CN101174090A - Photo-polymerization type lithographic printing plate - Google Patents
Photo-polymerization type lithographic printing plate Download PDFInfo
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- CN101174090A CN101174090A CNA2006101073768A CN200610107376A CN101174090A CN 101174090 A CN101174090 A CN 101174090A CN A2006101073768 A CNA2006101073768 A CN A2006101073768A CN 200610107376 A CN200610107376 A CN 200610107376A CN 101174090 A CN101174090 A CN 101174090A
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Abstract
The invention discloses a photopolymerisable type lithographic printing plate, comprising a body of the photopolymerisable lithographic printing plate, wherein, the body comprises a support body; a photopolymerisable photosensitive layer is arranged on the support body; a watery protective layer is attached on the photopolymerisable photosensitive layer; the watery protective layer comprises water-soluble functional dye, and the absorption spectrum of the water-soluble functional dye is in the visible light range. The invention has the advantages of good yellow light safety, anti-scratch, and better adaptability of manufacture technology and development process.
Description
Technical field
The present invention relates to a kind of lithographic plate that the photo-polymerization type light sensitive layer is arranged that on aluminum substrate, forms, relate to a kind of photo-polymerization type lithographic printing plate that can use directly laser Graphic specifically.
Background technology
The photosensitive polymer material now is penetrated into many fields of the national defence people's livelihood gradually as an important branch of functional high-polymer, its application is very extensive, as electronics industry, printing industry, printing ink industry, coatings industry and as recording materials, tackifier and medical material etc.Recording materials such as silver halide gelatin, dichromate etc. with other are compared, and the photosensitive polymer material has characteristics such as resolution height, imaging is stable, cost is low, easy to process, have therefore occupied critical role in actual applications gradually.
One of topmost application of photosensitive polymer material is a printing industry, has been widely used in lithographic plate, relief printing plate, intaglio plate, the plate-making of silk screen version.Be applied to bright chamber copy, colored pre-proof, printing-ink, glazing agent etc. in addition.The photosensitive polymer material is to high-tech sector development, especially laser imaging material in recent years.
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 kation), trigger monomer polymerization in excited state; Latter's photosensitizer at first absorbing light produces the polymerization of active seed trigger monomer with the light trigger effect then.
In such photopolymerization system, high sensitivityization is very important.And airborne oxygen can obviously reduce the sensitivity of plate.Airborne oxygen has the influence of two aspects to light initiation system, the excited state of the light trigger of can urging on the one hand to go out; The free radical that can urge on the other hand to go out and generate.Therefore coating one deck be that the protective seam of primary raw material comes starvation with polyvinyl alcohol (PVA) (PVA) on the photographic layer of such flat stamping version, thus raising plate sensitivity.
The protective seam of photopolymerization CTP plate is subjected to temperature, humidity effect bigger.When temperature raises, when humidity increases, protective seam causes that the oxygen perviousness of protective seam increases owing to expanded by heating, be subjected to wet swelling, causes that finally the plate sensitivity descends.Therefore the protective seam that adds moisture-proof, heat can prevent that the plate sensitivity from descending.
The photopolymerization plate sensitivity of adding protective seam obviously improves, but another problem of the thing followed is along with the plate sensitivity improves, plate photographic layer increased activity, the plate storage stability bad stability under will variation, particularly gold-tinted irradiation.Plate gold-tinted deterioration of safety will influence the usability of plate, just can not obtain the market approval.
Summary of the invention
Purpose of the present invention just is to provide a kind of photo-polymerization type lithographic printing plate.
Purpose of the present invention can realize by following measure:
The present invention includes the photo-polymerization type lithographic printing plate body; include support in the photo-polymerization type lithographic printing-plate body; it on support the optical polymerism photographic layer; on the optical polymerism photographic layer, has the water-based protective seam; this water-based protective seam includes the water-solubility function dyestuff, and the absorption spectrum of this water-solubility function dyestuff is at visible-range.
Also include the water-soluble composition that can cause the water-soluble polymers generation cross-linking reaction that contains carboxyl or hydroxyl among the present invention in the water-based protective seam.The weight percent concentration of water-solubility function dyestuff in protective finish in the water-based protective seam is 0.1-20%.The weight percent concentration of water-soluble composition in the water-based protective seam in protective finish is 0.01-10%; Preferable amount is 0.01-3%.The water-solubility function dyestuff, its absorption spectrum is between 300～600nm; Its consumption preferred weight percent concentration in the water-based protective seam is 0.1-5%.Water-soluble composition adopts boric acid, carbonic acid and corresponding alkali metal salt to include in potassium borohydride, sodium carbonate, the sodium bicarbonate any one or multiple combination; Its consumption is 0.01-10% for shared weight percent concentration in the water-based protective seam, and preferable amount is 0.05-5%.Also adding in the water-based protective seam has plastifier, this plastifier to include any one or more combination in propionamide, cyclohexanediol, glycerine, the sorbierite.Also adding in the water-based protective seam has water miscible acrylic acid series polymeric compounds or metha crylic polymer, and its amount of coating is 0.1g/m in dried weight
2-Yue 15g/m
2, be preferably 1.0g/m
2---5.0g/m
2Drying coated weight as protective finish is 0.5-10g/m
2, be preferably 1.0-5.0g/m
2In the photo-polymerization type lithographic printing plate body optical polymerism photographic layer contain at least have the ethene unsaturated group can polymeric compounds, in the light trigger, sensitizing coloring matter, adhesive resin a kind of or many in combination.
