight %) AN (acrylonitrile), 0.7gBPO (benzoyl peroxide), time for adding 1.5 hours, 0.3gAIBN (azodiisobutyronitrile) is added after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

Comparative example B01

The 1000ml four-hole boiling flask with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device adds 250g normal propyl alcohol, 75g deionized water, 5g sodium lauryl sulphate; 60g(60 weight % is dripped at 80 DEG C) SM (styrene), 40g (40 weight %) AN (acrylonitrile), 0.7gAIBN (azodiisobutyronitrile); time for adding 1.5 hours; adding 0.3gAIBN (azodiisobutyronitrile) after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

Comparative example B02

The 1000ml four-hole boiling flask with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device adds 250g normal propyl alcohol, 75g deionized water; at 80 DEG C 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); time for adding 1.5 hours; adding 0.3gAIBN (azodiisobutyronitrile) after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

Comparative example B03

The 1000ml four-hole boiling flask with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device adds 250g normal propyl alcohol, 75g deionized water, 5g sodium lauryl sulphate; 50g(50 weight % is dripped at 80 DEG C) SM (styrene), 30g (30 weight %) AN (acrylonitrile), 20g (20 weight %) example compound D4; 0.7gAIBN (azodiisobutyronitrile); time for adding 1.5 hours; adding 0.3gAIBN (azodiisobutyronitrile) after reacting 7.5 hours again, continuation terminates after reacting 12 hours again.

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

Comparative example B04

The 1000ml four-hole boiling flask with temperature control heating, mechanical agitation, condensing reflux and nitrogen protection device adds 325g butanone; 15g(15 weight %) example compound C2 (n is about 43～44), 15g(15 weight %) example compound D4; 55g(55 weight %) SM (styrene), 15g (15 weight %) AN (acrylonitrile), 0.7gAIBN (azodiisobutyronitrile); after back flow reaction 7 hours; adding 0.3gAIBN (azodiisobutyronitrile), continuation terminates after reacting 5 hours again.

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

Below in conjunction with embodiment, the present invention will be described, but the present invention is not by the restriction of these embodiments.

Embodiment 1

[making of photopolymerizable lithographic plate]

Curling for the aluminium sheet (support) of the thick 0.30mm aluminum for web-like (curling shape) is rolled up and is fixed on the machine of sending.In surface treatment with 10% sodium hydroxide, impregnate sending, from this, the aluminium sheet that machine sends continuously 60 seconds at 70 DEG C, after being etched, after washing with flowing water, use 20%HN0₃It is neutralized washing, washing.Sinusoidal wave alternately waveform-shaped current is used, with 300 coulombs/dm in 1% aqueous solution of nitric acid when VA=12.7V²Anode time electricity it is carried out electrolytic surface roughening process.Measuring its surface roughness, it is 0.6um (Ra represents).

Then impregnated in the H of 30%₂SO₄In aqueous solution, after carrying out 2 minutes crude removals at 55 DEG C, at 33 DEG C, 20%H₂SO₄In aqueous solution, the face of graining configures negative electrode, at electric current density 5A/dm²Under, carrying out anodic oxidation in 50 seconds, thickness is 2.7g/m².Additionally, now the anodic oxide coating at the back side is about 0.5g/m at the central part of aluminium sheet², it is about 1.0g/m in end²。

By following hydrophilic layer coating composition mixing, stir at 30 DEG C.After about 5 minutes, it has been found that heating, after reacting 60 minutes, content is transferred in other container, by adding 10000 parts by weight Methanol again, modulate primary coat coating.

(primary coat liquid composition)

Methanol 100 weight portion

Water 120 weight portion

Phosphoric acid (85% aqueous solution) 10 weight portions

3～methacryloxypropyl triethoxysilane 25 weight portion

This aqueous coatings is reached 0.1g/m to the above-mentioned aluminium sheet processed², it is dried until aluminum temperature reaches 70 DEG C, then carries out cooling down until aluminum temperature reaches less than 50 DEG C.

