CN104723656B - Purple laser photopolymerization sensitive lithographic plate and preparation method thereof - Google Patents
Purple laser photopolymerization sensitive lithographic plate and preparation method thereof Download PDFInfo
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Abstract
A kind of purple laser photopolymerization sensitive lithographic plate and preparation method thereof, include support in the photo-polymerization type lithographic printing plate, it is photo-polymerization type photosensitive layer on support, has water-based protective layer on photo-polymerization type photosensitive layer, photo-polymerization type photosensitive layer includes film-forming resin, unsaturated monomer and performed polymer, initiation system and other auxiliary agents, it is 10-30% that initiation system, which accounts for photo-polymerization type photosensitive layer total weight percent, the initiation system includes initiator, sensitising agent and aided initiating, wherein initiator amount accounts for initiation system percentage by weight as 20 40%, sensitising agent dosage accounts for initiation system percentage by weight as 40 60%, aided initiating dosage accounts for initiation system percentage by weight as 5 20%.Sensitive lithographic plate of the present invention greatly improves the preheating upper limit of plate.And the plate prepared accelerates coating molecule motion to be rapidly achieved stable state, plate is possessed higher sensitivity and storage stability after 90 DEG C of heating heating in 20 40 minutes or 50 DEG C 1 day.
Description
Technical field
The present invention relates to a kind of lithographic plate of the photo-polymerization type light sensitive layer formed on support, is specifically
It is related to a kind of photo-polymerization type lithographic printing plate that can use directly laser Graphic, further relates to the preparation method of the sensitive lithographic plate.
Background technology
Recently as the development of computer and semiconductor laser technique, photosensitive polymer material is as laser imaging material
Material is extensively studied and applied.Lithography technique moves towards to count comprehensively from traditional laser photo film copy PS platemaking technologies
The direct plate-making technology of calculation machine (abbreviation CTP technologies), CTP plates are also gradually popularized.CTP plate species is a lot, compares the bag of popularization
Include Silver Salt Diffusion Transfer CTP Plate material, UV-CTP versions, photopolymerization CTP plates, thermal CTP plate material etc..
So-called photopolymerization refers in the presence of light, the method for polymerizeing monomer.The direct light of light initiation polymerization point
Trigger two kinds of polymerization and photosensitive polymerization.The former, in the presence of light, light trigger generates active seed (free radical in excitation state
Or cation), trigger monomer polymerization；The latter's sensitising agent absorbs light first, and molecule is turned from ground state transition to excitation state by energy
Move or electronics transfer makes decomposition of initiator produce free radical, trigger the active material (containing double bond compound) in photosensitive layer to occur poly-
Close reaction.Thus required sensitive volume such as infrared light 830nm, green glow can be realized according to the absorption spectrum of sensitising agent
532nm, blue light 488nm and orchid light 405nm.
Purple laser c TP plates occur polymerisation and solidified through 405nm purple laser explosures, the photosensitive layer of exposure area,
There is dissolving to be changed into insoluble in developer solution.It is removed after the developed processing of unexposed area, forms printing plate clear area, exposure area is solid
Change remains, and forms printing plate image areas.Its lithography process is as follows：
Exposure → preheating → washing → development → washing → gluing → printing plate
Exposure stage, the sensitizing dye in photosensitive layer absorb laser energy, and molecule passes through energy from ground state transition to excitation state
Amount transfer or electronics transfer are sensitized initiator and decompose and produce free radical, trigger the active group in coating to polymerize
Solidification.Oxygen has strong inhibition to polymerisation, therefore in order to keep the high polymerization efficiency of photosensitive layer, the table of plate
Face is coated with protective layer used in starvation.
Preliminary drying makes the solidify coating (image-text area) after exposure, under the high temperature conditions further solidification, increase image areas with
The dissolving contrast in non-graphic area, improving the intensity of image areas increases resistance to print.The height of preliminary drying temperature is to important, preliminary drying of making a plate
Temperature is low, and areas can not fully solidify, and plate press resistance rate is low when causing to print；Preliminary drying temperature is too high, is easily caused non-graphic
Zone-coating reaction solidifies and scumming phenomenon occurs, dirty in printing.Particularly in lithography process, some plate developing machine preheating sections are not
Stable, temperature drift is larger, if plate preheating tolerance is narrow, scumming phenomenon just easily occurs.
Pre- washing purpose is to remove the water-soluble oxygen barrier layer on purple laser c TP versions surface before development.
Development is to remove uncured region, produces image.
Washing is to clean the printing plate from developing trough out.
The main hydrophily for being to maintain version base of gluing, avoid version base oxidation upper dirty；The alkaline residues of the space of a whole page are neutralized, are avoided
Its continuous action to image-text area, causes the change of press resistance rate.
In addition during plate natural storage, due to the motion and interaction of each material molecule in coating, make plate
Film speed rise or fall, it is not a kind of state of stabilization in use to cause plate.
The content of the invention
It is an object of the invention to provide a kind of purple laser photopolymerization sensitive lithographic plate and preparation method thereof, solves in lithography process
The scumming problem caused by plate preheating tolerance is narrow, provides a kind of sensitivity and storage stability that plate is improved by being heat-treated
Method.
The purpose of the present invention is realized by following measures：
A kind of purple laser photopolymerization sensitive lithographic plate, include support in the photo-polymerization type lithographic printing plate, in support
On be photo-polymerization type photosensitive layer, have water-based protective layer on photo-polymerization type photosensitive layer, photo-polymerization type photosensitive layer include into
Film resin, unsaturated monomer and performed polymer, system and other auxiliary agents, initiation system is triggered to account for photo-polymerization type photosensitive layer gross weight hundred
It is 10-30% to divide ratio, and the initiation system includes initiator, sensitising agent and aided initiating, and wherein initiator amount accounts for primosome
It is that percentage by weight is 20-40%, it is 40-60% that sensitising agent dosage, which accounts for initiation system percentage by weight, and aided initiating dosage accounts for
Initiation system percentage by weight is 5-20%.
