CN103698979A - Water-washable flexible resin plate and making method thereof - Google Patents
Water-washable flexible resin plate and making method thereof Download PDFInfo
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- CN103698979A CN103698979A CN201210368289.3A CN201210368289A CN103698979A CN 103698979 A CN103698979 A CN 103698979A CN 201210368289 A CN201210368289 A CN 201210368289A CN 103698979 A CN103698979 A CN 103698979A
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Abstract
The invention discloses a water-washable flexible resin plate and a making method thereof. The photosensitive elastomers of the water-washable flexible resin plate comprise a thermoplastic elastomer (A), a styrene-methacrylic acid-olyethoxylated methacryloyloxyethyl isocyanate copolymer (B), a butadiene-methyl methacrylate-methacrylic acid-divinylbenzene copolymer (C), a self-emulsifying active cross-linking monomer (D), a polymerizable vinyl monomer and its mixture (E), a radical initiator and its initiation system (F), and other additives (G) comprising a dye and the like. The above can be used to make the environmentally-friendly flexible resin plate, and the flexible resin plate has the advantages of short water washing time, good restoration of dots, independent points and independent lines.
Description
Technical field
The present invention relates to a kind of washing flexible resin plates and preparation method thereof, especially relate to a kind of water that directly makes and rinse plate, washing flexographic plate that can be printed on the machine and preparation method thereof.
Background technology
At present, flexographic plate is widely used in the printing of the easy distortion such as carton, flexible packaging, label or softer stock.
Conventionally, the film with pattern or word is placed on the unexposed flexographic plate that contains photosensitive elastomer body, ultraviolet exposure, the place that film is transparent sees through ultraviolet light, decomposition of initiator in photosensitive elastomer body becomes free radical, causes crosslinkable monomers and reacts and solidify.Do not see through ultraviolet region cross-linking reaction can not occur, utilize the difference of their solubleness in developer solution, rinse development and obtain the relief image that contains character pattern.Plate after development is dry, goes to glue, and post-exposure, guarantees the complete polymerization of photographic layer.The plate making is fixed on the cylinder of flexible printing press, can prepare printing.
Common flexible resin plates generally adopts solvent develop or environmentally friendly solvent to develop, in plate development dry run, the general 60-65 ℃ of baking temperature, having partial solvent volatilization overflows, be drained in atmosphere, cause environmental pollution, stay in for a long time in such environment and work, to operating personnel, may cause moral injury simultaneously.Therefore develop the flexible resin plates that water can rinse, can reduce solvent discharge, reduce solvent consumption, be beneficial to environmental protection.
Summary of the invention
The object of the present invention is to provide a kind of washing flexible resin plates and preparation method thereof, flexible resin plate provided by the invention, can wash punching version, and the washing punching version time is short, and site, independent point, independent lines etc. are reduced.
The present invention is achieved by the following technical solutions:
Washing flexible resin plates of the present invention, comprises support, bond coating, photosensitive elastomer body layer, resistance oxygen adherent layer, protective film, and the chief component of photosensitive elastomer body is: thermoplastic elastomer (A); Styrene-methacrylic acid-polyethoxy methylacryoyloxyethyl isocyanates multipolymer (B); Butadiene-methyl methacrylate-methacrylic acid-divinyl benzene copolymer (C); The active cross-linking monomer (D) of self-emulsifying; Polymerisable vinyl monomer and composition thereof (E); Radical initiator and initiator system thereof (F); Also contain other adjuvants (G) such as dyestuff.
Thermoplastic elastomer of the present invention (A), can be the multipolymer of phenylethylene/butadiene, the multipolymer of styrene/isoprene, vinyl cyanide/styrol copolymer, acrylonitrile/butadiene/styrene multipolymer, polyurethane, tygon etc., such example is as the star copolymer of polystyrene-poly butadiene-polystyrene triblock copolymer, polystyrene-poly isoprene-polystyrene triblock copolymer, polystyrene-poly ethylene butene-polystyrene block copolymer, polystyrene-poly isoprene, acrylonitrile/butadiene/styrene multipolymer etc.The best thermoplastic elastomer of the present invention is polystyrene-poly isoprene-polystyrene triblock copolymer.
Thermoplastic elastomer of the present invention (A), accounts for the 5-25% that washes flexographic plate photosensitive elastomer body layer total solid quality.
The multipolymer (B) of styrene-methacrylic acid of the present invention-polyethoxy methylacryoyloxyethyl isocyanates, chemical structural formula is as shown in (I):
（Ⅰ）
In above-mentioned (I) structural formula, St represents styrol structural unit; MAA represents methacrylic acid structural unit; MOI represents methylacryoyloxyethyl isocyanates structural unit; PEG represents polyethylene glycol structures unit; N is the integer of 50-1000.
Multipolymer (B) synthesis step of styrene-methacrylic acid-polyethoxy methylacryoyloxyethyl isocyanates is as follows: first synthesize polyethoxy methylacryoyloxyethyl isocyanates (MOI-PEG) monomer, then styrene, methacrylic acid, MOI-PEG monomer obtain multipolymer by emulsion or solution polymerization.
In the flask that has condenser pipe, nitrogen protection, thermometer, tap funnel and stirrer, add the polyglycol (being called for short PEG) of different trade mark meltings and the methylacryoyloxyethyl isocyanates (being called for short MOI) of equivalent; 40-100 ℃ of reaction under lauric acid diisobutyl tin (DBTDL) catalysis; reaction 1-3 hour, obtains (MOI-PEG) monomer.By infrared spectrum detection of active isocyanate group 2275 peaks, place, disappear for reaction complement mark.
Styrene-methacrylic acid-polyethoxy methylacryoyloxyethyl isocyanates (MOI-PEG) can be synthetic by copolymer emulsion or solution polymerization, then by saltouing, solvation processing, filtration, vacuum drying form polymkeric substance.
The multipolymer (B) of styrene-methacrylic acid of the present invention-polyethoxy methylacryoyloxyethyl isocyanates accounts for the 15-25% of total solid quality
The multipolymer of butadiene-methyl methacrylate-methacrylic acid-divinylbenzene of the present invention (C), the weight content of polybutadiene is preferably in more than 50%, it gives multipolymer elasticity, the content of methacrylic acid is preferably in below 10%, otherwise the acid number of polymkeric substance is too strong, washing or water-soluble swollen easily the distortion such as the picture and text that finally obtain, lines is large, can not truly reduce original copy.Such polymkeric substance can ShiJSR company DS-2, DS-57, TA906 etc., this polymkeric substance accounts for the 15-35% of total solid quality.
The active cross-linking monomer (D) of self-emulsifying of the present invention, its chemical structural formula is as shown in (II) or (III):
（Ⅱ）
In formula (II), R
1the side chain hydrogen carbon back that is aryl, contains aryl or the alkane substitute that contains aryl; R
2be-NH2, a kind of in Na, K, Li, BO is the alkoxy of the carbon atom of 1-5; AO is the alkoxy of the carbon atom of 2-4, and m is the integer of 0-100, and n is the integer of 1-2, and p is the integer of 0-100, and q is the integer of 0-10, X representative-CR
3=CH
2, R
3be hydrogen atom or-CH
3.
Show
（Ⅲ）
In formula (III), R
1hydrogen atom or methyl, R
2hydrogen atom or methyl, R
3oxygen atom or sulphur atom, R
4can be a kind of in methoxyl, ethoxy or propoxyl group, R
5be-NH2, a kind of in Na, K or Li, R
6be-OCO-, a kind of in-0-, methoxyl, ethoxy or propoxyl group, R
7be 1-19 carbon atom alkyl or
or any one in hydroxyl, carboxyl, m is the integer of 10-30, n is the integer of 1-40.