The present invention is owing to adopt said components, and the photo-polymerization type lithographic printing plate that makes thus has good gold-tinted security and resistance to marring.Thereby make photo-polymerization type lithographic printing plate of the present invention have more outstanding manufacturing process adaptability and development flexibility (adaptability) of operation.Carry out data declaration below by several embodiment (data of embodiment second portion) and comparative example.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 | Comparative example 2 | |
| The gold-tinted security (minute) | 45 | 38 | 36 | 42 | 40 | 32 | 18 | 22 |
| Resistance to marring | Excellent | Very | Very | Very | Excellent | Excellent | In | In |
Annotate: the gold-tinted security with the impregnable maximum duration of plate development under the gold-tinted (minute) be as the criterion.
Embodiment
The present invention does with detailed description below in conjunction with embodiment:
Embodiment first
Embodiment 1
The present invention includes the photo-polymerization type lithographic printing plate body; include support in the photo-polymerization type lithographic printing-plate body; it on support the optical polymerism photographic layer; on the optical polymerism photographic layer, has the water-based protective seam; this water-based protective seam includes the water-solubility function dyestuff, and the absorption spectrum of this water-solubility function dyestuff is at visible-range.
Also include the water-soluble composition that can cause the water-soluble polymers generation cross-linking reaction that contains carboxyl or hydroxyl in the water-based protective seam.
Embodiment 2
The present invention includes the photo-polymerization type lithographic printing plate body; include support in the photo-polymerization type lithographic printing-plate body; it on support the optical polymerism photographic layer; on the optical polymerism photographic layer, has the water-based protective seam; this water-based protective seam includes the water-solubility function dyestuff, and the absorption spectrum of this water-solubility function dyestuff is at visible-range.
Also include the water-soluble composition that can cause the water-soluble polymers generation cross-linking reaction that contains carboxyl or hydroxyl in the water-based protective seam.
The weight percent concentration of water-solubility function dyestuff in protective finish in the water-based protective seam is 0.1-20%.Specifically should adopt 0.1,0.2,0.5,1.0,1.5,3,5,7,9,12,15,17,18,19,20% etc. as required.
The weight percent concentration of water-soluble composition in the water-based protective seam in protective finish is 0.01-10%; Should adopt 0.01,0.02,0.05,0.1,1,2,3,4,5,6,7,8,9,10 etc. as required; Preferable amount is 0.01-3%, can be 0.015,0.018,0.025,0.03,0.06,0.09,1.2,1.5,1.8,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9,3% etc.
Water-solubility function dyestuff, its absorption spectrum can be 300,310,330,350,390,400,420,450,480,500,520,550,580,600nm etc. as required between 300～600nm; Its consumption preferred weight percent concentration in the water-based protective seam is 0.1-5%, can be 0.1,0.2,0.5,0.8,1.0,1.5,1.8,2.0,2.5,3.0,3.5,4.0,4.5,4.7,4.8,5% etc. as required.
Water-soluble composition adopts boric acid, carbonic acid and corresponding alkali metal salt to include in potassium borohydride, sodium carbonate, the sodium bicarbonate any one or multiple combination; Its consumption is 0.01-10% for shared weight percent concentration in the water-based protective seam, and preferable amount is 0.05-5%.Can be 0.01,0.02,0.05,0.1,1,2,3,4,5,6,7,8,9,10 etc. as required; Also can be 0.05,0.06,0.09,1.2,1.5,1.8,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9,3,3.5,4.5,4.8,4.9 etc.
Embodiment 3
The present invention includes the photo-polymerization type lithographic printing plate body; include support in the photo-polymerization type lithographic printing-plate body; it on support the optical polymerism photographic layer; on the optical polymerism photographic layer, has the water-based protective seam; this water-based protective seam includes the water-solubility function dyestuff, and the absorption spectrum of this water-solubility function dyestuff is at visible-range.
Also include the water-soluble composition that can cause the water-soluble polymers generation cross-linking reaction that contains carboxyl or hydroxyl in the water-based protective seam.
Also adding in the water-based protective seam has plastifier, this plastifier to include any one or more combination in propionamide, cyclohexanediol, glycerine, the sorbierite.
Also adding in the water-based protective seam has water miscible acrylic acid series polymeric compounds or metha crylic polymer, and its amount of coating is 0.1g/m in dried weight
2-Yue 15g/m
2, be preferably 1.0g/m
2---5.0g/m
2According to can be 0.1,0.2,0.5,1,2,3,4,4.5,5,6,7,8,9,10,11,12,13,14,14.5,15g/m
2Deng; Drying coated weight as protective finish is 0.5-10g/m
2, be preferably 1.0-5.0g/m
2Can be 0.5,0.6,0.8,1,2,3,4,4.5,5,6,7,8,8.5,9,9.5,9.8,9.9 as required, lOg/m
2Deng
In the photo-polymerization type lithographic printing plate body optical polymerism photographic layer contain at least have the ethene unsaturated group can polymeric compounds, in the light trigger, sensitizing coloring matter, adhesive resin a kind of or many in combination.
The consumption of composition is except that the concrete point value of illustrating and arbitrarily collocation is among above-mentioned each embodiment, also can get other arbitrary values and arrange in pairs or groups arbitrarily as required (other herewith) in scope separately.
The embodiment second portion
This photo-polymerization type sensitive offset press version of the present invention contains a kind of water-based protective seam (to call water-soluble protective finish or protective finish in the following text), and this protective finish comprises a kind of water-solubility function dyestuff and a kind of low macromolecule water-solubility composition.
Water-solubility function dyestuff, its absorption spectrum between 300～600nm, the compound of structure specific as follows:
Dye-1
λ
Absorb=360～510nm
Dye-2
λ
Absorb=360～580nm
Dye-3
λ
Absorb=410～590nm
The water-based protective finish, the weight percent concentration of water-solubility function dyestuff in protective finish is 0.1-20%.Specifically; described water-solubility function dyestuff all can absorb a large amount of visible lights at protective finish; particularly greater than the light of 410nm wavelength; even plate places under the gold-tinted like this; photographic layer below the protective seam also absorbs less than the light greater than 410nm; just can not cause the dark reaction of plate, thereby improve the gold-tinted security of plate.
