CN115678477B - Double-component solvent-free polyurethane laminating adhesive and preparation method thereof - Google Patents
Double-component solvent-free polyurethane laminating adhesive and preparation method thereof Download PDFInfo
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- CN115678477B CN115678477B CN202110861354.5A CN202110861354A CN115678477B CN 115678477 B CN115678477 B CN 115678477B CN 202110861354 A CN202110861354 A CN 202110861354A CN 115678477 B CN115678477 B CN 115678477B
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- 239000012939 laminating adhesive Substances 0.000 title claims abstract description 66
- 239000004814 polyurethane Substances 0.000 title claims abstract description 60
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000004970 Chain extender Substances 0.000 claims abstract description 9
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 7
- 229920005906 polyester polyol Polymers 0.000 claims description 117
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 57
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 35
- 150000002009 diols Chemical class 0.000 claims description 31
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 30
- 239000005056 polyisocyanate Substances 0.000 claims description 29
- 229920001228 polyisocyanate Polymers 0.000 claims description 29
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- 150000003077 polyols Chemical class 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 18
- 229920000570 polyether Polymers 0.000 claims description 18
- 229920005862 polyol Polymers 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 235000011037 adipic acid Nutrition 0.000 claims description 15
- 239000001361 adipic acid Substances 0.000 claims description 15
- 150000008064 anhydrides Chemical class 0.000 claims description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 11
- 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 11
- -1 polymethylene Polymers 0.000 claims description 10
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical class OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 claims description 9
- 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 9
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 9
- 150000002513 isocyanates Chemical class 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 7
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 7
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 7
- 229920001843 polymethylhydrosiloxane Polymers 0.000 claims description 7
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- 125000004018 acid anhydride group Chemical group 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- OZCRKDNRAAKDAN-UHFFFAOYSA-N but-1-ene-1,4-diol Chemical compound O[CH][CH]CCO OZCRKDNRAAKDAN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 abstract description 25
- 239000002131 composite material Substances 0.000 abstract description 8
- 238000010025 steaming Methods 0.000 abstract description 7
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 230000010354 integration Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000003292 glue Substances 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 241000519995 Stachys sylvatica Species 0.000 description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000003636 chemical group Chemical group 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 125000005375 organosiloxane group Chemical group 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- CPLASELWOOUNGW-UHFFFAOYSA-N benzyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CC1=CC=CC=C1 CPLASELWOOUNGW-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- GQVVQDJHRQBZNG-UHFFFAOYSA-N benzyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CC1=CC=CC=C1 GQVVQDJHRQBZNG-UHFFFAOYSA-N 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Abstract
The invention discloses a double-component solvent-free polyurethane laminating adhesive with a composite high-barrier structure and a preparation method thereof, wherein the solvent-free polyurethane laminating adhesive comprises a component A and a component B, wherein the component A is polyurethane prepolymer of isocyanate groups (NCO); the component B is polyhydroxy compound and also comprises at least one of adhesion promoter, leveling agent, tackifier or chain extender. The solvent-free polyurethane laminating adhesive prepared by the invention can be used for compounding high-barrier structures such as PET/AL and PET/VMPET, has no white spot bubbles in appearance after compounding, meets the steaming requirement of an aluminum-plastic structure, and has the advantages of compounding the high-barrier structures and steaming integration.
Description
Technical Field
The invention relates to the field of solvent-free type bi-component polyurethane adhesives, in particular to a bi-component solvent-free type polyurethane laminating adhesive meeting the requirements of high-barrier PET/VMPET and PET/AL structure compounding and aluminum plastic steaming and boiling and a preparation method thereof.
Background
Solvent-free compounding is a soft package compounding mode developed in recent years, and is gradually popularized in the domestic soft package industry by virtue of the advantages of environmental protection, safety, energy conservation, high efficiency and capability of obviously reducing cost. The packaging field of solvent-free composite which can be used at present is dry and light packaging, boiling packaging, high-temperature boiling inner packaging and the like, and the composite structure mainly comprises a PA/PE structure, a PET/PE structure, an OPP/CPP structure, an OPP/aluminized/PE structure and the like. However, for high-barrier structures such as PET/VMPET and PET/AL, because the two base materials are high-barrier structures, there is no flexibility between the film materials, shrinkage sliding easily occurs between the two high-barrier structures after compounding, meanwhile, the initial adhesion force of the solvent-free glue is lower, the glue can not bond the two base materials quickly, the problem of white point bubbles in appearance can occur when the solvent-free glue is used for compounding the high-barrier structures, the solvent-free glue is still used for compounding the high-barrier structures in the market at present, and the solvent can not stably compound the high-barrier structures such as PET/VMPET and PET/AL.