The concrete example of structural formula of the present invention (II) (sequence number 1)-(sequence number 8) is as follows, but is not limited to following structural formula:
(sequence number 3)
(sequence number 5)
(sequence number 7)
(sequence number 8)
The concrete example of structural formula of the present invention (III) (sequence number 9)-(sequence number 12) is as follows, but is not limited to following structural formula:
Structural formula (II) and structural formula (III) define respectively wider scope, and only there are these examples embodiment the inside, have probably just narrowed down in the future material that these are concrete.In addition in embodiment, preferably provide, the preparation method of every kind of structure.Suggestion for revision: (II) increased by 4 examples more, i.e. sequence number (1), sequence number (2), sequence number (7), sequence number (8), (III) has increased by 2 examples more, i.e. sequence number (11), sequence number (12).Aforementioned " the concrete example of structural formula of the present invention (II) (sequence number 1)-(sequence number 8) is as follows; but be not limited to following structural formula ", explain, patent examiner is appreciated that to know from experience and obtains, can only not limit to example sequence number (1)-sequence number (8).Besides these all can not be given an example out.Structural formula (III) is herewith managed.
(sequence number 9)
(sequence number 10)
(sequence number 11)
The active cross-linking monomer (D) of self-emulsifying of the present invention, can be chemical structural formula (II) or chemical structural formula (III), can use separately, also can chemical structural formula (II) and chemical structural formula (III) mixing use.The active cross-linking monomer (D) of self-emulsifying of the present invention, accounts for the 0.5-5% of total solid quality.
Polymerisable vinyl monomer of the present invention and composition thereof (E), in the vinyl monomer of polymerization, contain part of hydroxyl not esterified (methyl) acrylate, as pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five acrylate, two-trimethylolpropane tetra-acrylate, ethoxylated bisphenol a diacrylate etc.
Can be 2-(2 ethoxy ethoxy) ethyl propylene acid esters, isobornyl acrylate, 2-benzene oxygen ethyl propylene acid esters, tetrahydrofurfuryl alcohol acrylate, (methyl) acrylic acid-2-hydroxyl ethyl ester, acrylic acid-2-hydroxyl ethyl ester, (methyl) hydroxypropyl acrylate, butyl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) dodecylacrylate, (methyl) octadecyl acrylate, 1,3-PD two (methyl) acrylate, BDO two (methyl) acrylate, 1,5-PD two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, triethylene Glycol two (methyl) acrylate, four condensed ethandiol two (methyl) acrylate, five condensed ethandiol two (methyl) acrylate, propylene glycol diacrylate, tripropylene glycol two (methyl) acrylate, four contracting propylene glycol two (methyl) acrylate, neopentylglycol diacrylate, PDDA, phthalic acid tripropylene glycol diacrylate, ethoxylated bisphenol a diacrylate, ethoxylated trimethylolpropane triacrylate, glycerol propoxylate triacrylate, 2,2-bis-(p-hydroxybenzene)-propane two (methyl) acrylate, dihydroxy methylpropane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five acrylate, two-trimethylolpropane tetra-acrylate polyglycol two (methyl) acrylate, polybutadiene two (methyl) acrylate etc.In best polymerisable vinyl monomer, contain part of hydroxyl not esterified (methyl) acrylate, as pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five acrylate, two-trimethylolpropane tetra-acrylate, two-trimethylolpropane, 4 third methyl olefin(e) acid esters, ethoxylated bisphenol a diacrylate etc.
Polymerisable vinyl monomer of the present invention and composition thereof (E), accounts for the 5-17% of total solid quality.
The present invention also can the carboxylated polybutadiene of use side, increase the water development ability of photosensitive elastomer body, possesses heat cross-linking ability simultaneously, therefore mobility is very important for this system, hold carboxylated polybutadiene number-average molecular weight (Mn) General Requirements at 1050-5000, be preferably in 1050-3300, acid number is at 30-150 KOHmg/g.The carboxylated polybutadiene of such end can be the C-1000 of Nippon Soda, the CTPB I of Shandong Zibo Qi Long Chemical Co., Ltd., the Poly bd 45CT of Satomer company, Poly bd 2000CT, Poly bd 3000CT etc.The present invention also can the hydroxylated polybutadiene of use side, the polybutadiene of such terminal hydroxy group can be the G-1000 of Nippon Soda, G-2000, G-3000, the HTPB-I of Shandong Zibo Qi Long Chemical Co., Ltd., HTPB-II, HTPB-III, HTPB-IV, the Poly bd R-45HTLO of Satomer company, Poly bd R-20LM, Poly bd LF1, Poly bd LF2, Poly bd LF3, Poly bd 600E, Poly bd 605E, Krasol LBH 2000, Krasol LBH 3000, Krasol LBH-P 2000 Krasol LBH-P 3000, Krasol LBH 2040 etc.
Flexible photosensitive resin plate sensitization component of the present invention contains initiating agent or initiator system, can be that benzophenone, rice are sneered ketone, 4-acetoxyl group-4
,-diethylamide benzophenone, benzoin ethyl ether, Alpha-hydroxy cumene ketone, Alpha-hydroxy phenylcyclohexyl ketone, 2-phenyl-2; 2-dimethoxy acetyl benzophenone, 2-tertiary butyl anthraquinone, isopropyl thioxanthone, (morpholinyl benzoyl) 1-six bases 1,1(dimethylamino) propane, benzil, benzoin etc.Initiating agent or initiator system account for the 1-5% of flexible photosensitive resin plate sensitization component general assembly (TW).
In flexible photosensitive resin plate sensitization component of the present invention, can also add other auxiliary agents such as dyestuff, antioxidant, hot inhibitor, release agent, levelling agent, non-ionic surfactant.Such auxiliary agent dyestuff is as Neozapon
?red335, Neozapon
?red395, dimethyl diaminophenazine chloride (C.I.50040), the red T of alkali (C.I.50240), rhodamine indigo plant, Red Base 543, Neozapon Red 346, Valifast Red 3306, Valifast Red 3320, Solvent Red 52, Solvent Red 135, Solvent Red149, Solvent Red 179, Solvent Red 235, Solvent Orange 107 etc.Antioxidant can be BHT, IRGANOX 1010, IRGANOX 1076,168, hot inhibitor can be quinhydrones, p-dihydroxy-benzene, resorcinol etc., can also add the auxiliary agents such as Tween-20, Tween-30, Tween-85, Arlacel-20, Arlacel-40, Arlacel-60, Arlacel-85, cithrol, aliphatic amine polyoxyethylene ether, AEO, Methyl Benzene-o-dicarboxylate, ethyl phthalate, butyl phthalate, α-methyl styrene-styrene, Polyvinylchloride oligomer.Other adds the 1-8% that auxiliary agent weight accounts for photopolymer plate sensitization component general assembly (TW) dyestuff, antioxidant etc.
Above-mentioned material can by single screw rod or double screw extrusion machine metered charge, mixing, melt extrude to the certain thickness supports such as iron version, aluminium plate or PET sheet base that are coated with in advance bond coating, or by a certain proportion of water and dissolution with solvents above-mentioned composition, by curtain coating, be coated on the certain thickness supports such as iron version, aluminium plate or PET sheet base that are coated with in advance bond coating, evaporation water and solvent make the photosensitive elastomer body layer of washing flexographic plate, and photosensitive elastomer bulk layer thickness is at 0.1-1.70 mm.Support of the present invention can be poly-naphthalene-2 of having supportted, 6-bis-carbonic esters, polyethylene terephthalate, polybutylene terephthalate, Polyvinylchloride, polypropylene, polycarbonate, aluminium sheet, stainless steel version, copperplate etc., also can adopt other polymer sheet etc., thickness 0.05-0.5mm.The preferred iron version of the present invention, aluminium plate or PET sheet base, thickness is at 0.1-0.38mm.The surface treatment such as can wash in advance, deoil of such support.For PET sheet base support, in advance corona treatment.
