CN102533184B - Water-based pressure-sensitive adhesive of polyethylene protective film and preparation method thereof - Google Patents
Water-based pressure-sensitive adhesive of polyethylene protective film and preparation method thereof Download PDFInfo
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- CN102533184B CN102533184B CN201110422225.2A CN201110422225A CN102533184B CN 102533184 B CN102533184 B CN 102533184B CN 201110422225 A CN201110422225 A CN 201110422225A CN 102533184 B CN102533184 B CN 102533184B
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- sensitive adhesive
- water
- protective film
- pressure sensitive
- based pressure
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 106
- -1 polyethylene Polymers 0.000 title claims abstract description 65
- 230000001681 protective effect Effects 0.000 title claims abstract description 50
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 49
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000839 emulsion Substances 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 22
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 12
- 239000005056 polyisocyanate Substances 0.000 claims description 11
- 229920001228 polyisocyanate Polymers 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 239000004970 Chain extender Substances 0.000 claims description 9
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 5
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 3
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 3
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- QNNXAEJINMDKOM-UHFFFAOYSA-N CN(C)C.O=C=NCCCCCCN=C=O Chemical compound CN(C)C.O=C=NCCCCCCN=C=O QNNXAEJINMDKOM-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000004814 polyurethane Substances 0.000 abstract description 2
- 229920002635 polyurethane Polymers 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 37
- 239000000758 substrate Substances 0.000 description 25
- 239000012528 membrane Substances 0.000 description 18
- 229910001220 stainless steel Inorganic materials 0.000 description 15
- 239000010935 stainless steel Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 238000003851 corona treatment Methods 0.000 description 12
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000863032 Trieres Species 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Abstract
The invention discloses water-based pressure-sensitive adhesive of a polyethylene protective film and a preparation method thereof. The water-based pressure-sensitive adhesive comprises the following components by weight percentage: 95.0-99.9 percent of PUA (polyurethane/acrylate) emulsion ad 0.1-5.0 percent of curing agent. No environmental pollution can be caused by the water-based pressure-sensitive adhesive, the water-based pressure-sensitive adhesive has good adhesion to a polyethylene film, and the initial adhesion, stripping strength and cohesion can be well balanced.
Description
Technical field
The present invention relates to a kind of water-borne pressure sensitive adhesive and preparation method thereof, more particularly, the present invention relates to a kind of Water-based pressure-sensitive adhesive of polyethylene protective film and preparation method thereof.
Background technology
Protective membrane is a kind of surface protection for the protection of commodity surface, wrapping material; be attached to the surface of the commodity such as each metalloid, aluminium-plastic panel, plastic plate, coated steel, stainless steel plate, aluminium section bar, stone material, glass, instrument, furniture; make it in manufacture, transportation, secondary processing, storage and use procedure, protect surface, avoid commodity to be subject to polluting, to scratch and slow down the oxidation on commodity surface.The application of protective membrane, not only can improve product visual appearance, facilitate materials processing, simultaneously also can improve the utilization ratio of material, reduce production costs.
Protective membrane is comprised of substrate layer and pressure-sensitive adhesive layer, generally with coating method, carries out suitability for industrialized production, and on the membranaceous base material having made, the pressure-sensitive adhesive of coating emulsion state or solution state, then adds heat extraction solvent or dispersion agent, batches and obtains protective membrane.Protective membrane is generally usingd polyethylene (PE) film as base material, and the pressure sensitive adhesive of coating is generally solvent-based polyacrylate pressure sensitive adhesives, therefore has in process of production a large amount of volatile organic compounds (VOC) to discharge.These volatile organic compoundss not only can cause more serious environmental pollution, and also can cause larger harm to the healthy of user.For this reason, reducing volatile organic compounds is the significant problem that China's surface protection product industry will solve.
