CN101412861B - Aqueous ultraviolet cured paint - Google Patents
Aqueous ultraviolet cured paint Download PDFInfo
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- CN101412861B CN101412861B CN 200810227816 CN200810227816A CN101412861B CN 101412861 B CN101412861 B CN 101412861B CN 200810227816 CN200810227816 CN 200810227816 CN 200810227816 A CN200810227816 A CN 200810227816A CN 101412861 B CN101412861 B CN 101412861B
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- Prior art keywords
- methyl
- acrylate
- waterborne coatings
- percent
- curable waterborne
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- 239000003973 paint Substances 0.000 title abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims description 43
- -1 acrylic ester Chemical class 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- 230000001804 emulsifying effect Effects 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 125000000524 functional group Chemical group 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- OZCWUNHGNVXCCO-UHFFFAOYSA-N oxiran-2-ylmethyl hydrogen carbonate Chemical group OC(=O)OCC1CO1 OZCWUNHGNVXCCO-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 5
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- QXIQCNFSNJEMOD-UHFFFAOYSA-N 3-hydroxybutan-2-yl prop-2-enoate Chemical compound CC(O)C(C)OC(=O)C=C QXIQCNFSNJEMOD-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- QDHUQRBYCVAWEN-UHFFFAOYSA-N amino prop-2-enoate Chemical class NOC(=O)C=C QDHUQRBYCVAWEN-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 4
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 claims description 4
- TXCRQXPDLSLGSA-UHFFFAOYSA-N n-butyl-n-hydroxyprop-2-enamide Chemical compound CCCCN(O)C(=O)C=C TXCRQXPDLSLGSA-UHFFFAOYSA-N 0.000 claims description 4
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- NOVNFHQBYJQDJA-UHFFFAOYSA-N C1(=CC=CC=C1)CC(C)=O.OCCOCCO Chemical compound C1(=CC=CC=C1)CC(C)=O.OCCOCCO NOVNFHQBYJQDJA-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- SWTFBLUIBHXOAH-UHFFFAOYSA-N n-butylhydroxylamine Chemical compound CCCCNO SWTFBLUIBHXOAH-UHFFFAOYSA-N 0.000 claims description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 2
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 claims description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 claims 1
- 238000004945 emulsification Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000007888 film coating Substances 0.000 abstract 1
- 238000009501 film coating Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical group CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- LJRSZGKUUZPHEB-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxypropoxy)propoxy]propyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COC(C)COC(=O)C=C LJRSZGKUUZPHEB-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
Abstract
The invention relates to an aqueous ultraviolet light curing paint which consists of the following compositions in weight percentage: 25.0 to 60.0 percent of acrylate active oligomer, 1.0 to 10.0 percent of active oligomer with emulsification, 0 to 15.0 percent of latent solvent, 0.5 to 6.0 percent of light evocating agent, 0.1 to 2.0 percent of additive and 12.0 to 68.4 percent of water. The active oligomer with emulsification is an acrylate aqueous copolymer with 5,000 to 50,000 molecular weights; and at least two compounds containing olefinic unsaturated double bond and an evocating agent are used as initial materials, are subjected to copolymerization twice, are neutralized through a neutralizing agent to prepare the aqueous ultraviolet light curing paint. The active oligomer with emulsification in proper amount can emulsify a non-aqueous active oligomer, thereby realizing water solubility of the ultraviolet light curing paint; and the film coating performance of the aqueous ultraviolet light curing paint is basically equivalent to that of the non-aqueous ultraviolet light curing paint.
Description
Technical field
The present invention relates to a kind of UV-curable waterborne coatings.
Background technology
Ultraviolet-curing paint has environmental protection and energy conservation characteristic, therefore, has worldwide obtained paying attention to widely, and consumption has also obtained quick growth.But existing ultraviolet-curing paint is non-aqueous, and the combustion of coating, quick-fried grade are higher, and security is relatively poor between the usage period; In addition, need regulate the viscosity of living oligomer with reactive thinner, and these reactive thinners generally are acrylic ester compounds, it knows from experience generation certain pungency, supersensitivity to the people, also unfavorable to environment, its consumption is direct influence performances such as shrinking percentage, sticking power, flat appearance degree of filming not only, and before ultraviolet light polymerization, the wet film sagging phenomenon that produces because of reactive thinner is not volatile also can influence execution of coating.Straight line along with world oil chemical raw material price rises violently in recent years, and petroleum resources non-renewable makes that greatly developing water-borne coatings becomes trend of the times.But the film performance of UV-curable waterborne coatings still is difficult for reaching the level of non-aqueous ultraviolet-curing paint, has delayed coating Water-borne modification process.