In order to realize the compounding of the solvent-free polyurethane laminating adhesive to the PET/AL structure, research and development personnel carry out design improvement on a two-component solvent-free adhesive formula, but the research progress in the field is less so far. Chinese patent CN108517194a discloses a special double-component solvent-free polyurethane adhesive for high-barrier aluminum-plastic materials and a preparation method thereof. The peel strength of the PET/AL structure of the adhesive can reach 3.5N, but the appearance of the PET/AL structure still has white point bubbles when the adhesive is used, especially when the rotating speed reaches more than 100m/min, the appearance white point is increased, and the actual production requirement cannot be met.
Therefore, developing a solvent-free polyurethane laminating adhesive which can be used for producing composite high-barrier structures such as PET/VMPET and PET/AL is a problem which is urgently needed to be faced by the soft package industry.
Disclosure of Invention
In order to overcome the problems, the inventor conducts intensive research to break through the thought limitation that the initial adhesion of the solvent-free double-component laminating adhesive is low, the NCO content of the component A is reduced in the component A to improve the viscosity, and a crystalline temperature sensitive structure and a proper tackifier are introduced into the component B, so that the laminating adhesive has a sensitive temperature-viscosity change trend; the common solvent-free double-component polyurethane laminating adhesive has the viscosity of 300-4000 Pa.s at 25 ℃ and the application temperature of 35-45 ℃. By designing the formula structure, the viscosity of the solvent-free double-component polyurethane laminating adhesive at 25 ℃ is 30000-120000 mPa.s; the viscosity at 65 ℃ is 300-1400 Pa.s, and the application temperature is about 65 ℃. The room temperature viscosity of A, B component glue can be improved to ensure that the glue has enough initial adhesion immediately after compounding and can be rapidly adhered to PET and AL high-barrier substrates; meanwhile, the A, B glue has lower viscosity and good leveling property at the coating temperature so as to ensure that the PET/VMPET and PET/AL structures have good wettability in the compounding process and meet the requirements of aluminum-plastic steaming application.
In order to solve the problems in the prior art, the application adopts the following technical scheme:
The first aspect of the invention provides a two-component solvent-free polyurethane laminating adhesive, which comprises a component A and a component B, wherein the component A is a polyurethane prepolymer with an isocyanate group as a terminal group, which is formed by reacting a polyhydroxy compound I and polyisocyanate, and preferably, the polyurethane prepolymer has a viscosity of 500-1400 mPa.s, preferably 600-1200 mPa.s, at 65 ℃; the component B is polyhydroxy compound II.
Preferably, the NCO content of the A component is 8-16%, preferably 10-14%;
preferably, the isocyanate groups (NCO) in the a-component: the molar ratio of hydroxyl groups (OH) in the B component is 1.5-2.2, preferably 1.7-1.9.
Preferably, the polyisocyanate in the A component is at least one selected from aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate;
In some preferred embodiments of the present invention, the polyisocyanate is selected from one or more of diphenylmethane diisocyanate, liquefied MDI, dicyclohexylmethane diisocyanate, isophorone diisocyanate, polymethylene polyphenyl polyisocyanates; in a further preferred embodiment, the polyisocyanate comprises 5 to 50% by weight of isophorone diisocyanate and the isocyanate in the a-component is selected from diphenylmethane diisocyanate, isophorone diisocyanate. The isocyanate in the component A accounts for 40-80% of the weight of the component A, preferably 50-70%.
Preferably, the polyol I in the A component may be one or more of a polyester polyol and/or a polyether polyol which is a hydroxyl-terminated oligomer having a main chain having an ether bond and having a molecular weight of 400 to 2000, which is initiated with a hydroxyl group-containing, amino group-containing or low molecular weight compound having a hydroxyl group and an amino group as an initiator.
Preferably, the functionality of the polyhydroxy compound in the A component is two functionalities;
in a preferred embodiment of the invention, the polyol in the A-component is a difunctional polyether polyol.
Preferably, the mass content of the polyhydroxy compound I in the component A is 20-60%.
The B component polyhydroxy compound II is one or more of polyester polyol and/or polyether polyol, the B component has a hydroxyl value of 80-200mg KOH/g, preferably 100-150mg KOH/g, and a viscosity of 200-900 mPas, preferably 300-700 mPas, at 65 ℃.
The polyether polyol in the component B is a hydroxyl-terminated oligomer with a main chain containing ether bonds, wherein the main chain of the hydroxyl-terminated oligomer is 400-2000 in molecular weight and takes a low-molecular compound containing hydroxyl groups, amino groups or both hydroxyl groups and amino groups as an initiator. Preferably, the polyether polyol functionality in the B component is two functionalities; the mass ratio of the component B is 0-40%. The polyester polyol in the component B comprises a polyester polyol 1 and a polyester polyol 2, wherein in the component B, the mass ratio of the polyester polyol 1 is 20-60%, and the mass ratio of the polyester polyol 2 is 10-30%; preferably, the functionality of both polyester polyol 1 and polyester polyol 2 is difunctional.