The solids content weight percent concentration of water-solubility function dyestuff in protective finish is 0.1-20%.The solids content weight percent concentration is lower than 0.1% and does not have the effect of absorption greater than the 410nm wavelength; The solids content weight percent concentration is greater than 20%, and described water-solubility function dyestuff can absorb the light of 410nm wavelength in a large number, causes the plate sensitivity to descend.
Water-based protective finish, water-solubility function dyestuff can be a kind of in the dyestuff of aforesaid absorption wide spectrum between 300-600nm or more than one combination.Independent a kind of functional dye can play the effect of the light of a large amount of absorption 410nm wavelength, thereby has improved the gold-tinted security of plate.If adopt two kinds of above-mentioned three kinds of water-solubility function dyestuffs or two or more combinations, the effect that improves the security of plate gold-tinted is more obvious.
In the water-based protective finish, a kind of water-soluble composition wherein is boric acid, carbonic acid and corresponding alkali metal salt such as potassium borohydride, sodium carbonate, sodium bicarbonate etc.After above-mentioned water-soluble composition adds protective finish; in the protective finish dry run; can cause that the hydroxyl in the film-forming resin polyvinyl alcohol (PVA) (PVA) is (OH) crosslinked; thereby polyvinyl alcohol (PVA) (PVA) molecular weight is sharply increased; thereby improve the hardness of film, improve the scratch resistance ability of plate protective finish.
In the water-based protective finish, wherein a kind of water-soluble composition shared weight percent concentration in protective finish is 0.01-10%.Above-mentioned water-soluble composition such as boric acid, potassium borohydride, sodium carbonate, the sodium bicarbonate solid content weight percent concentration in the protective finish dry film is 0.01-10%.The solid content weight percent concentration is lower than 0.01%, does not have the effect of post bake; The solid content weight percent concentration can cause that greater than 10% the protective finish dry film hardness becomes big, influences the water-soluble variation of protective finish dry film, and influences the light transmission of protective finish dry film.So above-mentioned water-soluble composition such as boric acid, potassium borohydride, sodium carbonate, the sodium bicarbonate solid content weight percent concentration in the protective finish dry film is 0.01-10%.Preferred weight percent concentration is 0.01-3%.
In the water-based protective finish, wherein a kind of water-soluble composition can be a kind of effect that can play post bake of water-soluble composition such as boric acid, potassium borohydride, sodium carbonate, sodium bicarbonate.If two kinds or the combination of two or more water-soluble composition add in the protective finish, the post bake effect is more obvious.
Details are as follows with regard to the concrete manufacturing process of this kind photo-polymerization type lithographic printing plate below.
[support]
The support that uses among the present invention can use the aluminium of dimensionally stable or its alloy alloy of silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel (for example with).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 sheet can be the aluminium sheet that adopts common semi-continuous casting method (DC method) to make, and also can be the aluminium sheet 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 sheet preferably is about about 0.1mm-0.6mm.In addition, the plastic foil or the paper of aluminium, aluminium alloy that also can use lamination or evaporation.
[surface treatment of support]
When support is aluminium sheet, according to purpose various processing are implemented on its surface usually.As general disposal route, at first degreasing or electrolytic polishing are handled and crude removal is handled by aluminium sheet is carried out, and the aluminium surface is cleaned.Then, implement the mechanical surface roughened or/and the electrochemical surface roughened, give surface of aluminum plate fine concavo-convex.In addition, also increasing chemical etching processing and crude removal this moment 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.
In addition, between the reason, do not bring next into for the treating 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 be with the overflow waste liquid of the electrolytic solution that uses in the electrochemical surface roughened as the crude removal treating fluid, but the washing that can omit this moment after crude removal is handled is handled.
(degreasing-electrolytic polishing handle) removes the rolling oil that exists on the aluminium sheet, autoxidation epithelium, dirt etc., 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
(1) electrolytic polishing is handled
Can use the known aqueous solution that is used for electrolytic polishing.Preferably based on the aqueous solution of sulfuric acid or phosphoric acid, especially preferably based on the aqueous solution of phosphoric acid.Can be from phosphoric acid 20-90 weight % (preferred 40-80 weight %), liquid temperature 10-90 ℃ of (preferred 50-80 ℃), 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, hydrofluorite, 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.
(2) 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.The preferred 0.5-25 weight of the concentration of acidic aqueous solution %, the aluminium that more preferably dissolves in acidic aqueous solution are 0.5-5 weight %.The preferred 5-30 weight of the concentration of aqueous alkali %, the aluminium that more preferably dissolves in aqueous alkali are 30 weight %.(crude removal processing)
After etch processes, when the aqueous solution of using alkali has been 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,, can use the waste liquid of the electrolytic solution that in electrochemical surface roughened etc., uses, must be noted that not make the aluminium sheet drying that the one-tenth in the crude removal liquid analyzes as this acidic aqueous solution.After the crude removal processing finished, in order not bring treating 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 same aqueous solution, also can omit washing.
(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, tinsel granulation, sandblast granulation in this graining, but as a large amount of and continuous processing, brush granulated processed excellence.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.