On the priming coat so obtained, it is coated with the high sensitivity optical polymerism composition of following composition, makes drying coated weight reach 1.6g/m², it is dried until aluminum temperature reaches 100 DEG C, then carries out cooling down until aluminum temperature reaches less than 50 DEG C.

(photosensitive layer coating liquid compositions)

Polyurethane acrylate (SARTOMER company, CN970A60) 2.0 weight portions

Emulsion particle P011.0 weight portion

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

Multifunctional monomer (SARTOMER company, SR531) 1.5 weight portions

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

Photoepolymerizationinitiater initiater (CIBA, titanocene compound) 0.2 weight portion

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

Fluorine system nonionic surfactant (3M company, FC-4431) 0.03 weight portion

Methyl ethyl ketone 40 weight portion

Propylene glycol monomethyl ether acetate 40 weight portion

To protect coating applications to be coated with on this photosensitive layer by the following protection coating forming and being constituted, making drying coated weight is 2.0g/m², at drying section, blow dry wind temperature 120 DEG C 5 minutes with the wind speed 8m/ second, be dried and make polyvinyl alcohol dry, then carry out cooling down until aluminum temperature reaches less than 50 DEG C.

(protective layer coating solution compositions)

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

Polyvinyl pyrrolidone (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 portion

Embodiment 2-16

In embodiment 2-5, it is a difference in that in the photosensitive layer coating liquid compositions of embodiment 1 emulsion particle P01 and changes respectively that into emulsion particle P02-P16, all the other adopt methods similarly to Example 1 to manufacture photo-polymerization type lithographic printing plate.

Comparative example 1-4

In comparative example 1-4, and being a difference in that in the photosensitive layer coating liquid compositions of embodiment 1 emulsion particle P01 and change respectively outside into B01, B02, B03, B04 of embodiment 1, adopt method similarly to Example 1 to manufacture photo-polymerization type lithographic printing plate.

Photo-polymerization type lithographic printing plate sample is evaluated

Photosensitive layer developing performance evaluates (drop)

Take above-mentioned plate batten, wash away protective layer, dry, on placement platform, dripped developer solution with dropper every 5 seconds, drip 6 altogether, after dripping off last, wait 5 seconds.Horse back deionized water is rinsed well, measures the version base density of blank space with reflection densitometer, contrasts with the white version base density of uncoated photosensitive liquid, and with the first of equal densities for the clean time, the time is more short, and developing powder is more fast.Present invention developer solution is alkalescence, and its pH value is the developer solution of 8.5-9.5 lower than 10, PH.

Pressrun is evaluated

Photosensitive layer is carried out image exposure by the purple laser of 405 or 410nm with suitable light exposure by the photopolymerization sensitive lithographic plate prepared in aforementioned manners, makes to see that light is partially cured.By development treatment, what remove photopolymerization layer has no light part, it is possible to form image on aluminium sheet support surface.Present invention developer solution is alkalescence, and its pH value is the developer solution of 8.5-9.5 lower than 10, PH.

After image exposure between development, for the purpose of the curing degree improving photo-polymerization type photosensitive layer, it is possible to be arranged on the heating process carrying out 1 second-5 minutes at the temperature of 50 DEG C-150 DEG C.

Additionally, as mentioned above, it is known that arrange the protection coating with oxygen barrier performance on the photosensitive layer of the photosensitive lithographic plate of the present invention, the present invention uses developer solution to carry out the removal of protection coating and the method for the removal of photosensitive layer unexposed portion simultaneously.

So carry out the photosensitive lithographic plate of development treatment, wash water with water, the leacheate containing surfactant etc., the lipoprotein liquid of not feeling containing Radix Acaciae senegalis or starch derivatives etc. carry out post processing.The lithographic plate prepared by this process is installed on offset press, for the printing of multipage.

It can be seen that receive the low chemical treatment purple laser light polymerization version of micron particle containing the present invention from subordinate list 1, existing owing to receiving ammonia ester bond highly polar in micron particle, sensitive lithographic plate coating press resistance rate is higher；Simultaneously because it is better to receive the permeability of micron particle, and wherein contain acrylamide hydrophilic derivant construction unit, so plate has good developing performance.

