CN102533184A - 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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- CN102533184A CN102533184A CN2011104222252A CN201110422225A CN102533184A CN 102533184 A CN102533184 A CN 102533184A CN 2011104222252 A CN2011104222252 A CN 2011104222252A CN 201110422225 A CN201110422225 A CN 201110422225A CN 102533184 A CN102533184 A CN 102533184A
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- Prior art keywords
- sensitive adhesive
- pressure sensitive
- protective film
- polyethylene protective
- water
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 109
- -1 polyethylene Polymers 0.000 title claims abstract description 55
- 230000001681 protective effect Effects 0.000 title claims abstract description 52
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 36
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000000839 emulsion Substances 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 12
- 239000004970 Chain extender Substances 0.000 claims description 10
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 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
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 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
- 238000003756 stirring Methods 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 230000003472 neutralizing effect Effects 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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005056 polyisocyanate Substances 0.000 claims description 5
- 229920001228 polyisocyanate Polymers 0.000 claims description 5
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 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
- 239000012153 distilled water Substances 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
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- 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
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-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
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 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
- 239000004814 polyurethane Substances 0.000 abstract description 2
- 229920002635 polyurethane Polymers 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 37
- 239000000758 substrate Substances 0.000 description 25
- 239000012528 membrane Substances 0.000 description 17
- 229910001220 stainless steel Inorganic materials 0.000 description 15
- 239000010935 stainless steel Substances 0.000 description 15
- 229920000131 polyvinylidene Polymers 0.000 description 14
- 238000003851 corona treatment Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 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 6
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000002904 solvent 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
- 230000007613 environmental effect Effects 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
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 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
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical group CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 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
- 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
- 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 polyethylene protective film use pressure sensitive adhesive and preparation method thereof.
Background technology
Protective membrane is a kind of surface protection, wrapping material that are used to protect the commodity surface; It is attached to the surface of 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 manufacturing, transportation, secondary processing, storage and use, protect the surface, avoid commodity to receive pollution, scratch and slow down the oxidation on commodity surface.The application of protective membrane, not only can improve product visual appearance, make things convenient for materials processed, also can improve simultaneously the utilization ratio of material, reduce production costs.
Protective membrane is made up of substrate layer and pressure-sensitive adhesive layer, generally carries out suitability for industrialized production with coating method, and promptly on the membranaceous base material that has made, the pressure-sensitive adhesive of coating emulsion attitude or solution state adds heat extraction solvent or dispersion agent then, batches and the film that is protected.Protective membrane generally with Vilaterm (PE) film as base material, therefore the pressure sensitive adhesive of coating is generally solvent type polyacrylate class pressure sensitive adhesive, has a large amount of volatile organic compounds (VOC) to discharge in process of production.These volatile organic compoundss not only can cause the comparison serious environmental to pollute, and also can cause bigger 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 is solvent with water, compares with the solvent-borne type pressure sensitive adhesive, does not produce volatile organic solvent, and VOC (volatile organic compounds) is almost nil, has advantages such as cost is low, safe in utilization, pollution-free, is ideal " green " pressure sensitive adhesive.
Summary of the invention
The object of the present invention is to provide a kind of polyethylene protective film use pressure sensitive adhesive.This water-borne pressure sensitive adhesive environmentally safe has good sticking power to polyvinylidene 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 said water-borne pressure sensitive adhesive.
The objective of the invention is to realize through following technical scheme:
A kind of polyethylene protective film use pressure sensitive adhesive comprises following component by weight percentage:
PUA emulsion 95.0～99.9%;
Solidifying agent 0.1～5.0%.
Preferably, described polyethylene protective film use pressure sensitive adhesive comprises following component by weight percentage:
PUA emulsion 96.0～99.5%;
Solidifying agent 0.5～4.0%.
More preferably, described polyethylene protective film use pressure sensitive adhesive comprises following component by weight percentage:
PUA emulsion 97～99%;
Solidifying agent 1～3%;
Described solidifying agent is a 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 big, then the initial bonding strength of pressure sensitive adhesive is relatively poor.In the present invention, described PUA emulsion is composed of the following components by weight percentage:
Polyvalent alcohol 14.5～30.0%;
POLYMETHYLENE POLYPHENYLISOCYANATE 9.2～20.0%;
Catalyzer 0.1～0.5%;
Chainextender 0.1～1.5%;
The 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%;
POLYMETHYLENE POLYPHENYLISOCYANATE 15～20%;
Catalyzer 0.1～0.5%;
Chainextender 0.5～1.5%;
The 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 the polycaprolactone glycol, is preferably the mixture of polyoxypropyleneglycol and polyoxytrimethylene triol polyvalent alcohol.