(electrochemical surface roughened)
(1) use direct current the electrochemical surface roughened with hydrochloric acid or nitric acid aqueous solution as main body, can use the aqueous solution of in the electrochemical surface roughened of using common interchange, using, 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 aluminium nitrate, sodium nitrate, ammonium nitrate etc. use more than 1.The metal of in addition, can dissolved iron in based on the aqueous solution of hydrochloric acid or nitric acid, containing in the aluminium alloy such as copper, manganese, titanium, magnesium, silicon dioxide.The preferred use added aluminum chloride, aluminium nitrate so that aluminium ion reaches the liquid of 3-50g/L in hydrochloric acid or nitric acid 0.5-2 weight % aqueous solution.The preferred 10-60 of temperature ℃, more preferably 25-50 ℃.Use the treating apparatus that uses in the electrochemical surface roughening of direct current can use 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 direct current below 20% that the direct current that uses in the electrochemical surface roughening preferably uses pulsation rate.The preferred 10-200A/dm of current density
2, the preferred 10-1000C/dm of the electric weight when aluminium sheet is anode
2
Anode can be from ferrite, indium oxide, paper tinsel, known oxygen such as compound or plating paper tinsel takes place to use with selecting the 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 uses cathode for fuel cell.
(2) use the electrochemical surface roughened that exchanges with hydrochloric acid or nitric acid aqueous solution as main body, can use the aqueous solution of in the electrochemical surface roughened that common use exchanges, using, can add 1g/L in the hydrochloric acid of 1--100g/L or aqueous solution of nitric acid and have nitrate ion to saturated aluminium nitrate, sodium nitrate, ammonium nitrate etc., aluminum 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 based on the aqueous solution of hydrochloric acid or nitric acid, containing in the aluminium alloy such as copper, manganese, nickel, titanium, magnesium, silicon dioxide.
The preferred use added aluminum chloride, aluminium nitrate etc. so that aluminium ion reaches the liquid of 3-50g/L in hydrochloric acid or nitric acid 0.5-2 weight % aqueous solution.The preferred 10-60 of temperature ℃, more preferably 20-50 ℃.
(3) 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 electrolytic solution 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 is subjected to nature to produce the micro constitutent that increases easily is difficult for carrying out the generation sand holes of homogeneous.
(4) duty ratio of platform shape ripple interchange can use 1: 2-2: 1, in aluminium, do not use giving indirectly in the electric mode of conductive rollers, preferred duty ratio 1: 1.The frequency that platform shape ripple exchanges can be used 0.1--120Hz, preferred 50-70Hz on the equipment.If lower than 50Hz, the carbon electrode of main pole dissolves easily, if bigger than 70Hz, is subjected to the influence of the inductance composition on the electric power loop easily, the power supply cost up.But, when use contains aluminium alloy greater than the Cu of 0.1wt%, the interchange of preferred frequency of utilization 0.1--10Hz.The preferred 10-200A/dm of the peak value of the current waveform of current density
2
(5) electrolytic tank that uses in the electrochemical surface roughening can use the electrolytic tank that uses in longitudinal type, platypelloid type, the known surface treatment such as star-like, and the electrolytic solution that passes through in electrolytic tank can be parallel with advancing of aluminium net, also can drive in the wrong direction with it.
(6) in the AC power that can connect on the electrolytic tank more than 1.The anode of the interchange that adds on the aluminium sheet relative with main pole 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.By rectifier cell or on-off element, the part shunting that makes current value as with 2 central electrodes outside other groove on DC current on the impressed current anode that is provided with, can control participation cathode reaction current value that on the aluminium sheet relative, acts on and the ratio that participates in the current value of anode reaction with main pole.On the aluminium sheet relative, participate in the preferred 0.3-0.95 of ratio when anode (electric weight during negative electrode/electric weight) of the electric weight of anode reaction and cathode reaction with main pole.
(7) be in the aqueous solution of major 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.
((utilizing a sour alkalies) handled in chemical etching)
Removing with whole of the fine concavo-convex sand holes that will form in mechanical surface roughened, the electrochemical surface roughened, dirt etc. is purpose, carries out chemical etching and handles.The liquid temperature is preferably 25-90 ℃, preferably carries out 1-120 and handles second.The preferred 0.5-25 weight of the concentration of acidic aqueous solution %, the aluminium that more preferably dissolves in acidic aqueous solution are 0.5-5 weight %.The preferred 5-30 weight of the concentration of aqueous alkali %, the aluminium that more preferably dissolves in aqueous alkali are 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 is carried 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.
(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 is used 5-30%.In 20-60 ℃ temperature range, carry out 5-250 electrolytic treatments in second.Preferably in this electrolytic solution, contain aluminium ion.The current density of this moment is 1--50A/dm more preferably
2Under the situation of phosphoric acid method, under the temperature of the concentration of 5-50%, 30-60 ℃, 10-300 second, 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.
(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 treating fluid into subsequent processing.Preferably implementing sealing of hole after anodized handles.This sealing of hole is handled by 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.
[formation of undercoat]
In undercoat coating, painting bottom coating coating fluid and carry out drying on the surface of support aluminum substrate forms undercoat as required.As the mode that is coated with at this undercoat, condition, can utilize mode, the condition of a lot of aftermentioned coating photosensitive composite layers.That is, can utilize method, the method for using the extrusion type coating machine of using coating, the method for using sliding pearl coating machine.In addition, coating condition, liquid rerum natura etc. also can be utilized the condition of putting down in writing in the photosensitive composite layer.
[formation of photographic layer]
On undercoat, be coated with the coating of photo-polymerization type photosensitive composite and carry out drying, form photographic 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 (photographic layer) of the photo-polymerization type photosensitive composite that is coated with on the support aluminum substrate is different because of purposes, and preferred dried weight is 0.3-4.0g/m2 usually.Along with coating weight reduces, the exposure that is used to obtain image get final product less, but the film strength reduction.Along with coating weight increases, be essential with exposure, but light-sensitive surface strengthen, for example, when as galley, can obtain the galley of the number of pages many (high anti-brushes) that can print.In photosensitive composite, can add and be used to improve the surfactant of coated face matter, preferred especially fluorine class surfactant.