Water-borne pressure sensitive adhesive be take water as solvent, with solvent pressure-sensitive adhesive comparison, does not produce volatile organic solvent, and VOC (volatile organic compounds) is almost nil, has the advantages such as cost is low, use is safe, pollution-free, is ideal " green " pressure sensitive adhesive.
Summary of the invention
The object of the present invention is to provide a kind of Water-based pressure-sensitive adhesive of polyethylene protective film.This water-borne pressure sensitive adhesive environmentally safe, has good sticking power to polyethylene film, can realize the well balanced of initial bonding strength, stripping strength and force of cohesion.
Another object of the present invention is to provide the preparation method of described water-borne pressure sensitive adhesive.
The object of the invention is to be achieved through the following technical solutions:
A Water-based pressure-sensitive adhesive of polyethylene protective film, comprises following component by weight percentage:
PUA emulsion 95.0～99.9%;
Solidifying agent 0.1～5.0%.
Preferably, described Water-based pressure-sensitive adhesive of polyethylene protective film, comprises following component by weight percentage:
PUA emulsion 96.0～99.5%;
Solidifying agent 0.5～4.0%.
More preferably, described Water-based pressure-sensitive adhesive of polyethylene protective film, comprises following component by weight percentage:
PUA emulsion 97～99%;
Solidifying agent 1～3%;
Described solidifying agent is waterborne curing agent, is selected from three isocyanic acid triphenyl thiophosphatephosphorothioates, poly methylene poly phenyl poly isocyanate, 4, the mixture of one or more in 4-dimethylmethane-vulcabond.
Described PUA emulsion is the main component of pressure sensitive adhesive, if its consumption very little, pressure sensitive adhesive to hold viscous force too poor, be applied to the easy cull of polyethylene protective film; If its consumption is too large, the initial bonding strength of pressure sensitive adhesive is poor.In the present invention, described PUA emulsion is composed of the following components by weight percentage:
Polyvalent alcohol 14.5～30.0%;
Polyisocyanates 9.2～20.0%;
Catalyzer 0.1～0.5%;
Chainextender 0.1～1.5%;
Functional monomer 1～10%;
Soft monomer 15～40%;
Hard monomer 3～15%;
Initiator 0.1～0.8%.
Neutralizing agent 0.3～1.5%;
Distilled water surplus.
Preferably, described PUA emulsion is composed of the following components by weight percentage:
Polyvalent alcohol 18～28%;
Polyisocyanates 15～20%;
Catalyzer 0.1～0.5%;
Chainextender 0.5～1.5%;
Functional monomer 5～7%;
Soft monomer 30～35%;
Hard monomer 5～15%;
Initiator 0.1～0.6%;
Neutralizing agent 0.3～1.0%;
Distilled water surplus.
In PUA emulsion of the present invention, described polyvalent alcohol is selected from one or more the mixture in polyoxypropyleneglycol, polyoxytrimethylene triol, polytetrahydrofuran diol, polyester glycol, polyoxyethylene glycol, polycarbonate diol and polycaprolactone glycol, is preferably the mixture of polyoxypropyleneglycol and polyoxytrimethylene triol polyvalent alcohol.
In PUA emulsion of the present invention, described polyisocyanates is selected from one or two or more kinds the mixture in diphenylmethanediisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl-secondary methylbenzene vulcabond, trimethylammonium hexamethylene-diisocyanate, xylylene diisocyanate, is preferably the mixture of diphenylmethanediisocyanate and tolylene diisocyanate.
In PUA emulsion of the present invention, described catalyzer is selected from di-n-butyltin dilaurate, stannous octoate, triethylene diamine, triethylamine, N, the mixture of one or two or more kinds in N-dimethylethanolamine, N methyldiethanol amine, is wherein preferably the mixture of di-n-butyltin dilaurate, triethylene diamine and stannous octoate.
In PUA emulsion of the present invention, described chainextender is wetting ability chainextender, be selected from 1,4-butyleneglycol, 1, the mixture of one or two or more kinds in 6-hexylene glycol, neopentyl glycol, glycerol, TriMethylolPropane(TMP), triglycol, quadrol, dimethylol propionic acid, is wherein preferably the mixture of quadrol and dimethylol propionic acid.