Summary of the invention
The objective of the invention is: provide a kind of film performance the UV-curable waterborne coatings suitable, to promote the Water-borne modification of ultraviolet-curing paint with non-aqueous ultraviolet-curing paint.
The technical scheme that realizes the object of the invention is: a kind of UV-curable waterborne coatings, it is characterized in that, form by following component, the weight percentage of each component is as follows: esters of acrylic acid living oligomer 25.0～60.0%, the living oligomer 1.0～10.0% that emulsifying effect is arranged, solubility promoter 0～15.0%, light trigger 0.5～6.0%, auxiliary agent 0.1～2.0%, water 12.0～68.4%;
Described the living oligomer of emulsifying effect is arranged is that molecular weight is 5000～50000 acrylic ester aquosity multipolymer, and it is to contain the ethylenical unsaturated double bonds compound and initiator is a starting raw material with at least two kinds, through twice copolymerization, makes with the neutralizing agent neutralization again.
In the above-mentioned UV-curable waterborne coatings, the concrete preparation method of the described living oligomer that emulsifying effect arranged is as follows: having agitator, condenser, thermometer, add solvent in the reaction vessel of Dropping feeder, after being warmed up to backflow, dropping contains mixture and the insulation reaction that ethylenical unsaturated double bonds compound and initiator form by at least two kinds and finished a copolymerization at least in 6 hours, formation contains a polymkeric substance of the functional group that can further react, after residual free radical is removed in cooling, add (methyl) vinylformic acid again, (methyl) Propylene glycol monoacrylate, (methyl) Hydroxyethyl acrylate, n-methylolacrylamide, hydroxyl butyl acrylamide, in (methyl) vinylformic acid tertiary carbonic acid glycidyl ester one or more are warmed up to 80～90 ℃ together, make the functional group reactions that can further react that itself and polymkeric substance contain carry out the secondary copolymerization, continue insulation and cool to 40 ℃ after at least 4 hours, adding the neutralizing agent neutralization can make, and the functional group that can further react wherein is the Racemic glycidol ester group, carboxyl, the methylol amide base, hydroxyl butyl amide base or amide group.
In the above-mentioned UV-curable waterborne coatings, described at least two kinds to contain the ethylenical unsaturated double bonds compound be in (methyl) butyl acrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid tertiary carbonic acid glycidyl ester, vinylbenzene, vinyl acetate between to for plastic, (methyl) Propylene glycol monoacrylate, (methyl) Hydroxyethyl acrylate, (methyl) vinylformic acid, n-methylolacrylamide, hydroxyl butyl acrylamide, (methyl) acrylamide at least two kinds.
In the above-mentioned UV-curable waterborne coatings, described neutralizing agent is ammoniacal liquor, trolamine, diethanolamine, triethylamine, N, N-dimethyl benzylamine, sodium hydroxide or potassium hydroxide.
In the above-mentioned UV-curable waterborne coatings, described esters of acrylic acid living oligomer is the acrylate copolymer of epoxy acrylate, urethane acrylate, amino acrylates, band alkene double bond, in the polyester acrylate one or more, and they all are non-aqueous.
In the above-mentioned UV-curable waterborne coatings; described light trigger is 2-hydroxy-2-methyl-1-phenyl-acetone, α; α '-dimethyl benzil ketals, 1-hydroxy cyclohexyl phenylketone, 2-hydroxy-2-methyl-1-are to hydroxyethyl ether phenyl-acetone, 2-methyl isophthalic acid-(4-first sulfydryl phenyl)-2-morpholine-1-acetone, thioxanthone, 2; 4; 6-trimethylbenzoyl ethoxyl phenenyl phosphine oxide, benzophenone, two (2; 4,6-trimethylbenzoyl) one or more in the phenyl phosphine oxide.