The photo-polymerization type photosensitive composite of the photographic layer of the formation photosensitive lithographic plate that uses among the present invention is must composition with ethylenically unsaturated compounds, light trigger, macromolecule bond that can addition polymerization, as required can and with all cpds such as colorant, plastifier, heat polymerization inhibitors.
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 link 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 links 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 potpourri and their multipolymer etc.
Example as monomer and multipolymer 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 the glycol diacrylate of acrylate, triethylene glycol diacrylate, 1, the 3--butanediol diacrylate, 1, the 4--butanediol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloyl-oxy propyl group) ether, the trimethylolethane trimethacrylate acrylate, hexanediyl ester, 1,4--cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the dipentaerythritol diacrylate, dipentaerythritol five acrylate, dipentaerythritol acrylate, the sorbierite triacrylate, the sorbierite tetraacrylate, sorbierite five acrylate, sorbierite six acrylate, three (acrylyl oxy-ethyl) isocyanuric acid ester, polyester acrylic ester oligomer etc.
As methacrylate, comprise 1, the 4--butanediol dimethylacrylate, triethylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylol-propane trimethacrylate, the trimethylolethane trimethacrylate methacrylate, ethylene glycol dimethacrylate, 1, the 3--butanediol dimethylacrylate, hexanediol dimethacrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl acrylate, the dipentaerythritol dimethylacrylate, dipentaerythritol hexamethyl acrylate, dipentaerythritol pentamethyl acrylate, the sorbierite trimethyl acrylic ester, sorbierite tetramethyl acrylate, two [right--(3--methacryloxy-2--hydroxyl propoxyl group) phenyl] dimethylmethane, two [right--(methacryloxy ethoxy) phenyl] dimethylmethane etc.
As itaconate, comprise ethylene glycol bisthioglycolate itaconate, propylene glycol diitaconate, 1,3--butylene glycol diitaconate, 1,4--butylene glycol diitaconate, 1,4--butylene glycol diitaconate, pentaerythrite diitaconate, sorbierite four itaconates etc.
As crotonates, comprise ethylene glycol bisthioglycolate crotonates, 1,4--butylene glycol two crotonatess, pentaerythrite two crotonatess, sorbierite four crotonatess 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 potpourri 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, diethylene triamine three acrylamides, xylylene bisacrylamide, the two Methacrylamides of xylylene etc.
In addition, the use amount of these ethylenically unsaturated compounds is with the 5-80 weight % of the full composition of photographic layer, and the scope of preferred 30-70 weight % is used.
In addition, the Photoepolymerizationinitiater initiater that contains in the photographic 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.
When with the luminous ray more than the 400nm, Ar laser, the 2nd high harmonic of semiconductor laser, SHG-YAG laser, when radiating the ultrared Solid State Laser of wavelength 760nm-1200nm and semiconductor laser and being light source, various light initiation systems have been proposed, for example rose-red, eosin, algae is red etc., or the system that adopts dyestuff and initiating agent to make up, for example composite initiation system of dyestuff and amine, the paralled system of six aryl bisglyoxalines and radical initiator and dyestuff, six aryl bisglyoxalines and to the system of dialkyl amido benzal ketone, the system of ring-type cis-Q--dicarbonyl compound and dyestuff, the system of ring-type triazine and merocyanine pigment, the system of 3--oxo coumaran and activating agent, bisglyoxaline, styrene derivative, the system of mercaptan, the system of organic peroxide and pigment, the system of dyestuff and active halogen compound, the system of dyestuff and borate compound, system with pigment and free radical generating agent of rhodanine ring, the system of two luxuriant titaniums and 3 one oxo coumaran pigments, two luxuriant titaniums and cluck ton pigment and contain amino or carbamate groups can addition polymerization the combined system of ethylenically unsaturated compounds, the system of two luxuriant titaniums and specific merocyanine pigment, the system of two luxuriant titaniums and pigment etc. with chromene ring.
In addition, developed the laser (violet laser) of 400nm-410nm wavelength recently, developed light initiation system, also used these light initiation systems the demonstration of the wavelength below 450nm high sensitivity to its induction.
For example, can enumerate kation 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, owing to excellence aspect sensitivity, therefore 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--and 2,3,4,5,6--phenyl-pentafluoride--1-base, dicyclopentadienyl-Ti--two--and 2,3,5,6--phenyl tetrafluoride--1--base, dicyclopentadienyl-Ti--two--and 2,4,6--trifluoro-benzene-1--base, dicyclopentadienyl-Ti--two--and 2,6--two fluorobenzene--1--base, dicyclopentadienyl-Ti--two--and 2,4--two fluorobenzene--1--base, two--methyl cyclopentadienyl-Ti--two--2,3,4,5,6--phenyl-pentafluoride--1--base, two--methyl cyclopentadienyl-Ti--two--2,6--two fluorobenzene--1--base, dicyclopentadienyl-Ti--two--and 2, the 6--difluoro--3--(pyrroles--the 1--yl)--benzene--1--base etc.
In addition, known as required by 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, at 0.05-100 weight portion, preferred 0.1--70 weight portion, more preferably use in the scope of 0.2-50 weight portion.
The macromolecule bond that uses in the photographic 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.This organic high molecular polymer, for example, if use the water dissolvable organic high molecular polymer, then can water development.As such organic high molecular polymer, comprise that side chain has adding of carboxylic acid group
Become polymkeric substance, i.e. methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid multipolymer, maleic acid, partial esterification maleic acid etc.
Comprise the acid cellulose derivant that has the carboxylic acid group equally at side chain in addition.Polymkeric substance 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] multipolymer and [(methyl) allyl acrylate/(methyl) acrylic acid/as required other addition polymerization sex ethylene base monomers] multipolymer.In addition, as water soluble organic polymer, polyvinyl pyrrolidone, polyethylene oxide 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 by importing the free radical reaction group at side chain.As functional group that can polyaddition reaction, can enumerate ethylenic unsaturated link base, amino, epoxy radicals, in addition, as the functional group that can become free radical by 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 link bases such as preferred especially acryloyl group, methacryl, allyl, styryl; in addition; from amino, hydroxyl, phosphonate group, phosphate, carbamyl, isocyanate group, urea groups, 1, the functional group that 3-urylene, sulfonic group, ammonium are selected also is useful.