Functional monomer is the acrylate soft monomer that contains hydroxyl, can effectively improve the cross-linking density of acrylate and urethane, the active group carrying can further be cross-linked, and can improve integrity and the force of cohesion of pressure sensitive adhesive, thereby further improves the over-all properties of product.In PUA emulsion of the present invention, described functional monomer is selected from one or two or more kinds the mixture in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, N hydroxymethyl acrylamide, is wherein preferably the mixture of Hydroxyethyl acrylate and N hydroxymethyl acrylamide.
Soft monomer forms the soft chain segment of polymkeric substance, and for pressure sensitive adhesive provides suitable wettability and tack, if its consumption very little, the wettability of pressure sensitive adhesive and initial bonding strength are too poor; If its consumption is too large, pressure sensitive adhesive to hold viscous force too poor.In PUA emulsion of the present invention, described soft monomer is selected from one or more the mixture in ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, Isooctyl methacrylate, lauryl acrylate and octadecyl acrylate, is wherein preferably the mixture of ethyl propenoate, butyl acrylate and Isooctyl acrylate monomer.
Hard monomer forms the hard segment of polymkeric substance, for pressure sensitive adhesive provides good force of cohesion and suitable stripping strength, if its consumption is very little, pressure sensitive adhesive to hold viscous force too poor; If its consumption is too large, the wettability of pressure sensitive adhesive and initial bonding strength are too poor.In PUA emulsion of the present invention, described hard monomer is selected from one or more the mixture in methyl acrylate, methyl methacrylate, butyl methacrylate, vinylbenzene and vinyl cyanide, is wherein preferably the mixture of methyl acrylate and methyl methacrylate.
In PUA emulsion of the present invention, described initiator is benzoyl peroxide or Diisopropyl azodicarboxylate.
In PUA emulsion of the present invention, described neutralizing agent is N, N-diethyl ethamine.
The preparation method of Water-based pressure-sensitive adhesive of polyethylene protective film of the present invention, comprises the following steps:
1) synthetic PUA emulsion: by after polyvalent alcohol underpressure distillation dehydration, add polyisocyanates, catalyst reaction, after adding wetting ability chainextender insulation reaction, add functional monomer, fully after reaction, be cooled to 45-50 ℃, add neutralizing agent, soft monomer, hard monomer, chainextender, distilled water, stir, add initiator fully to react, make after cooling;
2) PUA emulsion, waterborne curing agent are at room temperature stirred, make pressure sensitive adhesive glue.
Water-borne pressure sensitive adhesive of the present invention has good sticking power to polyethylene film, can realize the well balanced of initial bonding strength, stripping strength and force of cohesion; Because its viscosity is larger, be applicable to blade coating and produce polyethylene protective film, advantages such as thering is environmental friendliness, solidify fast and consume energy and be low.The key technical indexes that Water-based pressure-sensitive adhesive of polyethylene protective film of the present invention reaches is as follows: tack: >=No. 10 balls; 180 ° of stripping strengths: > 100N/m; Hold viscosity (25 ℃): > 96h does not come off.To adopt polyethylene protective film prepared by water-borne pressure sensitive adhesive of the present invention to be attached to stainless steel plate surface, under room temperature, place while tearing this protective membrane off after 6 months, without pressure sensitive adhesive, remain in stainless steel plate surface.
Compared with prior art, the present invention, by synthetic PUA emulsion, because it has the advantage of vinylformic acid and urethane concurrently, and contains crosslinkable active function groups, therefore can give the good viscosity of pressure sensitive adhesive, weathering resistance, water tolerance, and the performance of excellent high-temp resisting high-humidity resisting.