In the component B, the polyester polyol 1 and the polyester polyol 2 are polyester polyols obtained by the condensation polymerization reaction of dibasic acid and/or anhydride and dihydric alcohol.
Preferably, the diols used for synthesizing the polyester polyol 1 comprise linear diols without side groups, and the polyester polyol synthesized by the diols has good crystallinity, and the crystallization temperature is generally higher than room temperature (25 ℃); the invention characterizes the crystallinity by the content of diol with no side group and crystallization temperature. Polyester polyol 1 is a crystalline viscosity-temperature sensitive polyester polyol, and the viscosity can be rapidly changed at a specific temperature.
Preferably, the crystallization temperature of the polyester polyol 1 is lower than room temperature (25 ℃), and in order to ensure that the crystallization temperature of the polyester polyol 1 is lower than room temperature, the glycol for synthesizing the polyester polyol 1 further comprises one or more of diethylene glycol and 1, 4-cyclohexanedimethanol glycol, so that the segment rotation capacity of the polyester polyol 1 is improved, and the crystallization temperature is reduced. The mole content of diethylene glycol and 1, 4-cyclohexanedimethanol dihydric alcohol is more than 0.3 times of the total mole of dihydric alcohol.
Preferably, the molar ratio of the linear diol without side groups to the total diol content is less than 0.5, and the crystallization temperature of the synthesized polyester polyol can be below room temperature.
Further preferably, the molar content of the linear diol without side group is more than 0.1 times of the total molar amount of the diol, so that the crystallization temperature is lower than the room temperature and good temperature sensitivity is maintained.
The viscosity of the polyester polyol 1 can be further controlled by adjusting the molecular weight, the molecular weight is 400-5000, preferably 800-3000, the room temperature viscosity of the polyester polyol 1 can exceed 40000 mPa.s, and the initial adhesion is higher; in addition, the dibasic acid of the synthetic polyester polyol 1 comprises aliphatic dibasic acid/anhydride and aromatic dibasic acid/anhydride, preferably aromatic dibasic acid/anhydride, and the aromatic dibasic acid/anhydride has rigid structure and symmetry and has an effect of improving the heat resistance and cohesion of the polyester polyol. Preferably, the molar content of the aromatic dibasic acid and the anhydride is more than 5mol percent of the total amount of the dibasic acid; however, too high an amount of aromatic diacid or anhydride can affect the fluidity of the polyester polyol at high temperature, and according to the study of the invention, the polyester polyol synthesized by the molar content of aromatic diacid or anhydride being less than 20mol% of the total amount of diacid has excellent fluidity at high temperature and the viscosity decreasing trend is obvious with the change of temperature.
In some preferred embodiments of the present invention, the dibasic acid and/or anhydride of the polyester polyol 1 is synthesized to include one or more of adipic acid, isophthalic acid, terephthalic acid, phthalic anhydride, and sebacic acid, and the dibasic alcohol of the polyester polyol 1 is synthesized to include one or more of ethylene glycol, diethylene glycol, triethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, trimethylolpropane, and 1, 4-cyclohexanedimethanol-based dibasic alcohol, and preferably the dibasic acid and/or anhydride is one or more of adipic acid, isophthalic acid, and terephthalic acid, and the dibasic alcohol is one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, and 1, 4-cyclohexanedimethanol.
The polyester polyol 2 is polyester polyol containing a side methyl structure, and is matched with the polyester polyol 1 for use, so that the prepared laminating adhesive can improve the leveling property of the adhesive while ensuring the viscosity-temperature sensitivity, and the appearance of the laminating adhesive is free from white spots under high rotating speed. The molecular structure of the dihydric alcohol can influence the leveling property of the polyester polyol, and the dihydric alcohol with methyl structure in side chains such as neopentyl glycol, 2-methyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol and the like has a nonpolar structure-CH 3, so that the dihydric alcohol has good contact wettability with a base material, and the leveling property of a polyester polyol system can be improved. Therefore, the diol of the synthetic polyester polyol 2 comprises diol with a methyl structure in a side chain, the surface tension of the polyester polyol can be reduced to 40 along with the increase of the diol with the methyl structure in the side chain, and then the surface tension tends to be stable, but the introduction of the diol with excessive methyl structure in the side chain can influence the matching property between the polyester polyol and the ink, and when the mole ratio of the diol with the methyl structure in the side chain exceeds 80% of the total mole amount of the diol, the matching property of the polyester polyol ink is obviously reduced, which is not beneficial to practical application. Preferably, the molar ratio of the diol having a methyl structure in the side chain to the total amount of diol is in the range of 0.3 to 0.8.