Above-mentioned purple laser photopolymerization sensitive lithographic plate, the initiator are hexa-aryl bi-imidazole class.
Above-mentioned purple laser photopolymerization sensitive lithographic plate, the sensitising agent that described photo-polymerization type photosensitive layer is included are in 330nm-
450nm has the sensitizing material of maximum absorption band.
Above-mentioned purple laser photopolymerization sensitive lithographic plate, the aided initiating are the compound containing sulfydryl.
Above-mentioned purple laser photopolymerization sensitive lithographic plate, the compound containing sulfydryl are mercaptobenzothiazoler, mercaptobenzoxazole
Or any of sulfydryl triazole.
Above-mentioned purple laser photopolymerization sensitive lithographic plate, the photo-polymerization type photosensitive layer on support, with its dried amount of covering
Weight meter, it is 0.1g/m2- 10g/m2。
Above-mentioned purple laser photopolymerization sensitive lithographic plate, in the water-based protective layer in terms of the dried amount of covering weight, it is usually
0.5―10g/m2, preferably 1.0-4.0g/m2。
Above-mentioned purple laser photopolymerization sensitive lithographic plate, plate prepared by the above method pass through 90 DEG C of aging 20-40 minutes or 50 DEG C
After aging 1 day, plate possesses higher sensitivity and storage stability.
Above-mentioned purple laser photopolymerization sensitive lithographic plate, the unsaturated monomer and performed polymer are to be capable of the ethylenic of addition polymerization not
Saturated compounds, the ethylenically unsaturated compounds for being capable of addition polymerization account for the 5-80% of photo-polymerization type photosensitive layer gross weight, into
Film resin is polymer binder, and polymer binder accounts for the 10-90% of photo-polymerization type photosensitive layer gross weight.
Above-mentioned purple laser photopolymerization sensitive lithographic plate, heat polymerization inhibitors, thermal polymerization inhibition are also included in photo-polymerization type photosensitive layer
It is 0.01-5% that agent, which accounts for the poly- holotype photosensitive layer total weight percent of light,.
The present invention uses said components, greatly improves the preheating upper limit of plate, so as to provide a kind of more preferable light
It polymerize CTP plates.
The invention provides a kind of photo-polymerization type lithographic printing plate.The weight that its primosome is tied up in photo-polymerization type photosensitive layer
Percent concentration is 10-30%.It is 20-40% that preferred initiator amount, which accounts for initiation system percentage by weight, in the present invention, light
It is 40-60% that quick dose of dosage, which accounts for initiation system percentage by weight, and it is 5- that aided initiating dosage, which accounts for initiation system percentage by weight,
When 20%, this ratio, which can be, greatly improves the preheating upper limit of plate.And the plate prepared is by 90 DEG C of 20-40 points of heating
Clock or 50 DEG C heating 1 day after, accelerate coating molecule motion is rapidly achieved stable state, plate is possessed higher sensitivity and storage
Deposit stability.
Embodiment
The specific making with regard to this kind of photo-polymerization type lithographic printing plate is described as follows below.
[support and surface treatment]
The support used in the present invention can use the aluminium or its alloy of dimensionally stable.The thickness of aluminium plate is preferably about
0.6mm of 0.1mm mono- or so.
Processing method known to the surface treatment use of aluminium plate, first by carrying out degreasing and crude removal processing to aluminium sheet,
Aluminium surface is cleaned.Then, implement surface roughening treatment, give aluminium plate surface fine bumps；In order to improve aluminium sheet
The wearability on surface, implement anodized；Then aluminium surface is implemented at hydrophilicity-imparting treatment or/and sealing of hole as needed
Reason.
(processing of the electrolytic polishing of degreasing one) removes rolling oil, autoxidation epithelium, dirt etc. present on aluminium sheet, with equal
For the purpose of the surface roughening for carrying out electrochemistry evenly, the electrolytic polishing processing of aluminium sheet is carried out in acidic aqueous solution, or in acid
Or the chemical etching processing of aluminium sheet is carried out in aqueous alkali.The meltage of aluminium sheet caused by processing preferably dissolves 1--30g/m2.More
It is preferred that 1.5-20g/m of dissolving2。
(1) electrolytic polishing is handled
The known aqueous solution for being used for electrolytic polishing can be used.It is preferred that based on sulfuric acid or the aqueous solution of phosphoric acid, it is special
The aqueous solution not preferably based on phosphoric acid.Can be from the weight of phosphoric acid 20-90 % (preferably 40-80 weight %), liquid temperature 10 1
90 DEG C of (preferably 50 1 80 DEG C), current density 1-100A/dm2(preferably 5-80A/dm2), select in the electrolysis time scope of 180 seconds
Select.50 weight % sulfuric acid, chromic acid, hydrogen peroxide, citric acid, hydrofluoric acid, phthalic acid can be added in phosphate aqueous solution
Acid anhydride etc..Electric current can use direct current, pulse direct current or exchange, but preferably continuous direct current.Electrolytic processing apparatus can use flat type
The device that electrolysis processing known to groove, star-like groove etc. uses.Flow velocity can be cocurrent, any one of adverse current relative to aluminium sheet,
Chosen from 0.01--10000cm/ points of scope.
The distance of aluminium sheet and electrode preferred 0.3--10cm, particularly preferred 0.8-2cm.It can use to use to method for electrically and lead
Electric roller directly to electrically, can also use do not use conductive rollers indirectly to electrically (liquid is to electrically).Use
Electrode material, construction can use the known material used in electrolysis processing, construction, the preferred carbon of negative electrode material, anode material
It is preferred that ferrite, indium oxide or paper tinsel.