In the above-mentioned UV-curable waterborne coatings, described solubility promoter is one or more in ethanol, Virahol, butanols, acetone, ethylene glycol ethyl ether, butyl glycol ether, propylene glycol monomethyl ether, propylene glycol butyl ether, propylene-glycol ethyl ether, dimethyl formamide, the tetrahydrofuran (THF).
In the above-mentioned UV-curable waterborne coatings, described auxiliary agent is one or more in dispersion agent, flow agent, defoamer, the sterilant.
Technique effect of the present invention is: UV-curable waterborne coatings of the present invention contains an amount of living oligomer that emulsifying effect is arranged, it is to contain the ethylenical unsaturated double bonds compound and initiator is a starting raw material with at least two kinds, through twice copolymerization, the molecular weight that makes with the neutralizing agent neutralization is 5000～50000 acrylic ester aquosity multipolymer again, there are unsaturated double-bond and hydrophilic radical on its polymer chain, just can make esters of acrylic acid living oligomer (nonaqueous) emulsification form emulsion by simple mixing, realized the Water-borne modification of ultraviolet-curing paint, and since each set of dispense of the UV-curable waterborne coatings of technical solution of the present invention than suitable, make the filming quite of performance that gained is filmed and non-aqueous ultraviolet-curing paint, overcome the aforementioned various drawbacks that viscosity that non-aqueous ultraviolet-curing paint must use reactive thinner to regulate living oligomer is brought, also saved the petrochemical complex starting material.
Embodiment
Below in conjunction with embodiment the present invention is further elaborated, but the present invention is not limited to raw materials used and coating formula among the embodiment.The raw material that embodiment and comparative example adopted is the commercially available industrial goods of coating if no special instructions.
(1) preparation has the living oligomer of emulsifying effect
Embodiment 1
Having agitator, condenser, thermometer, add 50g propylene glycol monomethyl ether solvent in the reaction vessel of Dropping feeder, after being warmed up to backflow, dropping is by 5g vinylformic acid, 6g vinylformic acid tertiary carbonic acid glycidyl ester, the 20g butyl acrylate, 10g vinylbenzene, 8.5g five kinds of mixture and insulation reaction that contain ethylenical unsaturated double bonds compound and 0.5g benzoyl peroxide initiator composition of methyl methacrylate were finished a copolymerization at least in 6 hours, formation contains a polymkeric substance of the functional group's (Racemic glycidol ester group) that can further react, after residual free radical is removed in cooling, add 5g vinylformic acid again and be warmed up to 80～90 ℃ together, make the glycidyl ester radical reaction of a vinylformic acid and a polymkeric substance carry out the secondary copolymerization, continue insulation and cool to 40 ℃ after 4 hours, adding 2.5g concentration is 17% ammoniacal liquor neutralization, make the living oligomer A-1 of emulsifying effect, its molecular weight is 15000～25000, discharging, preserve, standby.
Embodiment 2
Having agitator, condenser, thermometer, add 50g propylene glycol monomethyl ether solvent in the reaction vessel of Dropping feeder, after being warmed up to backflow, dropping is by 10g vinylformic acid, the 20g butyl acrylate, the 10g Isooctyl acrylate monomer, 8.5g four kinds of mixture and insulation reaction that contain ethylenical unsaturated double bonds compound and 0.5g benzoyl peroxide initiator composition of butyl methacrylate were finished a copolymerization at least in 6 hours, formation contains a polymkeric substance of the functional group's (carboxyl) that can further react, after residual free radical is removed in cooling, add 6g vinylformic acid tertiary carbonic acid glycidyl ester again and be warmed up to 80～90 ℃ together, make the part carboxyl reaction of a vinylformic acid tertiary carbonic acid glycidyl ester and a polymkeric substance carry out the secondary copolymerization, continue insulation and cool to 40 ℃ after 4 hours, adding 2.5g concentration is 17% ammoniacal liquor neutralization, make the living oligomer A-2 of emulsifying effect, its molecular weight is 5000～15000, discharging, preserve, standby.