In PUA emulsion of the present invention; Described POLYMETHYLENE POLYPHENYLISOCYANATE is selected from a kind of or mixture more than two kinds in diphenylmethanediisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl-secondary methylbenzene vulcabond, trimethylammonium hexamethylene-diisocyanate, the 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; A kind of or mixture more than two kinds in N-dimethylethanolamine, the N methyldiethanol amine wherein is preferably the mixture of di-n-butyltin dilaurate, triethylene diamine and stannous octoate.
In PUA emulsion of the present invention; Described chainextender is the wetting ability chainextender; Be selected from 1; 4-butyleneglycol, 1, a kind of or mixture more than two kinds in 6-pinakon, NSC 6366, USP Kosher, TriMethylolPropane(TMP), triglycol, quadrol, the dimethylol propionic acid wherein is preferably the mixture of quadrol and dimethylol propionic acid.
The functional monomer is the propenoate soft monomer that contains hydroxyl; Can effectively improve the cross-linking density of propenoate and urethane; The reactive group that carries can be further crosslinked, can improve the integrity and the force of cohesion of pressure sensitive adhesive, thereby further improve The comprehensive performance.In PUA emulsion of the present invention; Described functional monomer is selected from a kind of or mixture more than two kinds in Hydroxyethyl acrylate, Rocryl 400, Propylene glycol monoacrylate, Rocryl 410, the N hydroxymethyl acrylamide, wherein is preferably the mixture of Hydroxyethyl acrylate and N hydroxymethyl acrylamide.
Soft monomer constitutes 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 big, then 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, Bing Xisuandingzhi, Isooctyl acrylate monomer, Isooctyl methacrylate, lauryl acrylate and the octadecyl acrylate, wherein is preferably the mixture of ethyl propenoate, Bing Xisuandingzhi and Isooctyl acrylate monomer.
Hard monomer constitutes 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 big, then 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, TEB 3K, NSC 20956, vinylbenzene and the vinyl cyanide, wherein is preferably the mixture of methyl acrylate and TEB 3K.
In PUA emulsion of the present invention, described initiator is Lucidol or Diisopropyl azodicarboxylate.
In PUA emulsion of the present invention, described neutralizing agent is N, N-diethylammonium ethamine.
The preparation method of polyethylene protective film use pressure sensitive adhesive of the present invention may further comprise the steps:
1) synthetic PUA emulsion: after polyvalent alcohol underpressure distillation dehydration; Add POLYMETHYLENE POLYPHENYLISOCYANATE, catalyst reaction, add the functional monomer after the adding wetting ability chainextender insulation reaction, fully be cooled to 45-50 ℃ after the reaction; Add neutralizing agent, soft monomer, hard monomer, chainextender, zero(ppm) water; Stir, add initiator and fully react, promptly make after the cooling;
2) PUA emulsion, waterborne curing agent are at room temperature stirred, make the pressure sensitive adhesive glue.
Water-borne pressure sensitive adhesive of the present invention has good sticking power to polyvinylidene film, can realize the well balanced of initial bonding strength, stripping strength and force of cohesion; Because its viscosity is bigger, be applicable to that blade coating produces polyethylene protective film, advantage such as it is low to have environmental friendliness, solidify fast and consume energy.The key technical indexes that polyethylene protective film use pressure sensitive adhesive of the present invention is reached is following: tack: >=No. 10 balls; 180 ° of stripping strength:＞100N/m; Hold viscosity (25 ℃):＞96h does not come off.The polyethylene protective film that adopts water-borne pressure sensitive adhesive preparation of the present invention is attached to the stainless steel plate surface, and when the room temperature held tore this protective membrane off after 6 months, no pressure sensitive adhesive remained in the stainless steel plate surface.
Compared with prior art; The present invention is through synthetic PUA emulsion, because it has the advantage of vinylformic acid and urethane concurrently, and contains crosslinkable active function groups; Therefore can give pressure sensitive adhesive viscosity, weathering resistance, water tolerance preferably, and the performance of excellent high-temp resisting high-humidity resisting.