(2) the chemical etching processing in acid or aqueous alkali
The chemical etching processing of aluminium sheet is carried out in acid or aqueous alkali can use these known means.Liquid temperature is preferred
For 25-90 DEG C, preferably carry out handling for 1-120 seconds.The concentration of acidic aqueous solution preferably 0.5-25 weight %, more preferably in acid
The aluminium dissolved in the property aqueous solution is 0.5-5 weight %.The concentration of aqueous alkali preferably 5-30 weight %, it is more preferably molten in buck
The aluminium dissolved in liquid is 30 weight %.(crude removal processing)
After etching process, when having carried out chemical etching using the aqueous solution of alkali, due to the Surface Creation dirt in aluminium,
Therefore typically with phosphoric acid, nitric acid, sulfuric acid, chromic acid or containing the sour nitration mixture of more than two kinds including these (crude removal is handled
Processing).The acidic aqueous solution used can dissolve 0-5 weight % aluminium, in liquid temperature from normal temperature to implementing at 70 DEG C, processing time
It is preferred that the 1-30 seconds.In addition, as the acidic aqueous solution, the electrolysis used in electrochemically grained processing etc. can be used
The waste liquid of liquid, it has to be noted that dry aluminium sheet, in decontamination thing liquid into analyzing.After crude removal processing terminates, in order to will not
Treatment fluid brings subsequent processing into, the washing that the liquid for preferably carrying out being carried out using nip rolls is removed and carried out using injection, but works as
When subsequent processing is the same aqueous solution, washing can also be omitted.
(electrochemically grained processing)
(1) using direct current electrochemically grained processing based on hydrochloric acid or the aqueous solution of nitric acid, can make
The aqueous solution used in the electrochemically grained processing using common exchange, can 1-100g/L hydrochloric acid or
1g/L is added in aqueous solution of nitric acid to the hydrochloric acid with salt acid ion such as the aluminum nitrate, sodium nitrate, ammonium nitrate of saturation or nitrification
1 of compound is used above.In addition, in based on the aqueous solution of hydrochloric acid or nitric acid can with dissolved iron, copper, manganese, titanium, magnesium,
The metal contained in the aluminium alloys such as silica.It is preferably used in hydrochloric acid or the weight % aqueous solution of nitric acid 0.5-2 and adds chlorination
Aluminium, aluminum nitrate are so that aluminium ion reaches 3-50g/L liquid.Temperature preferably 10 1 60 DEG C, more preferably 25-50 DEG C.Using straight
The electrochemically grained middle processing unit used of stream uses the device of direct current known to can use, using by a pair or
The device of more than two pairs of anode and negative electrode interaction arrangement.The electrochemically grained middle direct current used preferably uses pulsation rate
For less than 20% direct current.Current density preferably 10-200A/dm2, electricity preferably 10 1 1000C/dm when aluminium sheet is anode2。
Anode can be from ferrite, indium oxide, paper tinsel, the oxygen electrode known to compound or plating paper tinsel etc. on the valve metals such as titanium, niobium, zirconium
Middle selection uses.Negative electrode can select from carbon, paper tinsel, titanium, niobium, zirconium, stainless steel, the electrode that is used in cathode for fuel cell
Use.
(2) can be made based on hydrochloric acid or the aqueous solution of nitric acid using the electrochemically grained processing exchanged
The aqueous solution used in the common electrochemically grained processing using exchange, can be in 1--100g/L hydrochloric acid
Or add lg/L in aqueous solution of nitric acid there is nitrate ion, aluminium chloride, chlorination to the aluminum nitrate, sodium nitrate, ammonium nitrate of saturation etc.
There is the hydrochloric acid of salt acid ion or at least one of nitrate compound to use for sodium, ammonium chloride etc..In addition, using hydrochloric acid or nitric acid as
Metal that can be to contain in the aluminium alloys such as dissolved iron, copper, manganese, nickel, titanium, magnesium, silica in the aqueous solution of main body.
It is preferably used in hydrochloric acid or the weight % aqueous solution of nitric acid 0.5-2 and adds aluminium chloride, aluminum nitrate etc. so that aluminium ion
Reach 3-50g/L liquid.Preferably 10-60 DEG C, more preferably 20-50 DEG C of temperature.
(3) using nitric acid or hydrochloric acid as in the aqueous solution of principal component, using AC or DC, with 10---1000C/dm2's
Electricity carries out electrochemically grained processing to the aluminium sheet, in acidic aqueous solution, using electric current from 0 to peaking time
The platform shape ripple exchange for being 50---70Hz for 1-3msec and frequency.
(chemical etching processing (utilizing a sour alkalies))
So that the whole face of the fine concavo-convex sand holes formed in electrochemically grained processing, dirt etc. are removed as mesh
, carry out chemical etching processing.Liquid temperature is preferably 25-90 DEG C, preferably carries out handling for 1-120 seconds.The concentration of acidic aqueous solution
It is preferred that 0.5-25 weight %, the aluminium more preferably dissolved in acidic aqueous solution is 0.5-5 weight %.The concentration of aqueous alkali is excellent
5-30 weight % are selected, the aluminium more preferably dissolved in aqueous alkali is 1--30 weight %.Lost in acid or aqueous alkali
Processing is carved so that the meltage of aluminium sheet reaches 1g/m2Above, 30g/m2Below or the meltage of aluminium reaches 0.1g/m2Above, 3g/
m2Below.
In addition, when carrying out chemical etching using the aqueous solution of alkali, due to the Surface Creation dirt in aluminium, therefore in this feelings
Typically with phosphoric acid, nitric acid, sulfuric acid, chromic acid or containing the sour nitration mixture of more than two kinds including these (institute is etched under condition
The crude removal processing needed).(identical with above-mentioned crude removal record).
(anodized)
In order to improve the water-retaining property of surface of aluminum plate, abrasion performance, implement anodized.Anodic oxidation as aluminium sheet
The electrolyte used in processing, if forming porous oxidation epithelium, any electrolyte can be used.Usually using sulfuric acid, phosphorus
Acid, oxalic acid, chromic acid or their mixed liquor.The concentration of these electrolyte suitably determines because of the species of electrolyte.Anodic oxidation
Treatment conditions become because of used electrolyte, therefore cannot treat different things as the same, if the concentration of generally electrolyte is 1--
80wt%, liquid temperature are 5-70 DEG C, current density 1--60A/dm2, voltage 1--100V, electrolysis time 5 seconds --- the model of 300 seconds
It is appropriate in enclosing.Sulfuric acid process is generally handled with DC current, but can also use exchange.The amount of anodic oxide coating is
0.5—10g/m2Scope be appropriate.The concentration of sulfuric acid uses 5-30%.Within the temperature range of 20-60 DEG C carry out 5-
Electrolysis in 250 seconds is handled.It is preferred that contain aluminium ion in the electrolyte.The more preferably 1--50A/dm of current density now2.