Embodiment 3
Having agitator, condenser, thermometer, add 25g Virahol and two kinds of solvents of 25g butanols in the reaction vessel of Dropping feeder, after being warmed up to backflow, dropping is by 5g vinylformic acid, the 6g n-methylolacrylamide, the 20g butyl acrylate, 10g vinylbenzene, 8.5g five kinds of mixture and insulation reaction that contain ethylenical unsaturated double bonds compound and 0.5g benzoyl peroxide initiator composition of butyl methacrylate were finished a copolymerization at least in 6 hours, formation contains a polymkeric substance of the functional group's (methylol amide base) that can further react, after residual free radical is removed in cooling, add the 5g Propylene glycol monoacrylate again and be warmed up to 80～90 ℃ together, make the methylol amide radical reaction of a Propylene glycol monoacrylate and a polymkeric substance carry out the secondary copolymerization, continue insulation and cool to 40 ℃ after 4 hours, adding 2.5g concentration is 17% ammoniacal liquor neutralization, make the living oligomer A-3 of emulsifying effect, its molecular weight is 15000～25000, discharging, preserve, standby.
(2) preparation UV-curable waterborne coatings of the present invention
Embodiment 4～6
1, formulation for coating material sees Table 1, and each amounts of components of coating is the percentage ratio meter by weight.
Table 1
| Component | Material name | Consumption embodiment 4 | Consumption embodiment 5 | Consumption embodiment 6 |
| The esters of acrylic acid living oligomer | CN-120 (epoxy acrylate), CN-965 (urethane acrylate) amino acrylates | 40// | /40/ | //40 |
| The living oligomer that emulsifying effect is arranged | A-1 (embodiment 1 system) A-2 (embodiment 2 systems) A-3 (embodiment 3 systems) | 7// | /7/ | //7 |
| Solubility promoter | The Virahol propylene glycol monomethyl ether | 10/ | /10 | // |
| Light trigger | Runtecure11732,4,6-trimethylbenzoyl ethoxyl phenenyl phosphine oxide | 2/ | 11 | 2/ |
| Auxiliary agent flow agent defoamer | BYK331BYK052 | 0.80.2 | 0.80.2 | 0.80.2 |
| Water | Deionized water | 40 | 40 | 50 |
2, preparation method for coating
Press formula ratio in the table 1, the raw material of esters of acrylic acid living oligomer, the living oligomer that emulsifying effect is arranged, solubility promoter and light trigger is put into container to stir, the water that under the vigorous stirring state, progressively adds formula ratio then, after the basic emulsification of mixed solution, after stirring, the auxiliary agent of adding formula ratio promptly makes UV-curable waterborne coatings B-1 of the present invention, B-2 and the B-3 of embodiment 4～6 respectively.
Coating B-1, B-2 and B-3 are behind the intact moisture of 60 ℃ of flash distillations, and with the irradiation of 1kw medium pressure mercury lamp, coating B-1 and B-3 reach 180mj/cm at irradiation dose
2The time can completely solidified, coating B-2 reaches 240mj/cm at irradiation dose
2The time can completely solidified.
(3) preparation comparative example coating
Carry out film performance relatively for ease of coating with embodiment 4～6, identical esters of acrylic acid living oligomer, initiator and auxiliary agent and the identical proportioning of special employing formed non-aqueous ultraviolet-curing paint, concrete prescription sees Table 2, and each amounts of components of coating is the percentage ratio meter by weight;
The concrete preparation method of coating puts into container with the raw material of each component of table 2 formula ratio to stir, and promptly makes comparative example 1～3 non-aqueous ultraviolet-curing paint;
With the irradiation of 1kw medium pressure mercury lamp, the coating of comparative example 1 reaches 360mj/cm at irradiation dose
2Can completely solidified, the coating of comparative example 2 reaches 560mj/cm at irradiation dose
2Can completely solidified, the coating of comparative example 3 reaches 180mj/cm at irradiation dose
2Can completely solidified.
Table 2
| Component | Material name | Consumption comparative example 1 | Consumption comparative example 2 | Consumption comparative example 3 |
| The esters of acrylic acid living oligomer | CN-120 (epoxy acrylate) CN-965 (urethane acrylate) amino acrylates | 40// | /40/ | //97 |
| Reactive thinner | Viscoat 295 tri (propylene glycol) diacrylate ethoxy ethoxy acrylate | 1738/ | /2035 | /// |
| Light trigger | Runtecure11732,4,6-trimethylbenzoyl ethoxyl phenenyl phosphine oxide | 4/ | 22 | 2/ |
| Auxiliary agent flow agent defoamer | BYK331BYK052 | 0.80.2 | 0.80.2 | 0.80.2 |
In embodiment and comparative example:
CN-120 and CN-965 are the trade(brand)name of SARTOMER company product;
Runtecure1173 is 2-hydroxy-2-methyl-1-phenyl-acetone, is the trade(brand)name of Changzhou Huatai Chemistry Co., Ltd.'s product;
BYK331 and BYK052 are the trade(brand)name of German BYK company product.