Bond coating of the present invention, in advance one or more resins of the polymkeric substance that contains urethane acrylate, contain chlorine element, polyurethane, polyacrylate, EVA etc. are configured to solution, by modes such as scraper, post painting, anilox roll coatings, said components is coated on the supports such as iron version, aluminium plate or PET sheet base, utilize the drying and forming-films such as hot blast, steam, infrared, microwave, standby, coating thickness 1-5 μ m.
For the inhibition of anti-block to the photosensitive elastomer body of washing flexible resin plates; bonding to negative pattern of photosensitive elastomer body layer while simultaneously preventing from making a plate; the surface that is preferably in the photosensitive elastomer body of washing flexographic plate is coated with last layer resistance oxygen stick resistant compound coating; then on resistance oxygen stick resistant compound coating, be covered with one deck PET or PE diaphragm; or directly resistance oxygen compound coating is coated on PET or PE diaphragm; then laminating on photosensitive elastomer body of the present invention, prepare washing flexible resin plates.The present invention's resistance oxygen compound coating used is coated on PET or PE protection diaphragm base by methods such as scraper for coating, dip-coating, reticulate pattern roller coat, post paintings, coating dry weight 1-2g/m
2, then laminating on photosensitive elastomer body under the temperature of 50-100 ℃ and 1-3MP pressure, when using, user throws off PET or PE diaphragm, upper mechanism version.Such resistance oxygen compound can be polyvinyl alcohol (PVA) or polyvinyl alcohol (PVA)/ethylene glycol graft copolymer, polyvinylpyrrolidone, hydroxypropyl cellulose ester and composition thereof etc., the AIRVOL 203 of such polymkeric substance RuAir Products company, the PVI of Panchim company, the PVA-205 of Kuraray company, PVA-217, PVA-224, PVA-405, the Lubiksol K-90 of BASF AG, the Bilon200 of Toyobo company, the AS-L of Shin-Etsu company etc.The PET that the present invention is used or PE diaphragm, thickness 0.10-0.175mm.
By embodiments of the invention 1-4 and comparative example 1-3, be cut into the strip of 10cm * 60cm, in flexible platemaking apparatus KY1320(Guangzhou white clouds science and trade) upper back-exposure 20-30, throw off film PET, face exposure 10 minutes, in tap water, wash version 5 minutes, dry 1.5 hours for 60 ℃.Going under sticky fluorescent tube of wavelength 280nm, spacing 5cm, removes sticky 8-15 minute, UV-A post-exposure 5-10 minute, obtains plate, evaluates washing time length, the performances such as site, independent point, independent lines reduction.By embodiment 1-4 with to Billy 1-3 comparison, can obtain the standby plate washing time of system of the present invention short, the advantage such as site, independent point, independent lines are reduced.
The universal synthesis method of structure structural formula of the present invention (I):
PEG-MOI is synthetic: in the flask that has condenser pipe, nitrogen protection, thermometer, tap funnel and stirrer, add the different trades mark (hydroxyl value is through demarcating) PEG of melting and the MOI of equivalent; 60 ℃ of bulk reactions under lauric acid diisobutyl tin DBTDL catalysis; react reaction complement mark: disappear by peak, infrared spectrum detection of active isocyanate group 2275nm place about 1 hour.
Emulsion copolymerization: add alcohol solution in the flask that has condenser pipe, nitrogen protection, thermometer, tap funnel and stirrer; nitrogen replacement 0.5 hour; at 80 ℃, stir; drip St, AN, PEGMOI, AIBN (azoisobutyronitrile) blend; appropriate AIBN is added in centre or the later stage is introduced oxidation-reduction trigger system, and after 24 hours, reaction finishes.Then by saltouing, solvation processing, filtration, vacuum drying form polymkeric substance.
The concrete example of structural formula of the present invention (II) (sequence number 1)-(sequence number 8) synthesis step is as follows:
Synthesizing of structural formula sequence number (1):
In 2 liters of stainless steel autoclaves with stirring, thermometer and nitrogen gatherer, add different tridecanol 667.2 grams of (3.33mol) and 7 grams of catalyzer KOH.After the logical complete displaced air of nitrogen, add allyl glycidyl ether 380.0g(3.33mol at 92 ℃), then insulation reaction 6 hours at 90 ℃, obtains condensation reaction thing (A).At 130 ℃, to condensation reaction thing (A) 628 grams (2mol), add 880 grams, oxirane (30mol), be then incubated 2 hours and complete reaction, cooling discharge.
Reaction mass 314 grams (1.0mol) is put in the 4 neck glass flask with stirring, thermometer, nitrogen gatherer and tap funnel of 1.0L, logical nitrogen is cooled to 0-3 ℃, constantly stir 320 grams of chlorosulfonic acids of little slow dropping, maintain this thermotonus, after dropwising, insulation reaction 2 hours, the reaction product obtaining neutralizes by the aqueous solution of KOH, obtains the active cross-linking monomer of self-emulsifying of sequence number of the present invention (1) structural formula.
Synthesizing of structural formula sequence number (2):
The same sequence number of building-up process (1), finally by the aqueous solution of ammoniacal liquor replacement KOH, obtains the active cross-linking monomer of self-emulsifying of sequence number of the present invention (2) structural formula.
Synthesizing of structural formula sequence number (3):
In 3 liters of stainless steel autoclaves with stirring, thermometer and nitrogen gatherer, add nonylphenol 1101.75 grams of (5mol) and 10 grams of catalyzer KOH.After the logical complete displaced air of nitrogen, add methacrylic glycidol ether 641.0g(5mol at 95 ℃), then insulation reaction 5-6 hour at 90 ℃, obtains condensation reaction thing (B).At 130 ℃, to condensation reaction thing (B) 1045 grams (3mol), add 1320 grams, oxirane (30mol), be then incubated 2 hours and complete reaction, cooling discharge.
Reaction mass 394 grams (0.5mol) is put in the 4 neck glass flask with stirring, thermometer, nitrogen gatherer and tap funnel of 1.0L, logical nitrogen is cooled to 0-3 ℃, constantly stir 120 grams of chlorosulfonic acids of little slow dropping, maintain this thermotonus, after dropwising, insulation reaction 2 hours, the reaction product obtaining neutralizes with ammonia spirit, obtains the active cross-linking monomer of self-emulsifying of sequence number of the present invention (3) structural formula.
Synthesizing of structural formula sequence number (4):
Building-up process isostructure formula (sequence number 3), is used allyl glycidyl ether to substitute methacrylic glycidol ether, uses tridecyl phenol to substitute nonylphenol.Finally neutralization replaces ammonia spirit by NaOH aqueous solution, obtains the active cross-linking monomer of self-emulsifying of sequence number of the present invention (4) structural formula.
Synthesizing of structural formula sequence number (5):
Building-up process isostructure formula (sequence number 2), use methacrylic glycidol ether to substitute allyl glycidyl ether, use different tridecanol polyoxy ether (20) to substitute different tridecanol, obtain the active cross-linking monomer of self-emulsifying of sequence number of the present invention (5) structural formula.