Embodiment
Embodiment one:
1, synthetic PUA emulsion
After 100g polyoxypropyleneglycol, 50g polyoxytrimethylene triol underpressure distillation dehydration, add 100g diphenylmethanediisocyanate, 0.5g stannous octoate, 0.5g di-n-butyltin dilaurate, reacted 2 hours down at 80-85 ℃; Add the 0.5g quadrol; Insulation reaction adds the 100g Hydroxyethyl acrylate after 1 hour, reacted 1 hour, is cooled to 45-50 ℃; Add 3gN; N-diethylammonium ethamine, 0.5g dimethylol propionic acid, 80g Bing Xisuandingzhi, 70g ethyl propenoate, 30g methyl acrylate, 20g TEB 3K, 437g zero(ppm) water stirred 0.5-1 hour, added the 8g Diisopropyl azodicarboxylate; Reacted 3 hours down at 80 ℃, cooled and filtered promptly makes PUA emulsion (polyurethane/acrylic ester composite emulsion).
2, preparation water-borne pressure sensitive adhesive
95gPUA emulsion, 5g poly methylene poly phenyl poly isocyanate are at room temperature stirred, promptly 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 through on the polyvinylidene film of corona treatment, and spread is about 15g/m
2, dried by the fire 3 minutes down at 80 ℃ then, test each item technical performance index of pressure sensitive adhesive according to following testing method:
Tack: the spin slope according to GB 4852-1984 stops method (DOW method), uses Pressuresensitive Tape initial cohesiveness tester to test;
180 ° of stripping strengths:, use the desktop tension testing machine to test according to GB/T 2792-1998;
Hold viscosity:, use adhesive tape confining force trier to test according to GB/T 4851-1988.
The test result of each item performance technologies index is following:
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 preparation of present embodiment is attached to the stainless steel plate substrate surface, and when the room temperature held tore this protective membrane off after 6 months, no pressure sensitive adhesive remained in substrate surface.
And the water-borne pressure sensitive adhesive that ordinary method makes is evenly coated through on the polyvinylidene film of corona treatment, and spread is about 15g/m
2, dried by the fire 3 minutes down at 80 ℃ then, test each item technical performance index of pressure sensitive adhesive according to above testing method:
Tack:＜No. 10 balls;
180 ° of stripping strength:＜100N/m;
Hold viscosity:＜96h
The polyethylene protective film of the water-borne pressure sensitive adhesive preparation that ordinary method makes is attached to the stainless steel plate substrate surface, and when the room temperature held tore this protective membrane off after 6 months, pressure sensitive adhesive remained in substrate surface in a large number.
Embodiment two:
1, synthetic PUA emulsion
After 145g polyoxytrimethylene triol underpressure distillation dehydration, add 55g diphenylmethanediisocyanate, 37g tolylene diisocyanate, 1.5g triethylene diamine, 1g di-n-butyltin dilaurate, reacted 2 hours down at 80-85 ℃; Add the 0.5g dimethylol propionic acid; Insulation reaction adds the 35g Hydroxyethyl acrylate after about 1 hour, reacted about 1 hour, is cooled to 45-50 ℃; Add 15gN; N-diethylammonium ethamine, 0.5g dimethylol propionic acid, 320g Bing Xisuandingzhi, 80g Isooctyl acrylate monomer, 75g methyl acrylate, 75g TEB 3K, 158g zero(ppm) water stirred 0.5-1 hour, added the 1.5g Diisopropyl azodicarboxylate; Reacted about 3 hours down at 80 ℃, cooled and filtered promptly makes the PUA emulsion.
2, preparation water-borne pressure sensitive adhesive
With 98gPUA emulsion, 1g poly methylene poly phenyl poly isocyanate, 1g4,4-dimethylmethane-vulcabond at room temperature stirs, and promptly 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 through on the polyvinylidene film of corona treatment, and spread is about 15g/m
2, dried by the fire 3 minutes down at 80 ℃ then, according to each item performance technologies index of embodiment one described testing method test pressure sensitive adhesive.Test result is following:
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 preparation of present embodiment is attached to the stainless steel plate substrate surface, and when the room temperature held tore this protective membrane off after 6 months, no pressure sensitive adhesive remained in substrate surface.