Preferably, the dibasic acid of the synthetic polyester polyol 2 comprises dibasic acid and/or anhydride containing benzene ring, and the polyester polyol 2 prepared from the dibasic acid and/or anhydride containing benzene ring is matched with the polyester polyol 1 for use, so that the obtained adhesive has stronger cohesive force and is beneficial to improving the compound fastness of the adhesive.
Preferably, the dibasic acid and/or anhydride containing benzene ring accounts for 50% -90% of the total mole of the dibasic acid.
Preferably, the molecular weight of the polyester polyol 2 is 400 to 4000, preferably 800 to 3000, more preferably 800 to 2000.
The dibasic acid and/or anhydride of the synthetic polyester polyol 2 comprises one or more of adipic acid, isophthalic acid, terephthalic acid, phthalic anhydride and sebacic acid, preferably adipic acid, isophthalic acid and phthalic anhydride, and the dihydric alcohol of the synthetic polyester polyol 2 comprises ethylene glycol, diethylene glycol, triethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, 2-methyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, trimethylolpropane, glycerol and modified butylene glycol.
The modified butylene glycol is a product obtained by reacting 1, 4-butylene glycol with polymethylhydrosiloxane: the preparation method comprises the following steps: in a nitrogen atmosphere, 1, 4-butylene glycol and polymethylhydrosiloxane are added into a reaction kettle in a molar ratio of 1:1-1.5, heating to 70-90 ℃, adding 0.01-0.1% chloroplatinic acid catalyst, stirring, preserving heat for 0.5-1h, continuously heating to 90-120 ℃ for reacting for 5-8h, and removing the residual polymethylhydrosiloxane by rotary evaporation to obtain the final product of the modified butenediol.
Compared with the method of introducing methyl-containing organosiloxane in a physical mixing mode, the method has the advantages that the organosiloxane is directly grafted into the polyester polyol through a chemical modification method, so that the organosiloxane can be effectively and uniformly dispersed to avoid agglomeration, the surface tension of the polyester polyol can be reduced, and the leveling property is improved. However, the siloxane compound has too much side chain methyl, and larger steric hindrance, and the molar amount of the modified butylene glycol in the polyester polyol 2 is less than 0.3 of the total mole of the dihydric alcohol under the premise of ensuring a certain molecular weight. Preferably, the molar amount of the modified butenediol is 0.05 to 0.2 based on the total molar amount of the dihydric alcohol.
The polyester polyol 1 and the polyester polyol 2 have good synergistic effect when used together, and have excellent leveling property and high initial adhesion.
In addition, the component B also comprises one or more of an adhesion promoter, a leveling agent, a tackifier or a chain extender.
According to a preferred embodiment of the invention, a leveling agent is added to the component B to improve leveling wettability in the glue compounding process. The leveling agent is selected from one or more of organosilicon, acrylic and fluorocarbon. The content of the leveling agent accounts for 0-3% of the total mass of the component B; preferably, the content of the leveling agent accounts for 0-1% of the total mass of the component B.
According to a preferred embodiment of the present invention, an adhesion promoter is added to the component B to improve the compound fastness of the glue, the adhesion promoter is a silane coupling agent, and the adhesion promoter is selected from one or more of γ -aminopropyl triethoxysilane, γ -aminopropyl trimethoxysilane, N- (β -aminoethyl) - γ -aminopropyl triethoxysilane, γ -glycidyloxypropyl trimethoxysilane, benzyl triethoxysilane, or benzyl trimethoxysilane, preferably γ -glycidyloxypropyl trimethoxysilane, γ -aminopropyl triethoxysilane, and benzyl triethoxysilane, and the addition amount of the adhesion promoter is 0.5-5% of the total mass of the component B.
According to a preferred embodiment of the present invention, a tackifier is added to the B component for increasing the room temperature viscosity of the B component while maintaining low viscosity at high temperature, the tackifier being selected from one or more of rosin resins, modified rosin resins, polystyrene resins, petroleum resins, polyterpene resins; preferably, the tackifier is rosin resin or modified rosin resin. The addition amount is 0.1-5% of the total mass of the B component, preferably 0.5-3% of the total mass of the B component.
According to a preferred embodiment of the present invention, a chain extender is added to the component B to increase the molecular weight of the glue, wherein the chain extender is at least one selected from aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate; preferably, the polyisocyanate-based compound is selected from one or more of diphenylmethane diisocyanate, toluene diisocyanate, liquefied MDI, dicyclohexylmethane diisocyanate, isophorone diisocyanate, polymethylene polyphenyl polyisocyanate; more preferably, the isocyanate groups in the a-component are selected from diphenylmethane diisocyanate or toluene diisocyanate. The chain extender is added in an amount of 1-10% of the total mass of the B component, preferably in an amount of 3-8% of the total mass of the B component.