In order to keep the development of composition, macromolecule bond of the present invention preferably has suitable molecular weight, acid number, effectively uses weight-average molecular weight to be 5000-30 ten thousand, the acid number high molecular polymer as 10-200.
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 1/9-9/1.Preferred scope is 2/8-8/2, more 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 hydramine, N-nitroso-phenyl hydramine 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, poly-for the resistance that anti-block produces, can add the such advanced higher fatty acid derivative of mountain lush acid, mountain lush acid acid amides etc. as required, its surface of being partial to photographic 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 photographic layer, can add colorant.As colorant, comprise for example pigment such as phthualocyanine pigment, azo pigment, carbon black, titanium dioxide, 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 adjuvants such as plastifier 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 the photosensitive coated layer composition, be dissolved in the various organic solvents for using.As solvent used herein, comprise acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethylene, tetrahydrofuran, toluene, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, diacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, the 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, the N dimethyl formamide, dimethyl sulfoxide (DMSO), Y one butyrolactone, methyl lactate, ethyl lactate etc.These solvents can be used alone or as a mixture.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 photographic 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
20.5-3g/m more preferably
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.
[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 (PVA) and part ester, ether and acetal, or contain and make them have its multipolymer of the not substituted ethylene alcohol unit of essential water miscible real mass.As polyvinyl alcohol (PVA), can enumerate 71-100% hydrolysis, the degree of polymerization polyvinyl alcohol (PVA) in the 300-2400 scope.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-403, PVA-420, PVA-613, L-8 etc.As above-mentioned multipolymer, can enumerate 88-100% hydrolysed polyvinyl acetate chloracetate or propionic ester, polyvinyl formal and Pioloform, polyvinyl acetal and their multipolymer.As other useful polymkeric substance, can enumerate polyvinyl pyrrolidone, gelatin and gum arabic, these can use separately or and use.These water soluble polymers contain the ratio of 30-99% with respect to all solids composition of protective finish, the ratio of preferred 50-99%.
In protective finish, can also add the surfactant that is used to improve coating, the known adjuvants such as water miscible plastifier that are used to improve the epithelium rerum natura.As water miscible plastifier, 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
[processing of developing]
The goods of the finished photopolymerizable lithographic plate of sheet material are with for example the Solid State Laser and the semiconductor laser (760nm-1200nm) of carbon arc lamp, high-pressure mercury-vapor lamp, xenon lamp, metal halide lamp, fluorescent light, tungsten lamp, Halogen lamp LED, helium cadmium laser, argon laser, FD-YAG laser, He-Ne Lasers, semiconductor laser (350nm-600nm), infra-red-emitting carry out image exposure to photographic layer.After adopting these known in the past active rays to carry out image exposure,, can on aluminium sheet support surface, form image by development treatment.
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 photographic layer.
In addition, as mentioned above, the known protective finish with oxygen barrier performance that is provided with on the photographic layer of photosensitive lithographic plate of the present invention uses developer solution to carry out the method for the removal of the removal of protective finish and photographic layer unexposed portion simultaneously; Perhaps water, warm water are removed protective finish earlier, then the method by developing the photographic layer of unexposed portion being removed.Usual method is adopted in the development of the above-mentioned developer solution of employing of photosensitive lithographic plate among the present invention, under 0-60 ℃, preferred about 15-40 ℃ temperature, for example, the photosensitive lithographic plate that exposure-processed is crossed impregnated in the developer solution, carries out with brush wiping etc.
When so when using automatic processing machine to carry out development treatment, developer solution is tired because of treatment capacity, therefore can use to replenish liquid or fresh developer solution is replied processing power.
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 derivative etc. carry out aftertreatment.In the aftertreatment of photosensitive lithographic plate of the present invention, these processing can be carried out various being used in combination.Galley by above-mentioned Processing of Preparation can make anti-brush raising by adopting heat treated such as post-exposure processing, roasting.Lithographic plate by this Processing of Preparation is installed on the offset press, is used for the printing of multipage.
The present invention will be described below in conjunction with embodiment, but the present invention is not subjected to 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 sending.Surface treatment with 10% NaOH, down will send the aluminium sheet that machine sends continuously at 70 ℃ and flood for 60 seconds from this, carry out etching after, after washing with flowing water, use 20%HNO
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 surfaceness, it is 0.6um (Ra represents).
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 primary coat is mixed with coating composition, stir down at 30 ℃.After about 5 minutes, find heating, react after 60 minutes, content is transferred in the other container, by adding 10000 weight portion methyl alcohol again, modulation primary coat coating.
(primary coat liquid composition)
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 undercoat 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 acrylate (SARTOMER company, CN970A60) 2.0 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 (the powerful company in Changzhou, hexa-aryl bi-imidazole) 0.2 weight portion
Phthalocyanine (Shanghai reagent company of traditional Chinese medicines group) disperses thing 0.02 weight portion
Fluorine is non-ionic surfactant (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 photographic 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 the polyvinyl alcohol (PVA) drying, cool off then until the aluminium temperature and reach below 50 ℃.