Synthesizing of structural formula sequence number (6):
The same sequence number of building-up process (1), is used nonylphenol to substitute tridecyl phenol, obtains the active cross-linking monomer of self-emulsifying of sequence number of the present invention (6) structural formula.
Synthesizing of structural formula sequence number (7):
In 3 liters of stainless steel autoclaves with stirring, thermometer and nitrogen gatherer, add nonylphenol 1101.75 grams of (5mol) and 10 grams of catalyzer KOH.After the logical complete displaced air of nitrogen, add allyl glycidyl ether 571g(5mol at 90 ℃), then insulation reaction 5-6 hour at 90 ℃, obtains condensation reaction thing (C).At 130 ℃, to condensation reaction thing (C) 1003.7 grams (3mol), add 1980 grams, oxirane (45mol), be then incubated 2 hours and complete reaction, cooling discharge.
Reaction mass 498 grams (0.5mol) is put in the 4 neck glass flask with stirring, thermometer, nitrogen gatherer and tap funnel of 1.0L, logical nitrogen is cooled to 0-3 ℃, constantly stir 120 grams of chlorosulfonic acids of little slow dropping, maintain this thermotonus, after dropwising, insulation reaction 2 hours, the reaction product obtaining neutralizes with ammonia spirit, obtains the active cross-linking monomer of self-emulsifying of sequence number of the present invention (7) structural formula.
Synthesizing of structural formula sequence number (8):
The same sequence number of building-up process (7), oxirane is used 60mol, obtains the active cross-linking monomer of self-emulsifying of sequence number of the present invention (8) structural formula.
The concrete example of structural formula of the present invention (III) (sequence number 9)-(sequence number 12) is synthetic as follows:
Synthesizing of structural formula sequence number (9):
In 2 liters of stainless steel autoclaves with stirring, thermometer and nitrogen gatherer, add 516 grams (3.0mol) of nonyl acid, after the logical complete displaced air of nitrogen, add 10 grams of catalyzer boron trifluoride diethyl etherate, at 92 ℃, add acrylic acid glycidol ether 384g(3mol), then insulation reaction 6 hours at 90 ℃, obtains condensation reaction thing (D).Cooling discharge.
Reaction mass (D) 300 grams (1.0mol) is put in the 4 neck glass flask with stirring, thermometer, nitrogen gatherer and tap funnel of 1.0L, logical nitrogen is cooled to 0-3 ℃, constantly stir 320 grams of chlorosulfonic acids of little slow dropping, maintain this thermotonus, after dropwising, insulation reaction 2 hours, the reaction product obtaining neutralizes by the aqueous solution of year NaOH, obtains the active cross-linking monomer of self-emulsifying of sequence number of the present invention (9) structural formula.
Synthesizing of structural formula sequence number (10):
The same sequence number of building-up process (9), is used methyl propenoic acid glycidyl ether to replace acrylic acid glycidol ether, obtains the active cross-linking monomer of self-emulsifying of sequence number of the present invention (10) structural formula.
Synthesizing of structural formula sequence number (11):
The similar sequence number of building-up process (1), is used methyl propenoic acid glycidyl ether to replace allyl glycidyl ether, finally processes the aqueous solution that adopts NaOH, obtains the active cross-linking monomer of self-emulsifying of sequence number of the present invention (11) structural formula.
Synthesizing of structural formula sequence number (12):
The similar sequence number of building-up process (11), is used the different tridecanol of dodecyl acid substitution, and catalyzer replaces KOH by boron trifluoride diethyl etherate, finally processes and adopts ammonia spirit, obtains the active cross-linking monomer of self-emulsifying of sequence number of the present invention (12) structural formula.
With embodiment, describe the present invention in detail below, but the present invention is not limited thereto.
embodiment 1
The preparation of bond coating: 1400 grams of deionized waters, polyurethane TC-103(Guangdong Tian Yin Chemical Co., Ltd.) 700 grams, 14 grams of 10% KOH aqueous solution, surfactant FC-4430(3M company produces) 5 grams, under room temperature, stir 1 hour, obtain aqueous solution.
Support preparation: the thick PET of 0.125mm of 457 * 762mm specification.Speed by this aqueous solution with 5 ms/min is coated on the PET that thickness 0.125mm is thick, and 120 ℃ are dried 5 minutes, obtain the bond coating that coating thickness is 1.5 μ m.
Washing photosensitive elastomer body component:
7.5 grams of Kraton D1160 (KRATON company)
Styrene-methacrylic acid-polyethoxy methylacryoyloxyethyl isocyanates multipolymer
(mass ratio 60:7:33, n=34, acid number 51.7mgKOH/g resin, Lekai Hua Guang company) 25 grams
35 grams of DS-2 (JSR company)
3 grams of the present invention's's (sequence number 1) structural formulas
2 grams of the present invention's's (sequence number 4) structural formulas
2.84 grams of polyglycol (200) diacrylates (EM224, Changxing, Taiwan)
3.56 grams of polybutadiene dimethylacrylates
3.0 grams of 1,6-hexanediyl esters (the Tianjin proud son of heaven)
2.1 grams of dipentaerythritol five acrylate (the Tianjin proud son of heaven)
1.5 grams of HDDMAs (Xin Zhong village chemistry)
N-[3-dimethylamino-propyl] 3.0 grams of acrylamides
651 5.0 grams of light triggers
2.0 grams of 2,6-d-tert-butyl-p-cresols (Kowloon, Nanjing Chemical Co., Ltd.)
Neozapon
?red 395(BASF AG) 0.01 gram
0.4 gram of hydroxyethyl methylacrylate
C
12-142.5 grams of-tertiary alkyl amine ethoxylates (RW-150, Union Carbide Corp)
1.59 grams of Tween-20 (the gas Chemical Co., Ltd. of Foshan section)
Above-mentioned each component is mixed after 3-5 minute with double screw extrusion machine at 80-130 ℃, die head curtain coating by extruder is on the thick PET support of the 0.125mm of above-mentioned precoating bond coating, cold wind is cooled to room temperature, obtains the photosensitive elastomer body layer that contains support.Photosensitive elastomer body thickness 1.572mm.
The diaphragm preparation of coating resistance oxygen adherent layer:
By 50 grams of polyvinyl alcohol (PVA) AIRVOL 203 (Air Products company); 10 grams of PVI (Panchim company); 180 grams of deionized waters; 0.5 gram of Le-202 (Guangzhou Li Er chemistry); mix, use anilox roll, be coated on the PET sheet base diaphragm of 0.125mm; dry 20min at 90 ℃, resistance oxygen adherent layer thickness 2 μ m.Obtain being coated with the diaphragm of oxidation prevention layer, stay to obtain next step use.
Then by the diaphragm that contains resistance oxygen adherent layer at 70 ℃, laminating on the above-mentioned photosensitive elastomer body layer that contains PET support, obtain the washing flexible resin plates of 1.70mm thickness.
To under plate room temperature, place 3 days, in flexible platemaking apparatus KY1320(Guangzhou white clouds science and trade) upper back-exposure 20s, throws off diaphragm; enclose negative film, vacuumize, face exposure 12min; at the 5min of washing version from the beginning for the flat plate washing machine for flexographic plate of KMPXH900, dry 1.5 hours for 60 ℃.Going under sticky fluorescent tube of wavelength 280nm, spacing 5cm, goes sticky 9.5min, UV-A post-exposure 5 minutes, obtains plate, evaluates the performances such as site reduction.The plate washing of example 1 easily, 2%-95% reduction under the 122lpi of site, the independent point of 0.2mm and the clear reduction of 0.1mm independent lines, can meet the print request of 1.70mm plate.
embodiment 2
The preparation of bond coating: 1400 grams of deionized waters, polyurethane TC-103(Guangdong Tian Yin Chemical Co., Ltd.) 700 grams, 14 grams of 10% KOH aqueous solution, surfactant FC-4430(3M company produces) 5 grams, under room temperature, stir 1 hour, obtain aqueous solution.