The invention also provides a preparation method of the two-component solvent-free polyurethane laminating adhesive, which comprises the following steps:
1) Uniformly mixing the polyhydroxy compound I and polyisocyanate, and reacting at 60-90 ℃ for 2-3 hours to obtain a component A;
2) Uniformly mixing the polyhydroxy compound II, optional adhesion promoter, leveling agent, tackifier and chain extender at 60-90 ℃ for reaction for 1-2h to obtain a component B;
3) The A component and the B component are mixed according to isocyanate groups (NCO) in the A component: and mixing the component B with the hydroxyl (OH) molar ratio of 1.5-2.2 to obtain the double-component solvent-free polyurethane laminating adhesive.
By adopting the technical scheme, the invention has the following beneficial effects:
(1) The double-component solvent-free polyurethane laminating adhesive has the advantages that the viscosity of the prepared component B is high, the initial viscosity is good, the leveling property of the compounded adhesive is greatly improved, the composite PET/VMPET and PET/AL high-barrier structures still have no white spots in appearance at high rotating speed, the sizing speed is improved, and the double-component solvent-free polyurethane laminating adhesive is suitable for industrial application by virtue of the design of the component formula of A, B, in particular to the structural design of different polyester polyols.
(2) The film laminating adhesive with sensitive viscosity-temperature change is prepared by matching the type selection and the content of the two different types of polyester polyol and polyether polyol polyurethane prepolymer, the viscosity is greatly changed along with the temperature change, and the sizing cost is reduced.
(3) The double-component solvent-free polyurethane laminating adhesive has excellent steaming and boiling resistance and has the advantages of high-barrier aluminum foil structure compounding and steaming and boiling integration.
(4) The double-component solvent-free polyurethane laminating adhesive has the advantages of high compounding fastness, high compounding efficiency and environmental friendliness compared with solvent-free polyurethane laminating adhesive, and solves the problem that the existing solvent-free laminating adhesive cannot compound the industrial pain points of PET/VMPET and PET/AL high-barrier structures.
Detailed Description
The following examples will further illustrate the method provided by the present invention for a better understanding of the technical solution of the present invention, but the present invention is not limited to the examples listed but should also include any other known modifications within the scope of the claims of the present invention.
In the embodiment of the invention, the polyurethane laminating adhesive is prepared by the following steps:
1) Uniformly mixing a polyhydroxy compound and excessive polyisocyanate in a certain proportion, and reacting for 2 hours at 80 ℃ to obtain a component A;
2) Reacting the polyhydroxy compound II, the adhesion promoter, the leveling agent, the tackifier and the chain extender for 2 hours at 70 ℃ to obtain a component B;
3) The A component and the B component are mixed according to isocyanate groups (NCO) in the A component: and (2) mixing the component B with a hydroxyl (OH) molar ratio of 1.5-2.2 (the specific molar ratio is shown in Table 2) to obtain the double-component solvent-free polyurethane laminating adhesive.
The composite technological parameters of the two-component solvent-free polyurethane laminating adhesive prepared by the method on a professional solvent-free compounding machine are as follows:
table 1 parameters of polyurethane laminating adhesive for solvent-free compounding machine
The invention is further illustrated by the following more specific examples, which do not limit the scope of the invention in any way.
The raw materials used in the examples and comparative examples are as follows:
Polyether polyol:
polyether polyol 1: DL400, polyoxypropylene diol, molecular weight 400, manufactured by Shandong Lanxingdong Co., ltd;
Polyether polyol 2: DL1000D, polyoxypropylene diol, molecular weight 1000, manufactured by Shandong Lanxing Dong Co., ltd;
diethylene glycol: molecular weight 106, jinan Yuan Xiang chemical Co., ltd;
Polyester polyol:
Polyester polyol 0: 219g of adipic acid, 473g of terephthalic acid, 104g of neopentyl glycol, 159g of diethylene glycol, 62g of ethylene glycol, 134g of trimethylolpropane and 40ppm of tetrabutyl titanate catalyst are added into a four-neck flask with a thermometer, a stirrer, a condenser pipe and a nitrogen device, heated and stirred uniformly, and heated to 160 ℃ for 16 hours of reaction; continuously heating to 240 ℃, and vacuumizing at the temperature for about 10 hours to obtain polyester polyol 0 with a hydroxyl value of 57.3mg KOH/g and a molecular weight of 2000;