(protective layer coating solution composition 1)
Polyvinyl alcohol (PVA) (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
Water-solubility function dyestuff 0.0225 weight portion
Low macromolecule water-solubility compound (being aforementioned water-soluble composition) 0.00225 weight portion
Distilled water 300 weight portions
With the laser c OBAT4 of big nation with 150uJ/cm
2Exposure after under the condition of 200 line/inches this photopolymerizable lithographic plate being carried out image exposure, carry out the back heat treated with MASTERVIEW company photopolymerization version automatic processing machine, wash, with developer solution PD-1 (The Second Film Factory of Lucky Group's system, PD-1: water=1: 1) develop.The developer solution temperature is 25 ℃, and the dip time in developer solution is about 20 seconds.Washing, drying.
(embodiment 2)
In embodiment 1, except the protective layer coating solution composition change, adopt method similarly to Example 1 to make photo-polymerization type lithographic printing plate.
Protective layer coating solution composition 2
Polyvinyl alcohol (PVA) (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
Water-solubility function dyestuff 4.5 weight portions
Low macromolecule water-solubility compound (being aforementioned water-soluble composition) 0.00225 weight portion
Distilled water 300 weight portions
(embodiment 3)
In embodiment 3, except the protective layer coating solution composition change, adopt method similarly to Example 1 to make photo-polymerization type lithographic printing plate.
Protective layer coating solution composition 3
Polyvinyl alcohol (PVA) (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
Water-solubility function dyestuff 0.0225 weight portion
Low macromolecule water-solubility compound (being aforementioned water-soluble composition) 2.25 weight portions
Distilled water 300 weight portions
(embodiment 4)
In embodiment 4, except the protective layer coating solution composition change, adopt method similarly to Example 1 to make photo-polymerization type lithographic printing plate.
Protective layer coating solution composition 4
Polyvinyl alcohol (PVA) (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
Water-solubility function dyestuff 4.5 weight portions
Low macromolecule water-solubility compound (being aforementioned water-soluble composition) 2.25 weight portions
Distilled water 300 weight portions
(embodiment 5)
In embodiment 5, except the protective layer coating solution composition change, adopt method similarly to Example 1 to make photo-polymerization type lithographic printing plate.
Protective layer coating solution composition 5
Polyvinyl alcohol (PVA) (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
Water-solubility function dyestuff 2.0 weight portions
Low macromolecule water-solubility compound (being aforementioned water-soluble composition) 2.25 weight portions
Distilled water 300 weight portions
(embodiment 6)
In embodiment 6, except the protective layer coating solution composition change, adopt method similarly to Example 1 to make photo-polymerization type lithographic printing plate.
Protective layer coating solution composition 6
Polyvinyl alcohol (PVA) (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
Water-solubility function dyestuff 3.1 weight portions
Low macromolecule water-solubility compound (being aforementioned water-soluble composition) 1.3 weight portions
Distilled water 300 weight portions
Gold-tinted security and the protective finish resistance to marring just implementing plate of the present invention (embodiment 1-6 in the embodiment second portion) below and do not implement plate of the present invention (comparative example 1, comparative example 2) are done a pair of such as following table.We can be clearly seen that by following table, and it is all good than the gold-tinted security of not implementing plate of the present invention and resistance to marring to implement plate gold-tinted of the present invention security and resistance to marring.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 | Comparative example 2 | |
| The gold-tinted security (minute) | 45 | 38 | 36 | 42 | 40 | 32 | 18 | 22 |
| Resistance to marring | Excellent | Very | Very | Very | Excellent | Excellent | In | In |
Annotate: the gold-tinted security with the impregnable maximum duration of plate development under the gold-tinted (minute) be as the criterion.
Claims (9)
1. photo-polymerization type lithographic printing plate; it comprises the photo-polymerization type lithographic printing plate body; it is characterized in that: include support in the described photo-polymerization type lithographic printing-plate body; it on support the optical polymerism photographic layer; on the optical polymerism photographic layer, has the water-based protective seam; this water-based protective seam includes the water-solubility function dyestuff, and the absorption spectrum of this water-solubility function dyestuff is at visible-range.
2. photo-polymerization type lithographic printing plate according to claim 1 is characterized in that: also include the water-soluble composition that can cause the water-soluble polymers generation cross-linking reaction that contains carboxyl or hydroxyl in the described water-based protective seam.
3. photo-polymerization type lithographic printing plate according to claim 1 is characterized in that: the weight percent concentration of water-solubility function dyestuff in protective finish in the described water-based protective seam is 0.1-20%.
4. according to claim 1 or 2 or 3 described photo-polymerization type lithographic printing plates, it is characterized in that: the weight percent concentration of water-soluble composition in protective finish in the described water-based protective seam is 0.01-10%; Preferable amount is 0.01-3%.
5. photo-polymerization type lithographic printing plate according to claim 1 is characterized in that: described water-solubility function dyestuff, and its absorption spectrum is between 300～600nm; Its consumption preferred weight percent concentration in the water-based protective seam is 0.1-5%.
6. photo-polymerization type lithographic printing plate according to claim 1 is characterized in that: described water-soluble composition adopts boric acid, carbonic acid and corresponding alkali metal salt to include in potassium borohydride, sodium carbonate, the sodium bicarbonate any one or multiple combination; Its consumption is 0.01-10% for shared weight percent concentration in the water-based protective seam, and preferable amount is 0.05-5%.
7. according to claim 1 or 2 or 3 described photo-polymerization type lithographic printing plates, it is characterized in that: also adding in described water-based protective seam has plastifier, this plastifier to include any one or more combination in propionamide, cyclohexanediol, glycerine, the sorbierite.