In the case of phosphoric acid method, concentration 5-50%, at a temperature of 30-60 DEG C, 10-300 seconds, 1--15A/dm2Electric current
Handled under density.The amount of anodic oxide coating is preferably 1.0g/m2More than, more preferably 2.0-6.0g/m2Scope.
(hydrophilicity-imparting treatment)
After anodized is implemented, hydrophilicity-imparting treatment is implemented to aluminium surface as needed.In the method, in silicon
By support impregnation in acid sodium aqueous solution, or carry out electrolysis processing.(other processing (washing, sealing of hole))
After throughout reason terminates, in order to not bring treatment fluid into subsequent processing, remove and adopt using nip rolls liquid
The washing carried out with injection.It is preferred that implement sealing pores after anodized.The sealing pores by containing hot water and
Impregnate in the hydrothermal solution of inorganic salts or organic salt and carried out using water vapour bath.
[formation of photosensitive layer]
The coating of photo-polymerization type photosensitive composite is coated with priming coat and is dried, forms photosensitive layer.
Photo-polymerization type photosensitive composite is dissolved with 2-50 weight % solid component concentration, is scattered, is applied to support
On aluminum substrate and it is dried.The painting of the layer (photosensitive layer) for the photo-polymerization type photosensitive composite being coated with support aluminum substrate
Cloth amount is different because of purposes, it is usually preferred to which dried weight is 0.3-4.0g/m2.Use can be added in photosensitive composite
In the surfactant, the particularly preferred fluorine class surfactant that improve coated face matter.
The photo-polymerization type photosensitive composite of the photosensitive layer of the composition photosensitive lithographic plate used in the present invention is with energy
Ethylenically unsaturated compounds, light trigger, the macromolecule bonding agent of enough addition polymerizations are essential component, as needed can be simultaneously
With the various compounds such as colouring agent, plasticizer, heat polymerization inhibitors.
So-called ethylenically unsaturated compounds, when referring to that photo-polymerization type photosensitive composite receives active ray irradiation, tool
Favourable addition polymerization, crosslinking, the compound of the ethylenic unsaturated bond solidified with the effect of Photoepolymerizationinitiater initiater.
Compound containing the ethylenic double bond for being capable of addition polymerization, can from least with 1, preferably with 2 with
Arbitrarily selected in the compound of upper terminal ethylenic unsaturated bond.
Can have such as monomer, prepolymer, i.e. 2 aggressiveness, 3 aggressiveness and oligomer, or their mixture and they
Copolymer etc. chemical form.
As monomer and its example of copolymer, unsaturated carboxylic acid (such as acrylic acid, methacrylic acid, clothing can be enumerated
Health acid, crotonic acid, iso-crotonic acid, maleic acid etc.) and aliphatic polybasic alcoholic compound ester, unsaturated carboxylic acid and aliphatic polybasic
Acid amides of amines etc..
As aliphatic polybasic alcoholic compound and the concrete example of the monomer of the ester of unsaturated carboxylic acid, including：As acrylic acid
Glycol diacrylate, triethylene glycol diacrylate, 1,3-- butanediol diacrylates, the Isosorbide-5-Nitrae of ester -- the propylene of butanediol two
Acid esters, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane
Three (acryloxypropyl) ethers, methylolethane triacrylate, hexanediyl ester, Isosorbide-5-Nitrae -- cyclohexanediol dipropyl
Olefin(e) acid ester, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythrite tetrapropylene
Acid esters, dipentaerythritol diacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, sorbierite three
Acrylate, sorbierite tetraacrylate, the acrylate of sorbierite five, the acrylate of sorbierite six, three (acrylyl oxy-ethyls)
Isocyanuric acid ester, polyester acrylate oligomers etc..
As methacrylate, including Isosorbide-5-Nitrae -- butanediol dimethylacrylate, triethylene glycol dimethacrylate,
Neopentylglycol dimethacrylate, trimethylol-propane trimethacrylate, trimethylolethane trimethacrylate methacrylate,
Ethylene glycol dimethacrylate, 1,3-- butanediol dimethylacrylates, hexanediol dimethacrylate, pentaerythrite
Dimethylacrylate, pentaerythritol acrylate trimethyl, pentaerythritol tetramethylacrylate, dipentaerythritol dimethyl
Acrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylates, sorbierite trimethacrylate acid
Ester, sorbierite tetramethyl acrylate, two [p--(3-- methacryloxies -2-- hydroxy propyloxy groups) phenyl] dimethyl
Methane, two [p--(methacroyloxyethoxy) phenyl] dimethylmethanes etc..
As itaconate, including ethylene glycol diitaconate, propane diols diitaconate, the clothing health of 1,3-- butanediols two
Acid esters, Isosorbide-5-Nitrae -- butanediol diitaconate, Isosorbide-5-Nitrae -- butanediol diitaconate, pentaerythrite diitaconate, sorbierite four
Itaconate etc..
As crotonates, including the crotonates of ethylene glycol two, l, two bars of the crotonates of 4-- butanediols two, pentaerythrite
Beans acid esters, the crotonates of sorbierite four etc..
It is different as iso-crotonic acid ester, including the iso-crotonic acid ester of ethylene glycol two, the iso-crotonic acid ester of pentaerythrite two, sorbierite four
Crotonates etc..
As maleate, including ethylene glycol dimaleate, triethylene glycol dimaleate, the maleic acid of pentaerythrite two
Ester, the maleate of sorbierite four etc..
Further, it is also possible to enumerate the mixture of above-mentioned ester monomer.