Embodiment
Embodiment mono-:
1, synthetic PUA emulsion
By 100g polyoxypropyleneglycol, after 50g polyoxytrimethylene triol underpressure distillation dehydration, add 100g diphenylmethanediisocyanate, 0.5g stannous octoate, 0.5g di-n-butyltin dilaurate, at 80-85 ℃, react 2 hours, add 0.5g quadrol, insulation reaction adds 100g Hydroxyethyl acrylate after 1 hour, react 1 hour, be cooled to 45-50 ℃, add 3gN, N-diethyl ethamine, 0.5g dimethylol propionic acid, 80g butyl acrylate, 70g ethyl propenoate, 30g methyl acrylate, 20g methyl methacrylate, 437g distilled water, stir 0.5-1 hour, add 8g Diisopropyl azodicarboxylate, at 80 ℃, react 3 hours, cooled and filtered makes PUA emulsion (polyurethane/acrylic ester composite emulsion).
2, prepare water-borne pressure sensitive adhesive
95gPUA emulsion, 5g poly methylene poly phenyl poly isocyanate are at room temperature stirred, make water-borne pressure sensitive adhesive of the present invention.
3, basic mechanical design feature index determining
Prepared water-borne pressure sensitive adhesive is evenly coated on the polyethylene film through corona treatment, and spread is about 15g/m
2, then at 80 ℃, dry 3 minutes, according to following testing method, test every technical performance index of pressure sensitive adhesive:
Tack: stop method (DOW method) according to the spin slope of GB 4852-1984, test with Pressuresensitive Tape initial cohesiveness tester;
180 ° of stripping strengths: according to GB/T 2792-1998, test with desktop tension testing machine;
Hold viscosity: according to GB/T 4851-1988, with adhesive tape retention trier, test.
The test result of properties technical indicator is as follows:
Tack: No. 11 balls;
180 ° of stripping strength: 115N/m;
Hold viscosity: > 96h.
The polyethylene protective film that adopts the prepared water-borne pressure sensitive adhesive of the present embodiment to prepare is attached to stainless steel plate substrate surface, under room temperature, places while tearing this protective membrane off after 6 months, without pressure sensitive adhesive, remain in substrate surface.
And the water-borne pressure sensitive adhesive that ordinary method makes is evenly coated on the polyethylene film through corona treatment, spread is about 15g/m
2, then at 80 ℃, dry 3 minutes, according to above testing method, test every technical performance index of pressure sensitive adhesive:
No. 10 balls of tack: <;
180 ° of stripping strengths: < 100N/m;
Hold viscosity: < 96h
Polyethylene protective film prepared by the water-borne pressure sensitive adhesive that ordinary method makes is attached to stainless steel plate substrate surface, places while tearing this protective membrane off after 6 months under room temperature, and pressure sensitive adhesive remains in substrate surface in a large number.
Embodiment bis-:
1, synthetic PUA emulsion
By after 145g polyoxytrimethylene triol underpressure distillation dehydration, add 55g diphenylmethanediisocyanate, 37g tolylene diisocyanate, 1.5g triethylene diamine, 1g di-n-butyltin dilaurate, at 80-85 ℃, react 2 hours, add 0.5g dimethylol propionic acid, insulation reaction added 35g Hydroxyethyl acrylate after approximately 1 hour, react approximately 1 hour, be cooled to 45-50 ℃, add 15gN, N-diethyl ethamine, 0.5g dimethylol propionic acid, 320g butyl acrylate, 80g Isooctyl acrylate monomer, 75g methyl acrylate, 75g methyl methacrylate, 158g distilled water, stir 0.5-1 hour, add 1.5g Diisopropyl azodicarboxylate, at 80 ℃, react approximately 3 hours, cooled and filtered makes PUA emulsion.
2, prepare water-borne pressure sensitive adhesive
By 98gPUA emulsion, 1g poly methylene poly phenyl poly isocyanate, 1g4,4-dimethylmethane-vulcabond at room temperature stirs, and makes water-borne pressure sensitive adhesive of the present invention.