8. according to claim 1 or 2 or 3 described photo-polymerization type lithographic printing plates; it is characterized in that: also adding in described water-based protective seam has water miscible acrylic acid series polymeric compounds or metha crylic polymer; and its amount of coating is 0.1g/m in dried weight
2-Yue 15g/m
2, be preferably 1.0g/m
2---5.0g/m
2Drying coated weight as protective finish is 0.5-10g/m
2, be preferably 1.0-5.0g/m
2
9. according to claim 1 or 2 or 3 described photo-polymerization type lithographic printing plates, it is characterized in that: in the described photo-polymerization type lithographic printing plate body optical polymerism photographic layer contain at least have the ethene unsaturated group can polymeric compounds, in the light trigger, sensitizing coloring matter, adhesive resin a kind of or many in combination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101073768A CN101174090A (en) | 2006-11-02 | 2006-11-02 | Photo-polymerization type lithographic printing plate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101073768A CN101174090A (en) | 2006-11-02 | 2006-11-02 | Photo-polymerization type lithographic printing plate |
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| Publication Number | Publication Date |
|---|---|
| CN101174090A true CN101174090A (en) | 2008-05-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2006101073768A Pending CN101174090A (en) | 2006-11-02 | 2006-11-02 | Photo-polymerization type lithographic printing plate |
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| CN102317337A (en) * | 2009-02-12 | 2012-01-11 | 拜尔材料科学股份公司 | Method for preparing holographic photopolymer on polymer film |
| CN101770170B (en) * | 2008-12-30 | 2012-03-21 | 乐凯集团第二胶片厂 | Photosensitive composition suitable for heat-sensitive positive computer to plate (CTP) and lithographic plate containing same |
| CN102582312A (en) * | 2011-12-23 | 2012-07-18 | 乐凯华光印刷科技有限公司 | Low chemical treatment violet laser photopolymerization type planographic printing plate |
| CN103085526A (en) * | 2011-11-03 | 2013-05-08 | 中国科学院化学研究所 | Printing plate material for ink-jet printing direct-to-plate and preparation method of printing plate material |
| CN104213172A (en) * | 2014-08-08 | 2014-12-17 | 太仓欧锐智能化工程有限公司 | Device for stabilizing electrolytes in PS plate producing process |
| CN104630873A (en) * | 2013-11-08 | 2015-05-20 | Lg电子株式会社 | Exterior decor panel for home appliance and method of manufacturing the same |
| CN106364209A (en) * | 2016-11-04 | 2017-02-01 | 中国科学院理化技术研究所 | Thermosensitive treatment-free lithographic printing plate material containing thermosensitive protective layer and application |
| CN107735699A (en) * | 2015-07-10 | 2018-02-23 | 迪睿合株式会社 | Phosphor plates, the white light source device for possessing the phosphor plates and the display device for possessing the white light source device |
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| CN101770170B (en) * | 2008-12-30 | 2012-03-21 | 乐凯集团第二胶片厂 | Photosensitive composition suitable for heat-sensitive positive computer to plate (CTP) and lithographic plate containing same |
| CN102317337B (en) * | 2009-02-12 | 2014-11-26 | 拜尔材料科学股份公司 | Method for preparing holographic photopolymer on polymer film |
| CN102317337A (en) * | 2009-02-12 | 2012-01-11 | 拜尔材料科学股份公司 | Method for preparing holographic photopolymer on polymer film |
| CN103085526A (en) * | 2011-11-03 | 2013-05-08 | 中国科学院化学研究所 | Printing plate material for ink-jet printing direct-to-plate and preparation method of printing plate material |
| CN102582312A (en) * | 2011-12-23 | 2012-07-18 | 乐凯华光印刷科技有限公司 | Low chemical treatment violet laser photopolymerization type planographic printing plate |
| CN102582312B (en) * | 2011-12-23 | 2016-06-29 | 乐凯华光印刷科技有限公司 | A kind of low chemical treatment violet laser photopolymerization type planographic printing plate |
| CN104630873A (en) * | 2013-11-08 | 2015-05-20 | Lg电子株式会社 | Exterior decor panel for home appliance and method of manufacturing the same |
| US9746765B2 (en) | 2013-11-08 | 2017-08-29 | Lg Electronics Inc. | Exterior décor panel for home appliance and method of manufacturing the same |
| CN104213172A (en) * | 2014-08-08 | 2014-12-17 | 太仓欧锐智能化工程有限公司 | Device for stabilizing electrolytes in PS plate producing process |
| US10529899B2 (en) | 2015-07-10 | 2020-01-07 | Dexerials Corporation | Phosphor sheet, white light source device including the phosphor sheet, and display device including the white light source device |
| CN107735699A (en) * | 2015-07-10 | 2018-02-23 | 迪睿合株式会社 | Phosphor plates, the white light source device for possessing the phosphor plates and the display device for possessing the white light source device |
| US11183617B2 (en) | 2015-07-10 | 2021-11-23 | Dexerials Corporation | Phosphor sheet, white light source device including the phosphor sheet, and display device including the white light source device |
| CN106364209A (en) * | 2016-11-04 | 2017-02-01 | 中国科学院理化技术研究所 | Thermosensitive treatment-free lithographic printing plate material containing thermosensitive protective layer and application |
| EP3536513A4 (en) * | 2016-11-04 | 2020-09-02 | Technical Institute of Physics and Chemistry of the Chinese Academy of Sciences | Heat-sensitive processless planographic printing plate material containing thermosensitive protection layer, and use |
| CN106364209B (en) * | 2016-11-04 | 2018-11-09 | 中国科学院理化技术研究所 | Thermosensitive treatment-free lithographic printing plate material containing thermosensitive protective layer and application |
| WO2019076584A1 (en) * | 2017-10-17 | 2019-04-25 | Agfa Nv | A lithographic printing plate precursor |
| EP3474073A1 (en) * | 2017-10-17 | 2019-04-24 | Agfa Nv | A lithographic printing plate precursor |
| CN111213091A (en) * | 2017-10-17 | 2020-05-29 | 爱克发有限公司 | Lithographic printing plate precursor |
| US11635693B2 (en) | 2017-10-17 | 2023-04-25 | Agfa Offset Bv | Lithographic printing plate precursor |
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