And the water-borne pressure sensitive adhesive that ordinary method makes is evenly coated through on the polyvinylidene film of corona treatment, and spread is about 15g/m
2, dried by the fire 3 minutes down at 80 ℃ then, test each item technical performance index of pressure sensitive adhesive according to embodiment one described testing method:
Tack:＜No. 10 balls;
180 ° of stripping strength:＜100N/m;
Hold viscosity:＜96h
The polyethylene protective film of the water-borne pressure sensitive adhesive preparation that ordinary method makes is attached to the stainless steel plate substrate surface, and when the room temperature held tore this protective membrane off after 6 months, pressure sensitive adhesive remained in substrate surface in a large number.
Embodiment three:
1, synthetic PUA emulsion
After 300g polyoxytrimethylene triol underpressure distillation dehydration, add 200g tolylene diisocyanate, 2g stannous octoate, 3g di-n-butyltin dilaurate, reacted 2 hours down at 80-85 ℃; Add the 5g quadrol, insulation reaction adds 5g Hydroxyethyl acrylate, 5gN-NMA after about 1 hour, reacted about 1 hour; Be cooled to 45-50 ℃, add 4gN, N-diethylammonium ethamine, 10g dimethylol propionic acid, 120g Bing Xisuandingzhi, 130g Isooctyl acrylate monomer, 30g methyl acrylate, 185g zero(ppm) water; Stirred 0.5-1 hour; Add the 1g Diisopropyl azodicarboxylate, reacted about 3 hours down at 80 ℃, cooled and filtered promptly makes the PUA emulsion.
2, preparation water-borne pressure sensitive adhesive
With 99.9gPUA emulsion, 0.1g4,4-dimethylmethane-vulcabond at room temperature stirs, and promptly 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 through on the polyvinylidene film of corona treatment, and spread is about 15g/m
2, dried by the fire 3 minutes down at 80 ℃ then, according to each item performance technologies index of embodiment one described testing method test pressure sensitive adhesive.Test result is following:
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 preparation of present embodiment is attached to the stainless steel plate substrate surface, and when the room temperature held tore this protective membrane off after 6 months, no pressure sensitive adhesive remained in substrate surface.
And the water-borne pressure sensitive adhesive that ordinary method makes is evenly coated through on the polyvinylidene film of corona treatment, and spread is about 15g/m
2, dried by the fire 3 minutes down at 80 ℃ then, according to each item technical performance index of embodiment one described testing method test pressure sensitive adhesive.Test result is following:
Tack:＜No. 10 balls;
180 ° of stripping strength:＜100N/m;
Hold viscosity:＜96h
The polyethylene protective film of the water-borne pressure sensitive adhesive preparation that routine makes is attached to the stainless steel plate substrate surface, and when the room temperature held tore this protective membrane off after 6 months, pressure sensitive adhesive remained in substrate surface in a large number.
Embodiment four:
1, synthetic PUA emulsion
After 120g polyoxypropyleneglycol, 80g polyoxytrimethylene triol underpressure distillation dehydration, add 150g diphenylmethanediisocyanate, 1g stannous octoate, 1g di-n-butyltin dilaurate, reacted about 2 hours down at 80-85 ℃; Add 0.3g quadrol, 0.2g dimethylol propionic acid; Insulation reaction adds the 20g Propylene glycol monoacrylate after about 1 hour, reacted 1 hour, is cooled to 45-50 ℃; Add 5gN; N-diethylammonium ethamine, 1.5g dimethylol propionic acid, 80g Bing Xisuandingzhi, 120g Isooctyl acrylate monomer, 40g TEB 3K, 379.7g zero(ppm) water stirred 0.5-1 hour, added the 1.3g Diisopropyl azodicarboxylate; Reacted about 3 hours down at 80 ℃, cooled and filtered promptly makes the PUA emulsion.
2, preparation water-borne pressure sensitive adhesive
With 96gPUA emulsion, 4g4,4-dimethylmethane-vulcabond at room temperature stirs, and promptly 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 through on the polyvinylidene film of corona treatment, and spread is about 15g/m
2, dried by the fire 3 minutes down at 80 ℃ then, according to each item performance technologies index of embodiment one described testing method test pressure sensitive adhesive.Test result is following:
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 preparation of present embodiment is attached to the stainless steel plate substrate surface, and when the room temperature held tore this protective membrane off after 6 months, no pressure sensitive adhesive remained in substrate surface.
And the water-borne pressure sensitive adhesive that ordinary method makes is evenly coated through on the polyvinylidene film of corona treatment, and spread is about 15g/m
2, dried by the fire 3 minutes down at 80 ℃ then, according to each item technical performance index of embodiment one described testing method test pressure sensitive adhesive.Test result is following:
Tack:＜No. 10 balls;
180 ° of stripping strength:＜100N/m;
Hold viscosity:＜96h
The polyethylene protective film of the water-borne pressure sensitive adhesive preparation that routine makes is attached to the stainless steel plate substrate surface, and when the room temperature held tore this protective membrane off after 6 months, pressure sensitive adhesive remained in substrate surface in a large number.