Support preparation: the thick PET of 0.125mm of 457 * 762mm specification.Speed by this aqueous solution with 3 ms/min is coated on the PET that thickness 0.125mm is thick, and 120 ℃ are dried 6 minutes, obtain the bond coating that coating thickness is 1.6 μ m.
Washing photosensitive elastomer body component:
15 grams of Kraton D1160 (KRATON company)
Styrene-methacrylic acid-polyethoxy methylacryoyloxyethyl isocyanates multipolymer
(mass ratio 60:7:33, n=34, acid number 51.7mgKOH/g resin, Lekai Hua Guang company) 20 grams
32.5 grams of TA906 (JSR company)
5 grams of the present invention's's (sequence number 2) structural formulas
2.84 grams of polyglycol (200) diacrylates (EM224, Changxing, Taiwan)
3.56 grams of polybutadiene dimethylacrylates (Sartomer company)
3.0 grams of 1,6-hexanediyl esters (the Tianjin proud son of heaven)
2.1 grams of dipentaerythritol five acrylate (the Tianjin proud son of heaven)
1.5 grams of HDDMAs (Xin Zhong village chemistry)
N-[3-dimethylamino-propyl] 3.0 grams of acrylamides
5.0 grams of 651 light triggers (Jingjiang Hong Tai Chemical Co., Ltd.)
2.0 grams of 2,6-d-tert-butyl-p-cresols (Kowloon, Nanjing Chemical Co., Ltd.)
Neozapon
?red 395(BASF AG) 0.01 gram
0.4 gram of hydroxyethyl methylacrylate
C
12-142.5 grams of-tertiary alkyl amine ethoxylates (RW-150, Union Carbide Corp)
1.59 grams of Tween-20 (the gas Chemical Co., Ltd. of Foshan section)
Above-mentioned each component is mixed after 3-5 minute with double screw extrusion machine at 80-130 ℃, die head curtain coating by extruder is on the thick PET support of the 0.125mm of above-mentioned precoating bond coating, cold wind is cooled to room temperature, obtains the photosensitive elastomer body layer that contains support.Photosensitive elastomer body thickness 1.572mm.
The diaphragm preparation of coating resistance oxygen adherent layer:
By 50 grams of polyvinyl alcohol (PVA) AIRVOL 203 (Air Products company); 10 grams of PVI (Panchim company); 180 grams of deionized waters; 0.5 gram of Le-202 (Guangzhou Li Er chemistry); mix, use anilox roll, be coated on the PET sheet base diaphragm of 0.125mm; dry 20min at 90 ℃, resistance oxygen adherent layer thickness 2 μ m.Obtain being coated with the diaphragm of oxidation prevention layer, stay to obtain next step use.
Then by the diaphragm that contains resistance oxygen adherent layer at 70 ℃, laminating on the above-mentioned photosensitive elastomer body layer that contains PET support, obtain 1.70mm thickness washing flexible resin plates.
To under plate room temperature, place 3 days, in flexible platemaking apparatus KY1320(Guangzhou white clouds science and trade) upper back-exposure 20s, throws off diaphragm; enclose negative film, vacuumize, face exposure 12min; at the 6min of washing version from the beginning for the flat plate washing machine for flexographic plate of KMPXH900, dry 1.5 hours for 60 ℃.Going under sticky fluorescent tube of wavelength 280nm, spacing 5cm, goes sticky 10min, UV-A post-exposure 5 minutes, obtains plate, evaluates the performances such as site reduction.The plate washing of example 2 easily, 2%-95% reduction under the 122lpi of site, the independent point of 0.15mm and the clear reduction of 0.1mm independent lines, can meet the print request of 1.70mm plate.
embodiment 3
The preparation of bond coating: 1400 grams of deionized waters, polyurethane TC-103(Guangdong Tian Yin Chemical Co., Ltd.) 700 grams, 14 grams of 10% KOH aqueous solution, surfactant FC-4430(3M company produces) 5 grams, under room temperature, stir 1 hour, obtain aqueous solution.
Support preparation: the thick PET of 0.175mm of 457 * 762mm specification.Speed by this aqueous solution with 5 ms/min is coated on the PET that thickness 0.175mm is thick, and 120 ℃ are dried 5 minutes, obtain the bond coating that coating thickness is 1.5 μ m.
Washing photosensitive elastomer body component:
15 grams of Kraton D1160 (KRATON company)
Styrene-methacrylic acid-polyethoxy methylacryoyloxyethyl isocyanates multipolymer
(mass ratio 60:7:33, n=34, acid number 51.7mgKOH/g resin,, Lekai Hua Guang company) and 23.5 grams
32.5 grams of DS-2 (JSR company)
1.5 grams of the present invention's's (sequence number 2) structural formulas
2.84 grams of polyglycol (200) diacrylates (EM224, Changxing, Taiwan)
3.56 grams of polybutadiene dimethylacrylates (Sartomer company)
3.0 grams of 1,6-hexanediyl esters (the Tianjin proud son of heaven)
2.1 grams of dipentaerythritol five acrylate (the Tianjin proud son of heaven)
1.5 grams of HDDMAs (Xin Zhong village chemistry)
N-[3-dimethylamino-propyl] 3.0 grams of acrylamides
5.0 grams of 651 light triggers (Jingjiang Hong Tai Chemical Co., Ltd.)
2.0 grams of 2,6-d-tert-butyl-p-cresols (Kowloon, Nanjing Chemical Co., Ltd.)
Neozapon
?red 395(BASF AG) 0.01 gram
0.4 gram of hydroxyethyl methylacrylate
C
12-144.0 grams of-tertiary alkyl amine ethoxylates (RW-150, Union Carbide Corp)
1.59 grams of Tween-20 (the gas Chemical Co., Ltd. of Foshan section)
Above-mentioned each component is mixed after 3-5 minute with double screw extrusion machine at 80-130 ℃, die head curtain coating by extruder is on the thick PET support of the 0.125mm of above-mentioned precoating bond coating, cold wind is cooled to room temperature, obtains the photosensitive elastomer body layer that contains support.Photosensitive elastomer body thickness 0.963 mm.
The diaphragm preparation of coating resistance oxygen adherent layer:
By 50 grams of polyvinyl alcohol (PVA) AIRVOL 203 (Air Products company); 10 grams of PVI (Panchim company); 180 grams of deionized waters; 0.5 gram of Le-202 (Guangzhou Li Er chemistry); mix, use anilox roll, be coated on the PET sheet base diaphragm of 0.125mm; dry 20min at 90 ℃, resistance oxygen adherent layer thickness 2 μ m.Obtain being coated with the diaphragm of oxidation prevention layer, stay to obtain next step use.
Then by the diaphragm that contains resistance oxygen adherent layer at 70 ℃, laminating on the above-mentioned photosensitive elastomer body layer that contains PET support, obtain the washing flexible resin plates of 1.14mm thickness.