Polyester polyol 1-1: adding 511g of adipic acid, 141g of isophthalic acid, 144g of 1, 4-cyclohexanedimethanol and 45g of diethylene glycol 321 g of 1, 4-butanediol into a four-neck flask with a thermometer, a stirrer, a condenser pipe and a nitrogen device, adding 40ppm of tetrabutyl titanate catalyst, heating and stirring uniformly, heating to 160 ℃, and reacting for 16 hours; continuously heating to 240 ℃, and vacuumizing at the temperature for about 7 hours to obtain polyester polyol 1-1 with a hydroxyl value of 54.6mg KOH/g and a molecular weight of 2000;
Polyester polyol 1-2: 584g of adipic acid, 58g of isophthalic acid, 144g of 1, 4-cyclohexanedimethanol, 59g of diethylene glycol 15 g of 1, 4-butanediol 180g of 1, 6-hexanediol and 59g of tetrabutyl titanate catalyst with 40ppm are added into a four-neck flask with a thermometer, a stirrer, a condenser and a nitrogen device, and the mixture is heated and stirred uniformly, and the temperature is raised to 160 ℃ for reaction for about 16 hours; continuously heating to 240 ℃, and vacuumizing at the temperature for about 7 hours to obtain polyester polyol 1-2 with a hydroxyl value of 57.4mg KOH/g and a molecular weight of 2000;
polyester polyol 2-1: adding 314g of adipic acid, 365g of isophthalic acid, 90g of neopentyl glycol 104g of 2-methyl-1, 3-propanediol, 265g of diethylene glycol, 45g of 1, 4-butanediol into a four-neck flask with a thermometer, a stirrer, a condenser pipe and a nitrogen device, adding 40ppm of tetrabutyl titanate catalyst, heating and stirring uniformly, heating to 160 ℃, and reacting for about 16 hours; continuously heating to 240 ℃, and vacuumizing at the temperature for about 5 hours to obtain polyester polyol 2-1 with a hydroxyl value of 108.5mg KOH/g and a molecular weight of 1000;
Polyester polyol 2-2: 66g of adipic acid, 647g of isophthalic acid, 45g of neopentyl glycol 104g of 2-methyl-1, 3-propanediol, 265g of diethylene glycol, 90g of 1, 4-butanediol, 40ppm of tetrabutyl titanate catalyst and the like are added into a four-neck flask with a thermometer, a stirrer, a condenser and a nitrogen device, and the mixture is heated and stirred uniformly, and the temperature is raised to 160 ℃ for reaction for about 16 hours; continuously heating to 240 ℃, and vacuumizing at the temperature for about 5 hours to obtain polyester polyol 2-2 with a hydroxyl value of 112.5mg KOH/g and a molecular weight of 1000;
Polyester polyol 2-3: 66g of adipic acid, 647g of isophthalic acid, 45g of neopentyl glycol 78g of 2-methyl-1, 3-propanediol, 265g of diethylene glycol, 90g of 1, 4-butanediol, 77.5g of modified butylene glycol, 40ppm of tetrabutyl titanate catalyst and the like are added into a four-neck flask with a thermometer, a stirrer, a condenser pipe and a nitrogen device, and the mixture is heated and stirred uniformly, and the temperature is raised to 160 ℃ for reaction for about 16 hours; continuously heating to 240 ℃, and vacuumizing at the temperature for about 5 hours to obtain polyester polyol 2-3 with a hydroxyl value of 115.2mg KOH/g and a molecular weight of 1000;
Polyester polyol 2-4: 66g of adipic acid, 647g of isophthalic acid, 90g of neopentyl glycol 208,2-methyl-1, 3-propanediol, 53g of diethylene glycol, 45g of 1, 4-butanediol and 310g of modified butylene glycol are added into a four-neck flask with a thermometer, a stirrer, a condenser pipe and a nitrogen device, and the mixture is heated and stirred uniformly, and the temperature is raised to 160 ℃ for reaction for about 16 hours; continuously heating to 240 ℃, and vacuumizing at the temperature for about 5 hours to obtain polyester polyol 2-4 with a hydroxyl value of 114.8mg KOH/g and a molecular weight of 1000;
The preparation method of the modified butylene glycol comprises the following steps: 1767 g of 1, 4-butylene glycol and 533g of polymethyl hydrogen siloxane are added into a reaction kettle, in a nitrogen atmosphere, the temperature is raised to 80 ℃ and the mixture is stirred, 0.5g of chloroplatinic acid catalyst is added, the mixture is stirred and kept for 0.5h, the temperature is continuously raised to 110 ℃ and the reaction is carried out for 6h, and the rest polymethyl hydrogen siloxane is removed by rotary evaporation, so that the final product of the modified butylene glycol is obtained.
Organic isocyanate: MDI-50, nco% = 33.5wt%, manufactured by vancomic chemical group limited;
organic isocyanate: MDI-100, nco% = 33.5wt%, manufactured by vancomic chemical group limited;
Organic isocyanate: IPDI, NCO% = 37.79wt%, manufactured by vancomic chemical group limited;
adjuvant 1, gamma glycidyl ether oxypropyl trimethoxysilane, chemically pure, and aladine;
Auxiliary 2: siloxane modified polyether, chemically pure, pick chemistry;
Auxiliary agent 3: modified rosin resin, guangzhou sub-standard technology Co., ltd;
Polymethylhydrosiloxane: molecular weight 222, beijing Baoling technologies Co., ltd;
1, 4-butene diol: chemically pure, shanghai Meilin Biochemical technologies Co.