Embodiment five:
1, synthetic PUA emulsion
After 250g polyoxytrimethylene triol underpressure distillation dehydration, add 60g diphenylmethanediisocyanate, 60g tolylene diisocyanate, 1g triethylene diamine, 2g di-n-butyltin dilaurate, reacted about 2 hours down at 80-85 ℃; Add 0.5g quadrol, 1.5g dimethylol propionic acid; Insulation reaction adds 20g Hydroxyethyl acrylate, 30g Rocryl 410 after about 1 hour, reacted 1 hour, is cooled to 45-50 ℃; Add 10gN; N-diethylammonium ethamine, 1g dimethylol propionic acid, 100g Bing Xisuandingzhi, 80g Isooctyl acrylate monomer, 40g methyl acrylate, 20g TEB 3K, 322g zero(ppm) water stirred 0.5-1 hour, added the 2g Diisopropyl azodicarboxylate; Reacted about 3 hours down at 80 ℃, cooled and filtered promptly makes the PUA emulsion.
2, preparation water-borne pressure sensitive adhesive
With 97gPUA emulsion, 3g4,4-dimethylmethane-vulcabond at room temperature stirs, and promptly 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 through on the polyvinylidene film of corona treatment, and spread is about 15g/m
2, dried by the fire 3 minutes down at 80 ℃ then, according to each item performance technologies index of embodiment one described testing method test pressure sensitive adhesive.Test result is following:
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 preparation of present embodiment is attached to the stainless steel plate substrate surface, and when the room temperature held tore this protective membrane off after 6 months, no pressure sensitive adhesive remained in substrate surface.
And the water-borne pressure sensitive adhesive that ordinary method makes is evenly coated through on the polyvinylidene film of corona treatment, and spread is about 15g/m
2, dried by the fire 3 minutes down at 80 ℃ then, according to each item technical performance index of embodiment one described testing method test pressure sensitive adhesive.Test result is following:
Tack:＜No. 10 balls;
180 ° of stripping strength:＜100N/m;
Hold viscosity:＜96h
The polyethylene protective film of the water-borne pressure sensitive adhesive preparation that routine makes is attached to the stainless steel plate substrate surface, and when the room temperature held tore this protective membrane off after 6 months, pressure sensitive adhesive remained in substrate surface in a large number.
Embodiment six:
1, synthetic PUA emulsion
After 180g polyoxytrimethylene triol underpressure distillation dehydration, add 70g diphenylmethanediisocyanate, 40g tolylene diisocyanate, 3g triethylene diamine, 1g di-n-butyltin dilaurate, reacted about 2 hours down at 80-85 ℃; Add the 1g dimethylol propionic acid; Insulation reaction adds the 40g Hydroxyethyl acrylate after about 1 hour, reacted 1 hour, is cooled to 45-50 ℃; Add 6gN; N-diethylammonium ethamine, 3g dimethylol propionic acid, 210g ethyl propenoate, 90g Isooctyl acrylate monomer, 50g methyl acrylate, 50g TEB 3K, 254.4g zero(ppm) water stirred 0.5-1 hour, added the 1.6g Diisopropyl azodicarboxylate; Reacted about 3 hours down at 80 ℃, cooled and filtered promptly makes the PUA emulsion.
2, preparation water-borne pressure sensitive adhesive
With 95.5gPUA emulsion, 2.5g poly methylene poly phenyl poly isocyanate, 2g4,4-dimethylmethane-vulcabond at room temperature stirs, and promptly 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 through on the polyvinylidene film of corona treatment, and spread is about 15g/m
2, dried by the fire 3 minutes down at 80 ℃ then, according to each item performance technologies index of embodiment one described testing method test pressure sensitive adhesive.Test result is following:
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 preparation of present embodiment is attached to the stainless steel plate substrate surface, and when the room temperature held tore this protective membrane off after 6 months, no pressure sensitive adhesive remained in substrate surface.