In addition, as aliphatic polybasic amines and the concrete example of the monomer of the acid amides of unsaturated carboxylic acid, including methylene
Base pair-acrylamide, di-2-ethylhexylphosphine oxide -- Methacrylamide, 1,6-- hexamethylene bis -- acrylamide, 1,6-- hexa-methylenes
It is double -- the double methyl of Methacrylamide, the acrylamide of diethylenetriamines three, xylylene bisacrylamide, xylylene
Acrylamide etc..
In addition, the usage amount of these ethylenically unsaturated compounds is with 5-80 weight % of the full composition of photosensitive layer, preferably 30
One 70 weight % scope uses.
The macromolecule bonding agent used in photosensitive layer as the photosensitive lithographic plate of the present invention, due to serving not only as
The peel-forming agent of said composition and it is necessary to it is dissolved in alkaline developer, therefore use soluble or swellability in buck
Organic high molecular polymer.The organic high molecular polymer, if for example, using water dissolvable organic high molecular polymer,
Then can be with water development.There is the addition polymer of carboxylic acid group, i.e. methyl as such organic high molecular polymer, including side chain
Acrylic copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid-copolymers, maleic acid, partial esterification Malaysia
Acid copolymer etc..
In addition include that equally there is the acid cellulose derivative of carboxylic acid group in side chain.In addition gather in the addition with hydroxyl
Polymer of addition cyclic acid anhydride etc. is useful on compound.Wherein particularly preferably [(methyl) benzyl acrylate/(methyl) acrylic acid/
Other addition polymerization sex ethylene base monomers as needed] copolymer and [(methyl) allyl acrylate/(methyl) acrylic acid/
Other addition polymerization sex ethylene base monomers as needed] copolymer.In addition, as water soluble organic polymer, polyvinyl
Pyrrolidones, PEO etc. are useful.In addition, in order to improve the intensity of cured film, alcohol soluble polyamide, 2,
Polyethers of propane and epichlorohydrin etc. is also useful to 2-- bis- -- (4-- hydroxyphenyls) --.
These high molecular polymers can improve the strong of cured film by importing free-radical reactive group in side chain
Degree.As the functional group for being capable of polyaddition reaction, ethylenic unsaturated bond base, amino, epoxy radicals can be enumerated, in addition, making
For the functional group of free radical can be turned into by illumination, sulfydryl, mercapto, halogen atom, triazine structure, salt knot can be enumerated
Structure etc., in addition, as polar group, carboxyl, imino group etc. can be enumerated.As the above-mentioned function for being capable of polyaddition reaction
Group, the ethylenic unsaturated bond base such as particularly preferred acryloyl group, methylacryloyl, pi-allyl, styryl, in addition, from ammonia
Base, hydroxyl, phosphonate group, phosphate, carbamoyl, NCO, urea groups, l, 3- urylenes, sulfonic group, ammonium selection
Functional group be also useful.
In order to maintain the developability of composition, macromolecule bonding agent of the invention preferably has appropriate molecular weight, acid number,
Effectively using the high molecular polymer that weight average molecular weight is 5000-30 ten thousand, acid number is 10-200.
These organic high molecular polymers can mix arbitrary amount in all compositions.But when more than 90 weights
When measuring %, undesirable result is produced in image intensity of formation etc..Preferably 10-90%, more preferably 30-
80%.Furthermore, it is possible to which the ethylenically unsaturated compounds and organic high molecular polymer of photopolymerization are represented with weight ratio, it is preferably
L/9-9/l scope.Preferred scope is 2/8-8/2, more preferably 3/7-7/3.
In addition, as in the photosensitive layer of the photosensitive lithographic plate of the present invention containing including Photoepolymerizationinitiater initiater, photosensitive
Agent and the initiation component of aided initiating.
Wherein Photoepolymerizationinitiater initiater, according to known to can selecting suitably in patent, document etc. the wavelength of the light source used
Various light triggers, or the paralled system (light initiation system) of light trigger of more than two kinds use.Concrete example is exemplified below, but
It is not limited to these.
When with more than 400nm luminous ray, Ar laser, the 2nd high harmonic of semiconductor laser, SHG-YAG laser, putting
When the Solid State Laser and semiconductor laser of the 1200nm of injection wavelength 760nm mono- infrared ray are light source, it is proposed that various light-initiated
System, such as rose-red, eosin, algae red etc., or the system combined using dyestuff and initiator, such as dyestuff and the compound of amine are drawn
Hair system, six aryl bisglyoxalines and the paralled system of radical initiator and dyestuff, six aryl bisglyoxalines and to dialkyl amido
System, the ring-type of benzal ketone be cis-body of the system of Q-- dicarbonyl compounds and dyestuff, ring-type triazine and merocyanine pigment
System, the system of 3-- oxos coumaran and activating agent, bisglyoxaline, styrene derivative, the system of mercaptan, organic peroxide and
The system of pigment, the system of dyestuff and active halogen compound, the system of dyestuff and borate compound, there is rhodanine ring
The system of pigment and free radical generating agent, the system of titanocenes and 3 one oxo coumaran pigments, titanocenes and cluck ton pigment and
Combined system, titanocenes and the spy of the ethylenically unsaturated compounds for being capable of addition polymerization containing amino or carbamate groups
System, titanocenes and system of pigment with chromene ring of fixed merocyanine pigment etc..
In the present invention, it is preferred to use hexa-aryl bi-imidazole compound, most preferably with adjacent chloro hexa-aryl bi-imidazole.
According to the wavelength of the light source used, the sensitising agent being used in mixed way with adjacent chloro hexa-aryl bi-imidazole can be Michaelis
Ketone, cumarin, dyestuff etc..The sensitising agent of the present invention is the sensitizing material for having in 330nm-450nm maximum absorption band.
In addition, 2-- mercaptobenzothiazolers, 2-- mercaptobenzimidazoles, 2-- are added in above-mentioned light trigger as needed
The amines such as the thiol moieties such as mercaptobenzoxazole, N-- phenylglycines, N, N-- dialkyl amido aromatic alkyl esters
Deng the hydrogen property given compound as aided initiating, light-initiated ability can be further improved.
Aided initiating preferably uses thiol moiety in the present invention, more preferably using 2-- mercaptobenzothiazolers.