To under plate room temperature, place 3 days; directly throw off diaphragm; enclose negative film; vacuumize in flexible platemaking apparatus KY1320(Guangzhou white clouds science and trade) on directly throw off diaphragm; enclose negative film, vacuumize, face exposure 12min; at the 5min of washing version from the beginning for the flat plate washing machine for flexographic plate of KMPXH900, dry 1.5 hours for 60 ℃.Going under sticky fluorescent tube of wavelength 280nm, spacing 5cm, goes sticky 10min, UV-A post-exposure 5 minutes, obtains plate, evaluates the performances such as site reduction.The plate washing of example 3 easily, 2%-95% reduction under the 150lpi of site, the independent point of 0.10mm and the clear reduction of 0.1mm independent lines, can meet the print request of 1.14mm flexographic plate.
embodiment 4
The preparation of bond coating: 1400 grams of deionized waters, polyurethane TC-103(Guangdong Tian Yin Chemical Co., Ltd.) 700 grams, 14 grams of 10% KOH aqueous solution, surfactant FC-4430(3M company produces) 5 grams, under room temperature, stir 1 hour, obtain aqueous solution.
Support preparation: the thick PET of 0.125mm of 457 * 762mm specification.Speed by this aqueous solution with 3 ms/min is coated on the PET that thickness 0.125mm is thick, and 120 ℃ are dried 6 minutes, obtain the bond coating that coating thickness is 1.6 μ m.
Washing photosensitive elastomer body component:
25 grams of Kraton D1160 (KRATON company)
Styrene-methacrylic acid-polyethoxy methylacryoyloxyethyl isocyanates multipolymer
(mass ratio 60:7:33, n=34, acid number 51.7mgKOH/g resin, Lekai Hua Guang company) 20 grams
32.5 grams of DS-2 (JSR company)
1 gram of the present invention's's (sequence number 2) structural formula
2.84 grams of polyglycol (200) diacrylates (EM224, Changxing, Taiwan)
3.56 grams of polybutadiene dimethylacrylates
2.0 grams of 1,6-hexanediyl esters (the Tianjin proud son of heaven)
2.1 grams of dipentaerythritol five acrylate (the Tianjin proud son of heaven)
0.5 gram of HDDMA (Xin Zhong village chemistry)
N-[3-dimethylamino-propyl] 3.0 grams of acrylamides
651 3.0 grams of light triggers
2.0 grams of 2,6-d-tert-butyl-p-cresols (Kowloon, Nanjing Chemical Co., Ltd.)
Neozapon
?red 395(BASF AG) 0.01 gram
0.4 gram of hydroxyethyl methylacrylate
C
12-141.5 grams of-tertiary alkyl amine ethoxylates (RW-150, Union Carbide Corp)
1.59 grams of Tween-20 (the gas Chemical Co., Ltd. of Foshan section)
Above-mentioned each component is mixed after 3-5 minute with double screw extrusion machine at 80-130 ℃, die head curtain coating by extruder is on the thick PET support of the 0.125mm of above-mentioned precoating bond coating, cold wind is cooled to room temperature, obtains the photosensitive elastomer body layer that contains support.Photosensitive elastomer body thickness 1.572mm.
The diaphragm preparation of coating resistance oxygen adherent layer:
By 50 grams of polyvinyl alcohol (PVA) AIRVOL 203 (Air Products company); 10 grams of PVI (Panchim company); 180 grams of deionized waters; 0.5 gram of Le-202 (Guangzhou Li Er chemistry); mix, use anilox roll, be coated on the PET sheet base diaphragm of 0.125mm; dry 20min at 90 ℃, resistance oxygen adherent layer thickness 2 μ m.Obtain being coated with the diaphragm of oxidation prevention layer, stay to obtain next step use.
Then by the diaphragm that contains resistance oxygen adherent layer at 70 ℃, laminating on the above-mentioned photosensitive elastomer body layer that contains PET support, obtain washing flexible resin plates.
To under plate room temperature, place 3 days, in flexible platemaking apparatus KY1320(Guangzhou white clouds science and trade) upper back-exposure 20s, throws off diaphragm; enclose negative film, vacuumize, face exposure 12min; at the 5min of washing version from the beginning for the flat plate washing machine for flexographic plate of KMPXH900, dry 1.5 hours for 60 ℃.Going under sticky fluorescent tube of wavelength 280nm, spacing 5cm, goes sticky 10min, UV-A post-exposure 5 minutes, obtains plate, evaluates the performances such as site reduction.The plate washing of example 4 easily, 2%-95% reduction under the 122lpi of site, the independent point of 0.2mm and the clear reduction of 0.1mm independent lines, can meet the print request of 1.70mm plate.
comparative example 1
Be different from embodiment 1, does not add the present invention's's (sequence number 1) 5 grams of structural formulas.
The preparation of bond coating: 1400 grams of deionized waters, polyurethane TC-103(Guangdong Tian Yin Chemical Co., Ltd.) 700 grams, 14 grams of 10% KOH aqueous solution, surfactant FC-4430(3M company produces) 5 grams, under room temperature, stir 1 hour, obtain aqueous solution.
Support preparation: the thick PET of 0.125mm of 457 * 762mm specification.Speed by this aqueous solution with 5 ms/min is coated on the PET that thickness 0.125mm is thick, and 120 ℃ are dried 5 minutes, obtain the bond coating that coating thickness is 1.5 μ m.
Washing photosensitive elastomer body component:
12.5 grams of Kraton D1160 (KRATON company)
Styrene-methacrylic acid-polyethoxy methylacryoyloxyethyl isocyanates multipolymer
(mass ratio 60:7:33, n=34, acid number 51.7mgKOH/g resin, Lekai Hua Guang company) 25 grams
35 grams of DS-2 (JSR company)
2.84 grams of polyglycol (200) diacrylates (EM224, Changxing, Taiwan)
3.56 grams of polybutadiene dimethylacrylates
3.0 grams of 1,6-hexanediyl esters (the Tianjin proud son of heaven)
2.1 grams of dipentaerythritol five acrylate (the Tianjin proud son of heaven)
1.5 grams of HDDMAs (Xin Zhong village chemistry)
N-[3-dimethylamino-propyl] 3.0 grams of acrylamides
651 5.0 grams of light triggers
2.0 grams of 2,6-d-tert-butyl-p-cresols
Neozapon
?395 0.01 grams of Red
0.4 gram of hydroxyethyl methylacrylate
C
12-142.5 grams of-tertiary alkyl amine ethoxylates
1.59 grams of Tween-20 (the gas Chemical Co., Ltd. of Foshan section)
Above-mentioned each component is mixed after 3-5 minute with double screw extrusion machine at 80-130 ℃, die head curtain coating by extruder is on the thick PET support of the 0.125mm of above-mentioned precoating bond coating, cold wind is cooled to room temperature, obtains the photosensitive elastomer body layer that contains support.Photosensitive elastomer body thickness 1.572mm.
The diaphragm preparation of coating resistance oxygen adherent layer:
By 50 grams of polyvinyl alcohol (PVA) AIRVOL 203 (Air Products company); 10 grams of PVI (Panchim company); 180 grams of deionized waters; 0.5 gram of Le-202 (Guangzhou Li Er chemistry); mix, use anilox roll, be coated on the PET sheet base diaphragm of 0.125mm; dry 20min at 90 ℃, resistance oxygen adherent layer thickness 2 μ m.Obtain being coated with the diaphragm of oxidation prevention layer, stay to obtain next step use.
Then by the diaphragm that contains resistance oxygen adherent layer at 70 ℃, laminating on the above-mentioned photosensitive elastomer body layer that contains PET support, obtain the washing flexible resin plates of 1.70mm thickness.