3, basic mechanical design feature index determining
Prepared water-borne pressure sensitive adhesive is evenly coated on the polyethylene film through corona treatment, and spread is about 15g/m
2, then at 80 ℃, dry 3 minutes, according to the properties technical indicator of the testing method test pressure sensitive adhesive described in embodiment mono-.Test result is as follows:
Tack: No. 12 balls;
180 ° of stripping strength: 133N/m;
Hold viscosity: > 96h.
The polyethylene protective film that adopts the prepared water-borne pressure sensitive adhesive of the present embodiment to prepare is attached to stainless steel plate substrate surface, under room temperature, places while tearing this protective membrane off after 6 months, without pressure sensitive adhesive, remain in substrate surface.
And the water-borne pressure sensitive adhesive that ordinary method makes is evenly coated on the polyethylene film through corona treatment, spread is about 15g/m
2, then at 80 ℃, dry 3 minutes, according to the testing method described in embodiment mono-, test every technical performance index of pressure sensitive adhesive:
No. 10 balls of tack: <;
180 ° of stripping strengths: < 100N/m;
Hold viscosity: < 96h
Polyethylene protective film prepared by the water-borne pressure sensitive adhesive that ordinary method makes is attached to stainless steel plate substrate surface, places while tearing this protective membrane off after 6 months under room temperature, and pressure sensitive adhesive remains in substrate surface in a large number.
Embodiment tri-:
1, synthetic PUA emulsion
By after 300g polyoxytrimethylene triol underpressure distillation dehydration, add 200g tolylene diisocyanate, 2g stannous octoate, 3g di-n-butyltin dilaurate, at 80-85 ℃, react 2 hours, add 5g quadrol, insulation reaction added 5g Hydroxyethyl acrylate after approximately 1 hour, 5gN-n-methylolacrylamide, react approximately 1 hour, be cooled to 45-50 ℃, add 4gN, N-diethyl ethamine, 10g dimethylol propionic acid, 120g butyl acrylate, 130g Isooctyl acrylate monomer, 30g methyl acrylate, 185g distilled water, stir 0.5-1 hour, add 1g Diisopropyl azodicarboxylate, at 80 ℃, react approximately 3 hours, cooled and filtered makes PUA emulsion.
2, prepare water-borne pressure sensitive adhesive
By 99.9gPUA emulsion, 0.1g4,4-dimethylmethane-vulcabond at room temperature stirs, and makes water-borne pressure sensitive adhesive of the present invention.
3, basic mechanical design feature index determining
Prepared water-borne pressure sensitive adhesive is evenly coated on the polyethylene film through corona treatment, and spread is about 15g/m
2, then at 80 ℃, dry 3 minutes, according to the properties technical indicator of the testing method test pressure sensitive adhesive described in embodiment mono-.Test result is as follows:
Tack: No. 12 balls;
180 ° of stripping strength: 140N/m;
Hold viscosity: > 96h.
The polyethylene protective film that adopts the prepared water-borne pressure sensitive adhesive of the present embodiment to prepare is attached to stainless steel plate substrate surface, under room temperature, places while tearing this protective membrane off after 6 months, without pressure sensitive adhesive, remain in substrate surface.
And the water-borne pressure sensitive adhesive that ordinary method makes is evenly coated on the polyethylene film through corona treatment, spread is about 15g/m
2, then at 80 ℃, dry 3 minutes, according to every technical performance index of the testing method test pressure sensitive adhesive described in embodiment mono-.Test result is as follows:
No. 10 balls of tack: <;
180 ° of stripping strengths: < 100N/m;
Hold viscosity: < 96h
Polyethylene protective film prepared by the water-borne pressure sensitive adhesive that routine makes is attached to stainless steel plate substrate surface, places while tearing this protective membrane off after 6 months under room temperature, and pressure sensitive adhesive remains in substrate surface in a large number.