(4) detect film performance
By the concerned countries standard detection of existing coating industry, detecting used model is tinplate; Detected result sees Table 3.
Table 3
| Test event | Embodiment 4 | Comparative example 1 | Embodiment 5 | Comparative example 2 | Embodiment 6 | Comparative example 3 |
| Outward appearance | Smooth smooth | Smooth smooth | Smooth smooth | Smooth smooth | Smooth smooth | Smooth smooth |
| Gloss | 96 | 98 | 92 | 95 | 97 | 94 |
| Sticking power | 2 grades | 3 grades | 1 grade | 3 grades | 4 grades | 4 grades |
| Hardness | 3H | 3H | B | HB | 2H | 2H |
| Snappiness | 5mm | 10mm | 1mm | 2mm | 10mm | 10mm |
| Resistance to boiling water | 1 hour | 1 hour | 2 hours | 2 hours | 4 hours | 4 hours |
| Anti-3%NaOH | No change | No change | No change | No change | No change | No change |
| Anti-5% sulfuric acid | No change | No change | No change | No change | No change | No change |
| Water tolerance | January | January | January | January | 15 days | 15 days |
In table 3, resistance to boiling water is meant the obviously broken ring required time of filming in boiling water; Anti-3%NaOH and anti-5% sulfuric acid are meant that model soaks 48 hours situations of filming; Water tolerance is meant that test begins to the obvious foaming required time of filming.
The detected result of table 3 proves that the every performance of UV-curable waterborne coatings of the present invention is suitable substantially with corresponding non-aqueous ultraviolet-curing paint performance, and gloss is lower slightly and sticking power increases, and has actual application value; In addition, can also prove that the present invention who allocates appropriate amount in existing non-aqueous ultraviolet-curing paint into has the living oligomer of emulsifying effect just can make the basic UV-curable waterborne coatings suitable with non-aqueous ultraviolet-curing paint of film performance, very favourable to the Water-borne modification of ultraviolet-curing paint.
Claims (6)
1. UV-curable waterborne coatings, it is characterized in that, form by following component, the weight percentage of each component is as follows: esters of acrylic acid living oligomer 25.0～60.0%, the living oligomer 1.0～10.0% that emulsifying effect is arranged, solubility promoter 0～15.0%, light trigger 0.5～6.0%, auxiliary agent 0.1～2.0%, water 12.0～68.4%;
Described the living oligomer of emulsifying effect is arranged is that molecular weight is 5000～50000 acrylic ester aquosity multipolymer, and it is to contain the ethylenical unsaturated double bonds compound and initiator is a starting raw material with at least two kinds, through twice copolymerization, makes with the neutralizing agent neutralization again;
Described neutralizing agent is ammoniacal liquor, trolamine, diethanolamine, triethylamine, N, N-dimethyl benzylamine, sodium hydroxide or potassium hydroxide;
Described light trigger is 2-hydroxy-2-methyl-1-phenyl-acetone, α, α '-dimethyl benzil ketals, 1-hydroxy cyclohexyl phenylketone, 2-hydroxy-2-methyl-1-are to hydroxyethyl ether phenyl-acetone, 2-methyl isophthalic acid-(4-first sulfydryl phenyl)-2-morpholine-1-acetone, thioxanthone, 2,4,6-trimethylbenzoyl ethoxyl phenenyl phosphine oxide, benzophenone, two (2,4,6-trimethylbenzoyl) one or more in the phenyl phosphine oxide;
The concrete preparation method of the described living oligomer that emulsifying effect arranged is as follows: having agitator, condenser, thermometer, add solvent in the reaction vessel of Dropping feeder, after being warmed up to backflow, dropping contains mixture and the insulation reaction that ethylenical unsaturated double bonds compound and initiator form by at least two kinds and finished a copolymerization at least in 6 hours, formation contains a polymkeric substance of the functional group that can further react, after residual free radical is removed in cooling, add (methyl) vinylformic acid again, (methyl) Propylene glycol monoacrylate, (methyl) Hydroxyethyl acrylate, n-methylolacrylamide, hydroxyl butyl acrylamide, in (methyl) vinylformic acid tertiary carbonic acid glycidyl ester one or more are warmed up to 80～90 ℃ together, make the functional group reactions that can further react that itself and polymkeric substance contain carry out the secondary copolymerization, continue insulation and cool to 40 ℃ after at least 4 hours, adding the neutralizing agent neutralization can make.