Table 1 plate application performance table

Claims (8)

1. a low chemical treatment violet laser photopolymerization type planographic printing plate; described Photopolymerization type lithographic plate main body includes support; it it is photo-polymerization type photosensitive layer on support; with aqueous protective layer on photo-polymerization type photosensitive layer; it is characterized in that: in photo-polymerization type photosensitive layer, include one receive micron particle; it is a kind of high molecular polymerization granule existed with emulsion discrete form, and described micron particle of receiving is the vinyl multiple copolymer containing, for example lower construction unit:

A: styrol structural unit；

B:(methyl) acrylonitrile unit unit；

C: ammonia Esterification polyether self emulsifying construction unit；

In formula, R¹For hydrogen atom or methyl, R²For 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 formula, R³For hydrogen atom or methyl, R⁴For hydroxyl or sulfoamido.

2. low chemical treatment violet laser photopolymerization type planographic printing plate according to claim 1, it is characterised in that: it is 20000-150000 that described vinyl multiple copolymer receives the weight average molecular weight of micron particle；Glass transition temperature is 30-260 DEG C；Particle diameter is 15-300nm, and styrol structural unit A weight percent content in the copolymer is 30%-80%；(methyl) acrylonitrile unit unit B weight percent content in the copolymer is 0.5%-40%；Ammonia Esterification polyether self emulsifying construction unit C weight percent content in the copolymer is 0.5%-40%；Acrylamide hydrophilic derivant construction unit D weight percent content in the copolymer is 0.5%-40%.

3. low chemical treatment violet laser photopolymerization type planographic printing plate according to claim 1, it is characterised in that: it is 50000-100000 that described vinyl multiple copolymer receives the weight average molecular weight of micron particle；Glass transition temperature is 60-180 DEG C；Particle diameter is 55-200nm, and styrol structural unit A weight percent content in the copolymer is 50%-60%；(methyl) acrylonitrile unit unit B weight percent content in the copolymer is 10%-20%；Ammonia Esterification polyether self emulsifying construction unit C weight percent content in the copolymer is 10%-20%；Acrylamide hydrophilic derivant construction unit D weight percent content in the copolymer is 10%-20%.

4. the low chemical treatment violet laser photopolymerization type planographic printing plate described in 1 or 2 or 3 is wanted according to right, it is characterised in that: described vinyl multiple copolymer receives micron particle percentage by weight in photo-polymerization type lithographic printing plate photosensitive layer between 1-30%.

5. low chemical treatment violet laser photopolymerization type planographic printing plate according to claim 1, it is characterised in that: described photo-polymerization type photosensitive layer component includes carrying out the ethylene unsaturated group compound of photopolymerization reaction, one pack system or bi-component or multicomponent initiator system and coloring agent.

6. low chemical treatment violet laser photopolymerization type planographic printing plate according to claim 5, it is characterized in that: described ethylene unsaturated group compound is simple function group or multi-functional monomer, simple function group or multi-functional oligomer, any of the above or multiple combination, described ethylene unsaturated group compound weight percent concentration in photo-polymerization type photosensitive layer is 10-90%.

7. low chemical treatment violet laser photopolymerization type planographic printing plate according to claim 5, it is characterized in that: described one pack system or bi-component or multicomponent initiator system, including sensitizing dye, initiator and aided initiating or connection transfer agent, described one pack system or bi-component or multicomponent initiator system weight percent concentration in photo-polymerization type photosensitive layer are 5-30%.

8. low chemical treatment violet laser photopolymerization type planographic printing plate according to claim 5, it is characterised in that: described coloring agent is dyestuff or pigment, and its weight percent concentration in photo-polymerization type photosensitive layer is 0.5-20%；The dried coating weight of photo-polymerization type photosensitive layer is 0.1g/m²-10g/m²；With aqueous protective layer on photo-polymerization type photosensitive layer, its protective layer includes water-soluble high-molecular compound, surfactant and antimicrobial moiety, and the dried coating weight of aqueous protective layer is 0.5-10g/m²。