Embodiment tetra-:
1, synthetic PUA emulsion
By 120g polyoxypropyleneglycol, after 80g polyoxytrimethylene triol underpressure distillation dehydration, add 150g diphenylmethanediisocyanate, 1g stannous octoate, 1g di-n-butyltin dilaurate, at 80-85 ℃, react approximately 2 hours, add 0.3g quadrol, 0.2g dimethylol propionic acid, insulation reaction added 20g Propylene glycol monoacrylate after approximately 1 hour, react 1 hour, be cooled to 45-50 ℃, add 5gN, N-diethyl ethamine, 1.5g dimethylol propionic acid, 80g butyl acrylate, 120g Isooctyl acrylate monomer, 40g methyl methacrylate, 379.7g distilled water, stir 0.5-1 hour, add 1.3g Diisopropyl azodicarboxylate, at 80 ℃, react approximately 3 hours, cooled and filtered makes PUA emulsion.
2, prepare water-borne pressure sensitive adhesive
By 96gPUA emulsion, 4g4,4-dimethylmethane-vulcabond at room temperature stirs, and makes water-borne pressure sensitive adhesive of the present invention.
3, basic mechanical design feature index determining
Prepared water-borne pressure sensitive adhesive is evenly coated on the polyethylene film through corona treatment, and spread is about 15g/m
2, then at 80 ℃, dry 3 minutes, according to the properties technical indicator of the testing method test pressure sensitive adhesive described in embodiment mono-.Test result is as follows:
Tack: No. 12 balls;
180 ° of stripping strength: 133N/m;
Hold viscosity: > 96h.
The polyethylene protective film that adopts the prepared water-borne pressure sensitive adhesive of the present embodiment to prepare is attached to stainless steel plate substrate surface, under room temperature, places while tearing this protective membrane off after 6 months, without pressure sensitive adhesive, remain in substrate surface.
And the water-borne pressure sensitive adhesive that ordinary method makes is evenly coated on the polyethylene film through corona treatment, spread is about 15g/m
2, then at 80 ℃, dry 3 minutes, according to every technical performance index of the testing method test pressure sensitive adhesive described in embodiment mono-.Test result is as follows:
No. 10 balls of tack: <;
180 ° of stripping strengths: < 100N/m;
Hold viscosity: < 96h
Polyethylene protective film prepared by the water-borne pressure sensitive adhesive that routine makes is attached to stainless steel plate substrate surface, places while tearing this protective membrane off after 6 months under room temperature, and pressure sensitive adhesive remains in substrate surface in a large number.
Embodiment five:
1, synthetic PUA emulsion
By after 250g polyoxytrimethylene triol underpressure distillation dehydration, add 60g diphenylmethanediisocyanate, 60g tolylene diisocyanate, 1g triethylene diamine, 2g di-n-butyltin dilaurate, at 80-85 ℃, react approximately 2 hours, add 0.5g quadrol, 1.5g dimethylol propionic acid, insulation reaction added 20g Hydroxyethyl acrylate after approximately 1 hour, 30g Rocryl 410, react 1 hour, be cooled to 45-50 ℃, add 10gN, N-diethyl ethamine, 1g dimethylol propionic acid, 100g butyl acrylate, 80g Isooctyl acrylate monomer, 40g methyl acrylate, 20g methyl methacrylate, 322g distilled water, stir 0.5-1 hour, add 2g Diisopropyl azodicarboxylate, at 80 ℃, react approximately 3 hours, cooled and filtered makes PUA emulsion.
2, prepare water-borne pressure sensitive adhesive
By 97gPUA emulsion, 3g4,4-dimethylmethane-vulcabond at room temperature stirs, and makes water-borne pressure sensitive adhesive of the present invention.
3, basic mechanical design feature index determining
Prepared water-borne pressure sensitive adhesive is evenly coated on the polyethylene film through corona treatment, and spread is about 15g/m
2, then at 80 ℃, dry 3 minutes, according to the properties technical indicator of the testing method test pressure sensitive adhesive described in embodiment mono-.Test result is as follows:
Tack: No. 11 balls;
180 ° of stripping strength: 146N/m;
Hold viscosity: > 96h.