Preparation of A component
Adding the isocyanate component into a reaction device, adding polyether polyol raw materials, starting stirring, heating to 80 ℃, reacting for 2 hours, cooling to 60 ℃, and discharging to obtain the component A.
Table 2A component formulation and ratio (the addition amount of each component is in parts by weight)
| Category(s) | A1 | A2 | A3 | A4 | A5 | A6 |
| MDI-50 | 60 | 60 | 55 | 50 | 40 | 30 |
| IPDI | / | / | 5 | 10 | 20 | 30 |
| DL400 | 15 | 32 | 32 | 34 | 34 | 34 |
| DL1000D | 25 | 8 | 8 | 6 | 6 | 6 |
| NCO％ | 14.89 | 12.73 | 12.95 | 12.90 | 13.33 | 13.76 |
| Viscosity (65 ℃ C.) | 218 | 1178 | 1095 | 875 | 721 | 634 |
Preparation of component B
Adding polyether polyol into a reaction device, adding polyester polyol and related auxiliary agents, stirring, heating to 70 ℃, cooling to 40 ℃ after 2 hours, and discharging to obtain a component B.
Table 3B component formulas and proportions (the addition amount of each component is in parts by weight)
| Type(s) | B1 | B2 | B3 | B4 | B5 | B6 | B7 | B8 |
| MDI-100 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Polyester polyol 0 | 64.7 | / | / | / | / | / | / | / |
| Polyester polyol 1-1 | / | / | 64.7 | / | / | / | / | / |
| Polyester polyol 1-2 | / | / | / | 24.7 | 44.7 | 44.7 | 45 | 44.7 |
| Polyester polyol 2-1 | / | / | / | 30 | / | / | / | / |
| Polyester polyol 2-2 | / | 67.7 | / | / | 20 | / | / | / |
| Polyester polyol 2-3 | / | / | / | / | / | 20 | 20 | / |
| Polyester polyol 2-4 | / | / | / | / | / | / | / | 20 |
| Diethylene glycol | 5 | 2 | 5 | 5 | 5 | 5 | 5 | 5 |
| Auxiliary 1 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| DL400 | 20 | 20 | 20 | 30 | 20 | 20 | 20 | 20 |
| Auxiliary 2 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | / | 0.3 |
| Auxiliary 3 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Hydroxyl value mg KOH/g | 128 | 129 | 124 | 132 | 133 | 134 | 133 | 133 |
| Viscosity (65 ℃ C.) | 1027 | 832 | 302 | 608 | 645 | 665 | 691 | 675 |
Preparation of performance test samples:
Mixing the component A and the component B according to the ratio of R value = N (NCO): n (OH) = 1.5-2.2, compounding PET/AL film on a solvent-free compounding machine at 65 ℃ and at 50-180m/min, compounding the PET/AL film and the RCPP film after compounding, observing the appearance bubble white spot condition of the PET/AL film, curing the film in a curing chamber at 45 ℃ after the PET/AL/RCPP structure is compounded, observing the appearance of the cured film after curing for 3 days, and testing the compounding fastness and the digestion performance of the PET/AL/RCPP film.
PET/AL film appearance: visual inspection;
peel strength was tested according to standard GB/T8808-1988;
Table 4 performance test data for each example of laminating adhesive
TABLE 5 Compound fastness data for the examples
As can be seen from the results in Table 4, examples 4 and 6-9, the PET/AL appearance had no white spots at a machine speed of 140 m/min; comparative example 1 at a machine speed of 80m/min, white spots appear on the appearance of PET/AL because the viscosity of the A1 component in comparative example 1 is low, and the initial adhesion cannot resist sliding shrinkage between PET/AL substrates after compounding; the white point appears on the appearance of PET/AL at the machine speed of 50m/min in comparative example 2 because the viscosity-temperature sensitivity and leveling property of the common B1 component in comparative example 1 are poor, which is unfavorable for the compounding of PET/AL structure; in comparative examples 2 and 3, white spots also appear in the PET/AL appearance at a machine speed of 80m/min, because the polyester polyol 1 and the polyester polyol 2 are used alone, and the effects of high temperature sensitivity of the viscosity of the components and good leveling property cannot be satisfied at the same time. The above results demonstrate that the simultaneous use of polyester polyol 1 and polyester polyol 2 in component B is desirable to have a synergistic effect that is effective in improving the PET/AL appearance. The comparative results of examples 4,7,8,9 demonstrate that the modified butenediol incorporated into polyester polyol 2 provides a significant improvement in PET/AL appearance in the synergistic effect of polyester polyol 1. For the A component, examples 2-5 are compared with comparative example 1, as the viscosity of the A component is increased, the proper IPDI content is introduced simultaneously, so that the proper viscosity at high temperature can be ensured, the initial adhesion at room temperature is high, the composite appearance is obviously improved, but the viscosity of the component at room temperature is reduced due to the too high IPDI content, and the composite fastness is also unfavorable.