It is 10- that these photopolymerization, which trigger weight percent concentration of the usage amount of system in photo-polymerization type photosensitive layer,
30%, optimum amount 15-25%.
The ratio of initiator, sensitising agent, aided initiating compares improving preheating tolerance and plate stability in the present invention
It is important.Sensitising agent main function is to absorb laser energy, and molecule is turned from ground state transition to excitation state by energy transfer or electronics
Shifting is sensitized initiator and decomposes and produce free radical, and it is insensitive to heat；Initiator is i.e. to photaesthesia, also to thermo-responsive,
High temperature can also be allowed to produce free radical；Aided initiating thiol moiety serves not only as hydrogen donor and improves initiation energy in the present invention
Power, also serve as the storage stability that chain-transferring agent improves plate.
It is 20-40% that preferred initiator amount, which accounts for initiation system percentage by weight, in the present invention, and sensitising agent dosage, which accounts for, draws
It is 40-60% to send out system weight percentage, and it is 5-20% that aided initiating dosage, which accounts for initiation system percentage by weight,.
In addition, in the present invention, in addition to the basis more than, in the manufacture of photosensitive composite or in preservation,
In order to prevent the unnecessary thermal polymerization of polymerizable ethylenically unsaturated compounds, a small amount of heat polymerization inhibitors are preferably added.
As appropriate heat polymerization inhibitors, quinhydrones, p methoxy phenol, BHT, burnt tangerine phenol, the tert-butyl group can be enumerated
Catechol, benzoquinones, 4,4 '-thio two (3 methy 6 tert butyl phenols), the 2, (4- methyl -6- of 2 '-methylene two
Tert-butyl phenol), N- nitroso phenylhydroxylamines Asia cerium salt, N- nitroso phenylhydroxylamine aluminium salts etc..Heat polymerization inhibitors
Addition relative to the weight of all compositions, preferably from about 0.01%- about 5%.
In addition, for inhibition caused by anti-block, mountain lush acid, advanced as the lush acid acid amides of mountain can be added as needed
Derivative of fatty acid etc., it is set in drying process after coating to be partial to the presence of the surface of photosensitive layer.Advanced higher fatty acid derivative
Addition be preferably all compositions 0.5%-10%.
In addition, for the purpose of the coloring of photosensitive layer, colouring agent can be added.As colouring agent, including such as phthalocyanine system face
The pigment such as material, azo pigment, carbon black, titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone based dye, cyanine based dye.
The addition of dyestuff and pigment is preferably the 0.5%-20% of all compositions.
In addition, in order to improve the physical property of cured film, inorganic filler or dioctyl phthalate, adjacent benzene can be added
The additives such as the plasticizer such as dicarboxylic acid dimethyl ester, tricresyl phosphate.Their addition is preferably the 10% of all compositions
Below.
In photosensitive coated layer composition on support aluminium plate, it is dissolved in various organic solvents for using.As here
The solvent used, including acetone, methyl ethyl ketone, hexamethylene, ethyl acetate, dichloroethylene, tetrahydrofuran, toluene, ethylene glycol
It is monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, acetylacetone,2,4-pentanedione, cyclohexanone, double
Pyruvic alcohol, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, ethyleneglycol monopropylether, ethylene glycol monomethyl ether acetate,
3 one methoxypropanols, methoxymethoxy ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol (DEG)
Diethyl ether, propylene glycol methyl ether acetate, the Methoxypropylacetate of propylene glycol monoethyl ether acetate 1, the dimethyl of N, N mono-
Formamide, dimethyl sulfoxide (DMSO), the butyrolactone of Y mono-, methyl lactate, ethyl lactate etc..These solvents can be used alone or as a mixture.This
Outside, the concentration of the solid constituent in coating solution is that 50 weight % are appropriate.
In order to improve coated face matter, in the optical polymerism composition of the photosensitive layer of the photosensitive lithographic plate of the present invention
Surfactant can be added.Its amount of coating is in terms of dried weight, about 0.1g/m2- 10g/m2Scope be appropriate.More
Preferably 0.3-5g/m2.More preferably 0.5-3g/m2。
[formation of protective coating]
As the water soluble polymer containing hydrogen associativity group contained in protective coating, polyvinyl alcohol can be enumerated
And its part ester, ether and acetal, or contain the unsubstituted vinyl alcohol units of water miscible real mass necessary to there are them
Its copolymer.As polyvinyl alcohol, can enumerate 71-100% hydrolysis, the degree of polymerization 300-2400 scopes polyvinyl alcohol.
Can specifically enumerate PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H,
PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-2107, PVA-2177, PVA-
220, PVA-224, PVA-217EE, PVA-220, PVA-224 7PVA-217EE, PVA-217E, PVA-220E, PVA-
224E, PVA-405, PVA-420, PVA-613, L-8 etc..As above-mentioned copolymer, 88-100% hydrolysis can be enumerated
Polyvinyl acetate chloracetate or propionic ester, polyvinyl formal and Pioloform, polyvinyl acetal and their copolymer.Make
For other useful polymer, PVP, gelatin and gum arabic can be enumerated, these can be used alone
Or it is used in combination.These water soluble polymers relative to protective coating all solids composition, containing 30-99% ratio, preferably
50-99% ratio.
Surfactant, the water for improving epithelium physical property for improving coating can also be added in protective coating
Additive known to plasticizer of dissolubility etc..As water miscible plasticizer, including such as propionamide, cyclohexanediol, glycerine, mountain
Pears alcohol etc..Furthermore, it is possible to add water miscible (methyl) acrylic acid series polymeric compounds etc..Its amount of coating in terms of dried weight,
About 0.1g/m2- about 15g/m2Scope be appropriate.More preferably 1.0g/m2---5.0g/m2.Drying as protective coating
Coating weight, usually 0.5-10g/m2, preferably 1.0-5.0g/m2。
(coating method)
As photosensitive composite and the coating method of protective layer, the side for being coated with scraper (coating rod) can be used
Method, the method for extrusion type coating machine, method of ball coating machine (slide beald coater) etc., but it is not limited to these.