The polyethylene protective film that adopts the prepared water-borne pressure sensitive adhesive of the present embodiment to prepare is attached to stainless steel plate substrate surface, under room temperature, places while tearing this protective membrane off after 6 months, without pressure sensitive adhesive, remain in substrate surface.
And the water-borne pressure sensitive adhesive that ordinary method makes is evenly coated on the polyethylene film through corona treatment, spread is about 15g/m
2, then at 80 ℃, dry 3 minutes, according to every technical performance index of the testing method test pressure sensitive adhesive described in embodiment mono-.Test result is as follows:
No. 10 balls of tack: <;
180 ° of stripping strengths: < 100N/m;
Hold viscosity: < 96h
Polyethylene protective film prepared by the water-borne pressure sensitive adhesive that routine makes is attached to stainless steel plate substrate surface, places while tearing this protective membrane off after 6 months under room temperature, and pressure sensitive adhesive remains in substrate surface in a large number.
Embodiment six:
1, synthetic PUA emulsion
By after 180g polyoxytrimethylene triol underpressure distillation dehydration, add 70g diphenylmethanediisocyanate, 40g tolylene diisocyanate, 3g triethylene diamine, 1g di-n-butyltin dilaurate, at 80-85 ℃, react approximately 2 hours, add 1g dimethylol propionic acid, insulation reaction added 40g Hydroxyethyl acrylate after approximately 1 hour, react 1 hour, be cooled to 45-50 ℃, add 6gN, N-diethyl ethamine, 3g dimethylol propionic acid, 210g ethyl propenoate, 90g Isooctyl acrylate monomer, 50g methyl acrylate, 50g methyl methacrylate, 254.4g distilled water, stir 0.5-1 hour, add 1.6g Diisopropyl azodicarboxylate, at 80 ℃, react approximately 3 hours, cooled and filtered makes PUA emulsion.
2, prepare water-borne pressure sensitive adhesive
By 95.5gPUA emulsion, 2.5g poly methylene poly phenyl poly isocyanate, 2g4,4-dimethylmethane-vulcabond at room temperature stirs, and makes water-borne pressure sensitive adhesive of the present invention.
3, basic mechanical design feature index determining
Prepared water-borne pressure sensitive adhesive is evenly coated on the polyethylene film through corona treatment, and spread is about 15g/m
2, then at 80 ℃, dry 3 minutes, according to the properties technical indicator of the testing method test pressure sensitive adhesive described in embodiment mono-.Test result is as follows:
Tack: No. 12 balls;
180 ° of stripping strength: 138N/m;
Hold viscosity: > 96h.
The polyethylene protective film that adopts the prepared water-borne pressure sensitive adhesive of the present embodiment to prepare is attached to stainless steel plate substrate surface, under room temperature, places while tearing this protective membrane off after 6 months, without pressure sensitive adhesive, remain in substrate surface.
And the water-borne pressure sensitive adhesive that ordinary method makes is evenly coated on the polyethylene film through corona treatment, spread is about 15g/m
2, then at 80 ℃, dry 3 minutes, according to the testing method described in embodiment mono-, test every technical performance index of pressure sensitive adhesive:
No. 10 balls of tack: <;
180 ° of stripping strengths: < 100N/m;
Hold viscosity: < 96h
Polyethylene protective film prepared by the water-borne pressure sensitive adhesive that ordinary method makes is attached to stainless steel plate substrate surface, places while tearing this protective membrane off after 6 months under room temperature, and pressure sensitive adhesive remains in substrate surface in a large number.