To under plate room temperature, place 3 days, in flexible platemaking apparatus KY1320(Guangzhou white clouds science and trade) upper back-exposure 20s, throws off diaphragm; enclose negative film, vacuumize, face exposure 12min; at the 8min of washing version from the beginning for the flat plate washing machine for flexographic plate of KMPXH900, dry 1.5 hours for 60 ℃.Going under sticky fluorescent tube of wavelength 280nm, spacing 5cm, goes sticky 10min, UV-A post-exposure 5 minutes, obtains plate, evaluates the performances such as site reduction.2%-95% reduction under comparative example 1 site 122lpi, the independent point of 0.3mm and the clear reduction of 0.2mm independent lines.Comparative example 1 plate washing time is long, and independent point reduction is poor, can not meet the print request of 1.70mm plate.
comparative example 2
As different from Example 2, do not add multipolymer (the mass ratio 60:7:33 of styrene-methacrylic acid of the present invention-polyethoxy methylacryoyloxyethyl isocyanates, n=34, acid number 51.7mgKOH/g resin, Lekai Hua Guang company) 20 grams, TA906 addition increases to 52.5 grams.
The preparation of bond coating: 1400 grams of deionized waters, polyurethane TC-103(Guangdong Tian Yin Chemical Co., Ltd.) 700 grams, 14 grams of 10% KOH aqueous solution, surfactant FC-4430(3M company produces) 5 grams, under room temperature, stir 1 hour, obtain aqueous solution.
Support preparation: the thick PET of 0.125mm of 457 * 762mm specification.Speed by this aqueous solution with 3 ms/min is coated on the PET that thickness 0.125mm is thick, and 120 ℃ are dried 6 minutes, obtain the bond coating that coating thickness is 1.6 μ m.
Washing photosensitive elastomer body component:
15 grams of Kraton D1160 (KRATON company)
52.5 grams of TA906 (JSR company)
5 grams of the present invention's's (sequence number 2) structural formulas
2.84 grams of polyglycol (200) diacrylates (EM224, Changxing, Taiwan)
3.56 grams of polybutadiene dimethylacrylates
3.0 grams of 1,6-hexanediyl esters (the Tianjin proud son of heaven)
2.1 grams of dipentaerythritol five acrylate (the Tianjin proud son of heaven)
1.5 grams of HDDMAs (Xin Zhong village chemistry)
N-[3-dimethylamino-propyl] 3.0 grams of acrylamides
651 5.0 grams of light triggers
2.0 grams of 2,6-d-tert-butyl-p-cresols (Kowloon, Nanjing Chemical Co., Ltd.)
Neozapon
?red 395(BASF AG) 0.01 gram
0.4 gram of hydroxyethyl methylacrylate
C
12-142.5 grams of-tertiary alkyl amine ethoxylates (RW-150, Union Carbide Corp)
1.59 grams of Tween-20 (the gas Chemical Co., Ltd. of Foshan section)
Above-mentioned each component is mixed after 3-5 minute with double screw extrusion machine at 80-130 ℃, die head curtain coating by extruder is on the thick PET support of the 0.125mm of above-mentioned precoating bond coating, cold wind is cooled to room temperature, obtains the photosensitive elastomer body layer that contains support.Photosensitive elastomer body thickness 1.572mm.
The diaphragm preparation of coating resistance oxygen adherent layer:
By 50 grams of polyvinyl alcohol (PVA) AIRVOL 203 (Air Products company); 10 grams of PVI (Panchim company); 180 grams of deionized waters; 0.5 gram of Le-202 (Guangzhou Li Er chemistry); mix, use anilox roll, be coated on the PET sheet base diaphragm of 0.125mm; dry 20min at 90 ℃, resistance oxygen adherent layer thickness 2 μ m.Obtain being coated with the diaphragm of oxidation prevention layer, stay to obtain next step use.
Then by the diaphragm that contains resistance oxygen adherent layer at 70 ℃, laminating on the above-mentioned photosensitive elastomer body layer that contains PET support, obtain the washing flexible resin plates of 1.70mm thickness.
To under plate room temperature, place 3 days, in flexible platemaking apparatus KY1320(Guangzhou white clouds science and trade) upper back-exposure 20s, throws off diaphragm; enclose negative film, vacuumize, face exposure 12min; at the 8min of washing version from the beginning for the flat plate washing machine for flexographic plate of KMPXH900, dry 1.5 hours for 60 ℃.Going under sticky fluorescent tube of wavelength 280nm, spacing 5cm, goes sticky 10min, UV-A post-exposure 5 minutes, obtains plate, evaluates the performances such as site reduction.10%-95% reduction under comparative example 2 site 122lpi, the independent point of 0.3mm and the clear reduction of 0.2mm independent lines.Comparative example 2 plate washing times are long, and site, independent point are all reduced poor, can not meet the print request of 1.70mm plate.
comparative example 3
Difference from Example 3 is, neither adds the multipolymer of styrene-methacrylic acid of the present invention-polyethoxy methylacryoyloxyethyl isocyanates, also do not add the compound of the present invention's (sequence number 2).DS-2 is added into 57.5 grams.
The preparation of bond coating: 1400 grams of deionized waters, polyurethane TC-103(Guangdong Tian Yin Chemical Co., Ltd.) 700 grams, 14 grams of 10% KOH aqueous solution, surfactant FC-4430(3M company produces) 5 grams, under room temperature, stir 1 hour, obtain aqueous solution.
Support preparation: the thick PET of 0.175mm of 457 * 762mm specification.Speed by this aqueous solution with 5 ms/min is coated on the PET that thickness 0.175mm is thick, and 120 ℃ are dried 5 minutes, obtain the bond coating that coating thickness is 1.5 μ m.
Washing photosensitive elastomer body component:
15 grams of Kraton D1160 (KRATON company)
57.5 grams of DS-2 (JSR company)
2.84 grams of polyglycol (200) diacrylates (EM224, Changxing, Taiwan)
3.56 grams of polybutadiene dimethylacrylates
3.0 grams of 1,6-hexanediyl esters (the Tianjin proud son of heaven)
2.1 grams of dipentaerythritol five acrylate (the Tianjin proud son of heaven)
1.5 grams of HDDMAs (Xin Zhong village chemistry)
N-[3-dimethylamino-propyl] 3.0 grams of acrylamides
651 5.0 grams of light triggers
2.0 grams of 2,6-d-tert-butyl-p-cresols (Kowloon, Nanjing Chemical Co., Ltd.)
Neozapon
?red 395(BASF AG) 0.01 gram
0.4 gram of hydroxyethyl methylacrylate
C
12-144.0 grams of-tertiary alkyl amine ethoxylates (RW-150, Union Carbide Corp)
1.59 grams of Tween-20 (the gas Chemical Co., Ltd. of Foshan section)
Above-mentioned each component is mixed after 3-5 minute with double screw extrusion machine at 80-130 ℃, die head curtain coating by extruder is on the thick PET support of the 0.125mm of above-mentioned precoating bond coating, cold wind is cooled to room temperature, obtains the photosensitive elastomer body layer that contains support.Photosensitive elastomer body thickness 0.963 mm.
The diaphragm preparation of coating resistance oxygen adherent layer:
By 50 grams of polyvinyl alcohol (PVA) AIRVOL 203 (Air Products company); 10 grams of PVI (Panchim company); 180 grams of deionized waters; 0.5 gram of Le-202 (Guangzhou Li Er chemistry); mix, use anilox roll, be coated on the PET sheet base diaphragm of 0.125mm; dry 20min at 90 ℃, resistance oxygen adherent layer thickness 2 μ m.Obtain being coated with the diaphragm of oxidation prevention layer, stay to obtain next step use.
Then by the diaphragm that contains resistance oxygen adherent layer at 70 ℃, laminating on the above-mentioned photosensitive elastomer body layer that contains PET support, obtain the washing flexible resin plates of 1.14mm thickness.