The present invention will be described with reference to embodiments, but the present invention and is not limited to the examples restriction.
Embodiment 1-7 and comparative example 1-2
[making of photopolymerizable lithographic plate]
Thick 0.30mm aluminium sheet (support) curling is fixed on submitting machine for the aluminium volume of web-like (curly).On surface
Process part impregnates the aluminium sheet continuously sent out from the submitting machine 60 seconds with 10% sodium hydroxide, at 70 DEG C, is etched
Afterwards, after being washed with flowing water, 20%HN0 is used3Carry out neutralization washing, washing.Sine wave is used under conditions of VA=12.7V
Alternating waveform-shaped current, with 300 coulombs/dm in 1% aqueous solution of nitric acid2Anode when electricity to carry out electrolytic surface to it coarse
Change is handled.Its surface roughness is determined, it is 0.6u m (Ra expressions).
Then it is impregnated in 30% H2SO4In the aqueous solution, after carrying out 2 minutes crude removals at 55 DEG C, 33 DEG C, 20%
H2SO4In the aqueous solution, negative electrode is configured on the face of graining, in current density 5A/dm2Under, anodic oxidation in 50 seconds is carried out, it is thick
Spend for 2.7g/m2.In addition, now the anodic oxide coating at the back side in the central portion of aluminium sheet is about 0.5g/m2, it is about in end
1.0g/m2。
Following hydrophilic layer coating compositions is mixed, stirred at 30 DEG C.After about 5 minutes, heating is found, reacts 60 points
Zhong Hou, content is transferred in other container, by adding 10000 parts by weight Methanol again, modulates primary coat coating.
(primary coat liquid composition)
0.1g/m will be reached on the liquid coatings to above-mentioned treated aluminium sheet2, it is dried until aluminium temperature reaches
To 70 DEG C, cooling is then carried out until aluminium temperature reaches less than 50 DEG C.
On the priming coat so obtained, the high sensitivity optical polymerism composition of following compositions is coated with, is made drying coated heavy
Amount reaches 1.6g/m2, be dried until aluminium temperature reach 100 DEG C, then carry out cooling until aluminium temperature reach less than 50 DEG C.
(photosensitive layer coating liquid composition)
Wherein：
A:The copolymer (molecular weight 70,000, acid number 60mg-KOH/g) of methyl methacrylate/methacrylic acid, is film forming
Resin,
B:Polyurethane acrylate (SARTOMER companies, CN970A60), is performed polymer,
C:Acrylic ester oligomer (SARTOMER companies, CN549), is performed polymer,
D:Multifunctional monomer (SARTOMER companies, SR531), is unsaturated monomer,
E:Phthalocyanine color dispersion (acrylic resin cladding 15：1 CuPc), it is colouring agent,
F:Fluorine system nonionic surfactant (3M companies, FC-4431)
G:Adjacent chloro hexa-aryl bi-imidazole, it is initiator,
H:2-- mercaptobenzothiazolers
I:4- (4- (2- chlorphenyls) -2- phenyl -5- oxazolyls)-N, N- diethyl-aniline, is sensitising agent,
J:Methyl ethyl ketone, it is solvent,
K:Propylene glycol monomethyl ether acetate, it is solvent.
The protective coating that composition consisting of the following is coated with the photosensitive layer is coated on protective coating, makes drying coated weight
For 2.0g/m2, in drying section, dry air temperature 120 DEG C is blowed 5 minutes with the wind speed 8m/ seconds, being dried does polyvinyl alcohol
It is dry, cooling is then carried out until aluminium temperature reaches less than 50 DEG C.
(protective layer coating solution composition)
(method of testing)
(1) sensitometry
By analog gray scale step-wedge, (such as Ugra1982 or Stouffer21 levels step-wedge, the transmission density difference of adjacent two-stage are
0.15) it is bonded on the space of a whole page, with the platemaking machine of Escher-grad Cobalt 4 (optical maser wavelength 405nm, spot diameter 12um), equipment
Resolution ratio 2540dpi is exposed to the whole space of a whole page and (makes 175 lines/inch file on the spot).Gathered with Heights MAYA85 light
Close after version automatic processing machine is carried out and heat (110 DEG C of space of a whole page temperature), washed, with developer solution PPD (Lekai groups second
Photographic film plant's system) development.Liquid temperature of developing is 26 DEG C, and the dip time in developer solution is about 17 seconds, is washed, and is dried.With
3 grades of Stouffer21 levels ash ladder 6 grades clean on the spot or 2 grades of Ugra1982 ashes ladder 5 grades clean on the spot is proper exposure amount, it is corresponding
Laser value be expressed as sensitivity.Numerical value is bigger, and sensitivity is lower；Numerical value is smaller, and sensitivity is higher.
(2) measure of tolerance is preheated
With Heights MAYA85 developing machines, different preheating temperatures is set.With the PPD developer solutions (glue of Lekai group second
Piece factory system) to coating plate development, developer temperatur is 26 DEG C, and the dip time in developer solution is about 17 seconds, is washed, and is done
It is dry.The preheating upper limit of space of a whole page temperature when occurring scumming (curing of coatings) using the space of a whole page as plate.
Just implement the plate (embodiment 1-7) of the present invention below and plate (comparative example 1, the comparative example of the present invention is not carried out
2) imaging performance and the preheating temperature upper limit contrast such as following table.
| Example | Initiation system ratio % | Ratio of initiator % | Sensitising agent ratio % | Aided initiating ratio % | Sensitivity | Preheat the upper limit |
| Example 1 | 10% | 20 | 60 | 20 | 80 | 135℃ |
| Example 2 | 10% | 40 | 55 | 5 | 70 | 125℃ |
| Example 3 | 10% | 40 | 40 | 20 | 75 | 131℃ |
| Example 4 | 30% | 20 | 60 | 20 | 66 | 135℃ |
| Example 5 | 30% | 40 | 55 | 5 | 63 | 127℃ |
| Example 6 | 30% | 40 | 40 | 20 | 65 | 131℃ |
| Example 7 | 20% | 37 | 45 | 18 | 63 | 135℃ |
| Comparative example 1 | 10% | 50 | 20 | 30 | 105 | 116℃ |
| Comparative example 2 | 30% | 60 | 37 | 3 | 60 | 100℃ |
By upper table, we can be clearly seen that, implement the plate preheating temperature upper limit of the invention and imaging performance all than not
The preheating temperature upper limit and imaging performance for implementing plate of the present invention will get well.