Claims (6)
1. a Water-based pressure-sensitive adhesive of polyethylene protective film, comprises following component by weight percentage:
PUA emulsion 95.0～99.9%;
Solidifying agent 0.1～5.0%, wherein,
Described PUA emulsion is composed of the following components by weight percentage:
Wherein, described functional monomer is selected from one or two or more kinds the mixture in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, N hydroxymethyl acrylamide;
Described soft monomer is selected from one or more the mixture in ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, Isooctyl methacrylate, lauryl acrylate and octadecyl acrylate;
Described hard monomer is selected from one or more the mixture in methyl acrylate, methyl methacrylate, butyl methacrylate, vinylbenzene and vinyl cyanide;
The preparation method of described Water-based pressure-sensitive adhesive of polyethylene protective film, comprises the following steps:
1) synthetic PUA emulsion: by after polyvalent alcohol underpressure distillation dehydration, add polyisocyanates, catalyst reaction, after adding wetting ability chainextender insulation reaction, add functional monomer, fully after reaction, be cooled to 45-50 ℃, add neutralizing agent, soft monomer, hard monomer, chainextender, distilled water, stir, add initiator fully to react, make after cooling;
2) PUA emulsion, solidifying agent are at room temperature stirred, make pressure sensitive adhesive glue.
2. Water-based pressure-sensitive adhesive of polyethylene protective film according to claim 1, is characterized in that: described polyvalent alcohol is selected from one or more the mixture in polyoxypropyleneglycol, polyoxytrimethylene triol, polytetrahydrofuran diol, polyester glycol, polyoxyethylene glycol and polycarbonate diol.
3. Water-based pressure-sensitive adhesive of polyethylene protective film according to claim 1, is characterized in that: described polyisocyanates is selected from one or two or more kinds the mixture in diphenylmethanediisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl-secondary methylbenzene vulcabond, trimethylammonium hexamethylene-diisocyanate, xylylene diisocyanate.
4. Water-based pressure-sensitive adhesive of polyethylene protective film according to claim 1; it is characterized in that: described catalyzer is selected from di-n-butyltin dilaurate, stannous octoate, triethylene diamine, triethylamine, N the mixture of one or two or more kinds in N-dimethylethanolamine, N methyldiethanol amine.
5. Water-based pressure-sensitive adhesive of polyethylene protective film according to claim 1; it is characterized in that: described chainextender is selected from 1; 4-butyleneglycol, 1, the mixture of one or two or more kinds in 6-hexylene glycol, neopentyl glycol, glycerol, TriMethylolPropane(TMP), triglycol, quadrol, dimethylol propionic acid.
6. Water-based pressure-sensitive adhesive of polyethylene protective film according to claim 1; it is characterized in that: described solidifying agent is three isocyanic acid triphenyl thiophosphatephosphorothioates, poly methylene poly phenyl poly isocyanate, 4, the mixture of one or more in 4-dimethylmethane-vulcabond.
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| GB201404021D0 (en) | 2014-03-05 | 2014-04-23 | Lumina Adhesives Ab | Low cytotoxity switchable adhesive compositions, medical dressings and skin coverings, and methods of treatment using same |
| CN104387993A (en) * | 2014-10-30 | 2015-03-04 | 田琳琳 | Easily stripped adhesive |
| CN108285754A (en) * | 2017-12-14 | 2018-07-17 | 昆明和裕胶粘制品有限公司 | A kind of water-borne pressure sensitive adhesive temporary protective film and its preparation and application |
| CN109054701A (en) * | 2018-07-11 | 2018-12-21 | 江苏景宏新材料科技有限公司 | Low temperature resistant pressure-sensitive adhesive agent and preparation method thereof |
| CN110527034B (en) * | 2019-10-12 | 2022-05-20 | 佛山市湾厦新材料科技有限公司 | Waterborne polyurethane resin, preparation method thereof and waterborne baking varnish |
| CN113956432B (en) * | 2021-11-16 | 2023-07-07 | 广东城首新材料有限公司 | Degradable UV resin and degradable UV pressure-sensitive adhesive based on same |
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