To under plate room temperature, place 3 days; directly throw off diaphragm; enclose negative film; vacuumize in flexible platemaking apparatus KY1320(Guangzhou white clouds science and trade) on directly throw off diaphragm; enclose negative film, vacuumize, face exposure 12min; at the 15min of washing version from the beginning for the flat plate washing machine for flexographic plate of KMPXH900, dry 1.5 hours for 60 ℃.Going under sticky fluorescent tube of wavelength 280nm, spacing 5cm, goes sticky 10min, UV-A post-exposure 5 minutes, obtains plate, evaluates the performances such as site reduction.5%-90% reduction under comparative example 3 plate site 150lpi, the independent point of 0.20mm and the clear reduction of 0.3mm independent lines.The plate washing time of comparative example 3 is long, and site is original error also, and independent point and independent lines can not meet the requirement of 1.14mm flexographic printing.
Claims (9)
1. a washing flexible resin plates, comprises support, bond coating, photosensitive elastomer body layer, resistance oxygen adherent layer, protective film, it is characterized in that: the consisting of of described photosensitive elastomer body: thermoplastic elastic body A; Styrene-methacrylic acid-polyethoxy methylacryoyloxyethyl isocyanates multipolymer B; Butadiene-methyl methacrylate-methacrylic acid-divinyl benzene copolymer C; The active cross-linking monomer D of self-emulsifying; Polymerisable vinyl monomer and composition thereof E; Radical initiator and initiator system F thereof; Dyestuff and other adjuvant G.
2. washing flexible resin plates according to claim 1, is characterized in that: described thermoplastic elastic body A is polystyrene-poly isoprene-polystyrene ternary block polymer; Described thermoplastic elastic body A accounts for the 5-25% of photosensitive elastomer body total solid quality.
3. washing flexible resin plates according to claim 1 and preparation method thereof, is characterized in that: the multipolymer B chemical structural formula of styrene-methacrylic acid-polyethoxy methylacryoyloxyethyl isocyanates is as shown in (I):
（Ⅰ）
In said structure formula, St represents styrol structural unit; MAA represents methacrylic acid structural unit; MOI represents methylacryoyloxyethyl isocyanates structural unit; PEG represents polyethylene glycol structures unit; N is the integer of 50-1000; The multipolymer B of described styrene-methacrylic acid-polyethoxy methylacryoyloxyethyl isocyanates accounts for the 15-25% of photosensitive elastomer body total solid quality.
4. washing flexible resin plates according to claim 1, is characterized in that: the multipolymer C of described butadiene-methyl methacrylate-methacrylic acid-divinylbenzene accounts for the 15-35% of total solid quality.
5. washing flexible resin plates according to claim 1, is characterized in that: the active cross-linking monomer D of described self-emulsifying is more than one in material shown in chemical structural formula (II) or (III):
（Ⅱ）
In formula (II), R
1the side chain hydrogen carbon back that is aryl, contains aryl or the alkane substitute that contains aryl; R
2be-NH2, a kind of in Na, K, Li, BO is the alkoxy of the carbon atom of 1-5; AO is the alkoxy of the carbon atom of 2-4, and m is the integer of 0-100, and n is the integer of 1-2, and p is the integer of 0-100, and q is the integer of 0-10, X representative-CR
3=CH
2, R
3be hydrogen atom or-CH
3
（Ⅲ）
In formula (III), R
1hydrogen atom or methyl, R
2hydrogen atom or methyl, R
3oxygen atom or sulphur atom, R
4can be a kind of in methoxyl, ethoxy or propoxyl group, R
5be-NH2, a kind of in Na, K or Li, R
6be-OCO-, a kind of in-0-, methoxyl, ethoxy or propoxyl group, R
7be 1-19 carbon atom alkyl or
, or hydroxyl carboxyl in any one, m is the integer of 10-30, n is the integer of 1-40.
6. according to claim 1, claim 8, washing flexible resin plates claimed in claim 9, it is characterized in that: the active cross-linking monomer D of described self-emulsifying accounts for the 0.5-5% of photosensitive elastomer body total solid quality.
7. washing flexible resin plates according to claim 1, is characterized in that: polymerisable vinyl monomer and composition thereof E accounts for the 5-17% of photosensitive elastomer body total solid quality.
8. washing flexible resin plates according to claim 1, is characterized in that: radical initiator and initiator system F thereof account for the 1-5% of photosensitive elastomer body total solid quality.
9. one kind contains washing flexible resin plates described in any one and preparation method thereof in claim 1 ~ 13; comprise support, bond coating, photosensitive elastomer body layer, resistance oxygen adherent layer, protective film; it is characterized in that: photosensitive elastomer body layer material component by screw extruder metered charge, mixing, melt extrude to the supports such as the certain thickness iron version that contains bond coating, aluminium plate or PET sheet base; be covered with resistance oxygen adherent layer and protective film, make operable washing flexible resin plates.
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| CN103838079A (en) * | 2014-02-25 | 2014-06-04 | 东莞市梅居印刷材料有限公司 | Crude flexible printing plate and process for manufacturing mature plate by using same |
| CN104216229A (en) * | 2014-09-30 | 2014-12-17 | 乐凯华光印刷科技有限公司 | Flexible resin plate applied to printing LCD and preparation method thereof |
| CN106814540A (en) * | 2015-11-30 | 2017-06-09 | 乐凯华光印刷科技有限公司 | The preparation method of washing relief printing plate photosensitive composition, the washing relief printing plate containing the washing relief printing plate photosensitive composition and washing relief printing plate |
| CN109369470A (en) * | 2018-10-18 | 2019-02-22 | 南京林业大学 | A kind of allyl anion-nonionic emulsifier and preparation method thereof |
| CN111103763A (en) * | 2018-10-26 | 2020-05-05 | 乐凯华光印刷科技有限公司 | Photosensitive elastomer composition having excellent ink affinity and flexographic plate comprising the same |
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| CN103838079A (en) * | 2014-02-25 | 2014-06-04 | 东莞市梅居印刷材料有限公司 | Crude flexible printing plate and process for manufacturing mature plate by using same |
| CN104216229A (en) * | 2014-09-30 | 2014-12-17 | 乐凯华光印刷科技有限公司 | Flexible resin plate applied to printing LCD and preparation method thereof |
| CN104216229B (en) * | 2014-09-30 | 2019-12-13 | 乐凯华光印刷科技有限公司 | Flexible resin plate for LCD printing and preparation method thereof |
| CN106814540A (en) * | 2015-11-30 | 2017-06-09 | 乐凯华光印刷科技有限公司 | The preparation method of washing relief printing plate photosensitive composition, the washing relief printing plate containing the washing relief printing plate photosensitive composition and washing relief printing plate |
| CN106814540B (en) * | 2015-11-30 | 2020-04-10 | 乐凯华光印刷科技有限公司 | Photosensitive composition for washing relief printing plate, washing relief printing plate containing photosensitive composition for washing relief printing plate and preparation method of washing relief printing plate |
| CN109369470A (en) * | 2018-10-18 | 2019-02-22 | 南京林业大学 | A kind of allyl anion-nonionic emulsifier and preparation method thereof |
| CN111103763A (en) * | 2018-10-26 | 2020-05-05 | 乐凯华光印刷科技有限公司 | Photosensitive elastomer composition having excellent ink affinity and flexographic plate comprising the same |
| CN111103763B (en) * | 2018-10-26 | 2023-10-17 | 乐凯华光印刷科技有限公司 | Photoresist composition having excellent ink affinity and flexographic plate comprising the same |
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