And the water-borne pressure sensitive adhesive that ordinary method makes is evenly coated through on the polyvinylidene film of corona treatment, and spread is about 15g/m
2, dried by the fire 3 minutes down at 80 ℃ then, test each item technical performance index of pressure sensitive adhesive according to embodiment one described testing method:
Tack:＜No. 10 balls;
180 ° of stripping strength:＜100N/m;
Hold viscosity:＜96h
The polyethylene protective film of the water-borne pressure sensitive adhesive preparation that ordinary method makes is attached to the stainless steel plate substrate surface, and when the room temperature held tore this protective membrane off after 6 months, pressure sensitive adhesive remained in substrate surface in a large number.
Claims (10)
1. polyethylene protective film use pressure sensitive adhesive 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:
Polyvalent alcohol 14.5～30.0%;
POLYMETHYLENE POLYPHENYLISOCYANATE 9.2～20.0%;
Catalyzer 0.1～0.5%;
Chainextender 0.1～1.5%;
The 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.
2. polyethylene protective film use pressure sensitive adhesive 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, polycarbonate diol and the polycaprolactone glycol.
3. polyethylene protective film use pressure sensitive adhesive according to claim 1 is characterized in that: described POLYMETHYLENE POLYPHENYLISOCYANATE is selected from a kind of or mixture more than two kinds in diphenylmethanediisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl-secondary methylbenzene vulcabond, trimethylammonium hexamethylene-diisocyanate, the xylylene diisocyanate.
4. polyethylene protective film use pressure sensitive adhesive according to claim 1; It is characterized in that: described catalyzer is selected from di-n-butyltin dilaurate, stannous octoate, triethylene diamine, triethylamine, N, a kind of or mixture more than two kinds in N-dimethylethanolamine, the N methyldiethanol amine.
5. polyethylene protective film use pressure sensitive adhesive according to claim 1; It is characterized in that: described chainextender is selected from 1; 4-butyleneglycol, 1, a kind of or mixture more than two kinds in 6-pinakon, NSC 6366, USP Kosher, TriMethylolPropane(TMP), triglycol, quadrol, the dimethylol propionic acid.
6. polyethylene protective film use pressure sensitive adhesive according to claim 1 is characterized in that: described functional monomer is selected from a kind of or mixture more than two kinds in Hydroxyethyl acrylate, Rocryl 400, Propylene glycol monoacrylate, Rocryl 410, the N hydroxymethyl acrylamide.
7. polyethylene protective film use pressure sensitive adhesive according to claim 1 is characterized in that: described soft monomer is selected from one or more the mixture in ethyl propenoate, Bing Xisuandingzhi, Isooctyl acrylate monomer, Isooctyl methacrylate, lauryl acrylate and the octadecyl acrylate.
8. polyethylene protective film use pressure sensitive adhesive according to claim 1 is characterized in that: described hard monomer is selected from one or more the mixture in methyl acrylate, TEB 3K, NSC 20956, vinylbenzene and the vinyl cyanide.
9. polyethylene protective film use pressure sensitive adhesive 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.
10. the preparation method of a polyethylene protective film use pressure sensitive adhesive as claimed in claim 1 may further comprise the steps:
1) synthetic PUA emulsion: after polyvalent alcohol underpressure distillation dehydration; Add POLYMETHYLENE POLYPHENYLISOCYANATE, catalyst reaction, add the functional monomer after the adding wetting ability chainextender insulation reaction, fully be cooled to 45-50 ℃ after the reaction; Add neutralizing agent, soft monomer, hard monomer, chainextender, zero(ppm) water; Stir, add initiator and fully react, promptly make after the cooling;
2) PUA emulsion, solidifying agent are at room temperature stirred, make the pressure sensitive adhesive glue.
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| CN113956432A (en) * | 2021-11-16 | 2022-01-21 | 广东十辰十新材料有限公司 | Degradable UV resin and degradable UV pressure-sensitive adhesive based on same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US10703942B2 (en) | 2014-03-05 | 2020-07-07 | Lumina Adhesives Ab | Low cytotoxicity switchable adhesive compositions, medical dressings and skin coverings, and methods of treatment using same |
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| 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 |
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| CN110527034A (en) * | 2019-10-12 | 2019-12-03 | 佛山市湾厦新材料科技有限公司 | Waterborne polyurethane resin and preparation method thereof, water-based stoving paint |
| CN113956432A (en) * | 2021-11-16 | 2022-01-21 | 广东十辰十新材料有限公司 | Degradable UV resin and degradable UV pressure-sensitive adhesive based on same |
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| CN102533184B (en) | 2014-10-15 |
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