2. UV-curable waterborne coatings according to claim 1 and 2, it is characterized in that described at least two kinds to contain the ethylenical unsaturated double bonds compound be in (methyl) butyl acrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid tertiary carbonic acid glycidyl ester, vinylbenzene, vinyl acetate between to for plastic, (methyl) Propylene glycol monoacrylate, (methyl) Hydroxyethyl acrylate, (methyl) vinylformic acid, n-methylolacrylamide, hydroxyl butyl acrylamide, (methyl) acrylamide at least two kinds.
3. UV-curable waterborne coatings according to claim 2, it is characterized in that, described formation contains a polymkeric substance of the functional group that can further react, and the functional group that can further react wherein is Racemic glycidol ester group, carboxyl, methylol amide base, hydroxyl butyl amide base or amide group.
4. UV-curable waterborne coatings according to claim 1, it is characterized in that, described esters of acrylic acid living oligomer is the acrylate copolymer of epoxy acrylate, urethane acrylate, amino acrylates, band alkene double bond, in the polyester acrylate one or more, and they all are non-aqueous.
5. UV-curable waterborne coatings according to claim 1, it is characterized in that described solubility promoter is one or more in ethanol, Virahol, butanols, acetone, ethylene glycol ethyl ether, butyl glycol ether, propylene glycol monomethyl ether, propylene glycol butyl ether, propylene-glycol ethyl ether, dimethyl formamide, the tetrahydrofuran (THF).
6. UV-curable waterborne coatings according to claim 1 is characterized in that, described auxiliary agent is one or more in dispersion agent, flow agent, defoamer, the sterilant.
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| CN 200810227816 CN101412861B (en) | 2008-12-01 | 2008-12-01 | Aqueous ultraviolet cured paint |
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| CN101921374B (en) * | 2009-06-12 | 2012-01-25 | 成都市新津托展油墨有限公司 | Preparation method of polyacrylate-polyurethane resin binder for single-fluid general plastic gravure alcohol-soluble and water-soluble composite ink |
| CN102146228B (en) * | 2011-01-18 | 2012-11-21 | 深圳市嘉卓成科技发展有限公司 | UV (Ultra Voilet) radiation curing coating matched with waterborne primer and production and using methods thereof |
| CN102277038A (en) * | 2011-06-09 | 2011-12-14 | 深圳市科彩印务有限公司 | Aqueous ultraviolet-cured gravure gloss oil |
| CN103497669B (en) * | 2013-09-23 | 2015-02-25 | 迪爱生合成树脂（中山）有限公司 | Activated energy ray curing waterborne resin composition |
| CN103756533A (en) * | 2013-12-30 | 2014-04-30 | 苏州市邦成电子科技有限公司 | Ultraviolet light polymerization water-based paint universal for metal and non-metal and preparation method thereof |
| CN104804498A (en) * | 2015-05-22 | 2015-07-29 | 展辰涂料集团股份有限公司 | Aqueous UV (ultraviolet) paint for plastic |
| CN108359031B (en) * | 2018-03-23 | 2021-04-13 | 北京乾瑞科技有限公司 | Water-based light-cured resin and application thereof |
| CN110903742A (en) * | 2018-09-18 | 2020-03-24 | 上海弘业涂料科技发展有限公司 | Water-based ultraviolet curing coating |
| CN111154386A (en) * | 2020-01-16 | 2020-05-15 | 上海立邦长润发涂料有限公司 | Brushing LED transparent primer, preparation method and application |
| CN112143320B (en) * | 2020-09-25 | 2021-09-03 | 扬州工业职业技术学院 | Ultraviolet-curing acrylic resin water-based paint and preparation method thereof |
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