Another feature of the invention is that plate prepared by the above method passes through 90 DEG C of aging 20-40 minutes or 50 DEG C of agings
After 1 day, plate possesses higher sensitivity and storage stability.
Embodiment 8-13
The same identical of embodiment 3,5,7 formula identical method coating plate is respectively adopted in embodiment 8,9,10, after coating
Plate passes through 90 DEG C of aging 20-40 minutes, then carries out sensitivity and sensitivity stability test.
The same identical of embodiment 3,5,7 formula identical method coating plate, coating is respectively adopted in embodiment 11,12,13
Afterwards then plate carried out sensitivity and sensitivity stability test by 50 DEG C of agings 1 day.
| Example | The plate-making same day | Plate places January | Plate places March | Plate places June | Plate is placed 1 year |
| Embodiment 3 | 75 | 73 | 70 | 65 | 66 |
| Embodiment 5 | 63 | 61 | 58 | 55 | 55 |
| Embodiment 7 | 63 | 60 | 55 | 50 | 53 |
| Embodiment 8 | 65 | 65 | 65 | 65 | 65 |
| Embodiment 9 | 55 | 55 | 55 | 55 | 57 |
| Embodiment 10 | 50 | 50 | 50 | 50 | 50 |
| Embodiment 11 | 65 | 65 | 65 | 65 | 65 |
| Embodiment 12 | 55 | 55 | 55 | 55 | 55 |
| Embodiment 13 | 50 | 50 | 50 | 50 | 52 |
Seen by upper table, without 3,5,7 Example formulations heated in addition, during placing naturally, sensitivity has plate
One slow elevated trend, it is basicly stable after 6 months, plate by 90 DEG C heat 20-40 minutes or 50 DEG C heating 1 day after,
Plate reaches higher and stable sensitivity faster.
Claims (8)
1. a kind of purple laser photopolymerization sensitive lithographic plate, the purple laser photopolymerization sensitive lithographic plate includes support, on support
For photo-polymerization type photosensitive layer, has water-based protective layer on photo-polymerization type photosensitive layer, photo-polymerization type photosensitive layer includes film forming tree
Fat, unsaturated monomer and performed polymer, trigger system and other auxiliary agents, it is characterised in that：Initiation system accounts for photo-polymerization type photosensitive layer
Total weight percent is 10-30%, and the initiation system includes initiator, sensitising agent and aided initiating, wherein initiator amount
It is 20-40% to account for initiation system percentage by weight, and it is 40-60% that sensitising agent dosage, which accounts for initiation system percentage by weight, aided initiating
It is 5-20% that dosage, which accounts for initiation system percentage by weight,；The initiator is hexa-aryl bi-imidazole class；Described photo-polymerization type is photosensitive
The sensitising agent that layer is included is the sensitizing material for having in 330nm-450nm maximum absorption band；The aided initiating is containing sulfydryl
Compound.
2. purple laser photopolymerization sensitive lithographic plate according to claim 1, it is characterised in that：The compound containing sulfydryl is mercapto
Any of base benzothiazole, mercaptobenzoxazole or sulfydryl triazole.
3. purple laser photopolymerization sensitive lithographic plate according to claim 1, it is characterised in that：Photo-polymerization type on support
Photosensitive layer, it is 0.1g/m in terms of its dried amount of covering weight2- 10g/m2。
4. purple laser photopolymerization sensitive lithographic plate according to claim 1, it is characterised in that：Water-based protective layer is dried with its
The amount of covering weight meter, it is 0.5-10g/m2。
5. purple laser photopolymerization sensitive lithographic plate according to claim 1, it is characterised in that：Water-based protective layer is dried with its
The amount of covering weight meter, it is 1.0-4.0g/m2。
6. purple laser photopolymerization sensitive lithographic plate according to claim 1, it is characterised in that：Above-mentioned purple laser photopolymerization sensitive lithographic plate
After 90 DEG C of aging 20-40 minutes or 50 DEG C of agings 1 day, possess higher sensitivity and storage stability.
7. purple laser photopolymerization sensitive lithographic plate according to claim 1, it is characterised in that：The unsaturated monomer and performed polymer
It is the ethylenically unsaturated compounds for being capable of addition polymerization, the ethylenically unsaturated compounds for being capable of addition polymerization account for photo-polymerization type
The 5-80% of photosensitive layer gross weight, film-forming resin are polymer binders.
8. the purple laser photopolymerization sensitive lithographic plate according to any one of claim 1-7, it is characterised in that：Photo-polymerization type is photosensitive
Heat polymerization inhibitors are also included in layer, it is 0.01-5% that heat polymerization inhibitors, which account for photo-polymerization type photosensitive layer total weight percent,.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005309031A (en) * | 2004-04-21 | 2005-11-04 | Fuji Photo Film Co Ltd | Photosensitive lithographic printing plate |
| 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 |
| CN103365086A (en) * | 2012-03-28 | 2013-10-23 | 中国科学院理化技术研究所 | Positive ion-free radical mixed photopolymerisable imaging component based on vinylpyrrolidone copolymer resin |
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| JP3654422B2 (en) * | 2000-01-31 | 2005-06-02 | 三菱製紙株式会社 | Photosensitive composition and photosensitive lithographic printing plate material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005309031A (en) * | 2004-04-21 | 2005-11-04 | Fuji Photo Film Co Ltd | Photosensitive lithographic printing plate |
| 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 |
| CN103365086A (en) * | 2012-03-28 | 2013-10-23 | 中国科学院理化技术研究所 | Positive ion-free radical mixed photopolymerisable imaging component based on vinylpyrrolidone copolymer resin |
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