As is clear from the results of Table 5, the results of examples 4,8 and 9 show that the heat resistance of the adhesive is significantly improved by grafting the modified butenediol having a siloxane structure with the polyester polyol 2, and in particular, the strength after steaming can be 5N or more as compared with the result of example 9.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (36)
1. The double-component solvent-free polyurethane laminating adhesive comprises an A component and a B component, and is characterized in that the A component is a polyurethane prepolymer which is formed by reacting a polyhydroxy compound I and polyisocyanate and has an isocyanate-based end group, the viscosity of the polyurethane prepolymer is 500-1400 mPa.s at 65 ℃, the NCO content of the A component is 10-14%, and the polyhydroxy compound I in the A component is one or more of polyester polyol and/or polyether polyol; the component B is a polyhydroxy compound II; isocyanate (NCO) groups in the a component: the molar ratio of hydroxyl (OH) in the component B is 1.5-2.2;
the viscosity of the component B is 200-900 mPas at 65 ℃;
The B-component polyhydroxy compound II comprises polyester polyol, polyether polyol with the mass ratio of 0-40% and a chain extender, wherein the chain extender is at least one of aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate;
The polyester polyol in the B component comprises a polyester polyol 1 and a polyester polyol 2,
Synthesizing a dihydric alcohol of the polyester polyol 1 into a dihydric alcohol which is linear and does not contain side group, and synthesizing a polyester polyol 2 into a polyester polyol containing a side methyl structure;
The dibasic acid and/or anhydride for synthesizing the polyester polyol 1 comprises one or more of adipic acid, isophthalic acid, terephthalic acid, phthalic anhydride and sebacic acid, and the molar content of aromatic dibasic acid/anhydride in the dibasic acid for synthesizing the polyester polyol 1 is below 20mol% of the total amount of the dibasic acid; the dihydric alcohol for synthesizing the polyester polyol 1 comprises one or more of ethylene glycol, diethylene glycol, triethylene glycol, 1, 4-butanediol, 1, 6-hexanediol and 1, 4-cyclohexanedimethanol dihydric alcohol, and the dihydric alcohol for synthesizing the polyester polyol 1 at least comprises one of diethylene glycol and 1, 4-cyclohexanedimethanol dihydric alcohol;
the dibasic acid and/or anhydride of the synthetic polyester polyol 2 comprises one or more of adipic acid, isophthalic acid, terephthalic acid, phthalic anhydride and sebacic acid; diols of synthetic polyester polyol 2 include ethylene glycol, diethylene glycol, triethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, 2-methyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, and modified butenediol.
2. The polyurethane laminating adhesive according to claim 1, wherein the polyurethane prepolymer has a viscosity of 600-1200 mPa-s at 65 ℃.
3. The polyurethane laminating adhesive according to claim 1, wherein in the a component, the isocyanate groups (NCO): the molar ratio of hydroxyl groups (OH) in the component B is 1.7-1.9.
4. The polyurethane laminating adhesive according to claim 1, wherein the polyisocyanate in the a component is at least one selected from the group consisting of aromatic polyisocyanates, aliphatic polyisocyanates, and cycloaliphatic polyisocyanates.
5. The polyurethane laminating adhesive according to claim 4, wherein the polyisocyanate is one or more selected from the group consisting of diphenylmethane diisocyanate, liquefied MDI, dicyclohexylmethane diisocyanate, isophorone diisocyanate, polymethylene polyphenyl polyisocyanates.
6. The polyurethane laminating adhesive according to claim 5, wherein the polyisocyanate comprises 5 to 50wt% of isophorone diisocyanate.
7. The polyurethane laminating adhesive according to claim 4, wherein the isocyanate in the A component is selected from diphenylmethane diisocyanate and isophorone diisocyanate.
8. The polyurethane laminating adhesive according to claim 4, wherein the polyisocyanate in the component A accounts for 40-80% by mass.
9. The polyurethane laminating adhesive according to claim 8, wherein the polyisocyanate in the component A accounts for 50-70% by mass.
10. The polyurethane laminating adhesive according to claim 1, wherein the mass content of the polyhydroxy compound I in the component A is 20-60%.
11. The polyurethane laminating adhesive according to claim 1, wherein the polyether polyol is a hydroxyl-terminated oligomer having a main chain with an ether bond having a molecular weight of 400 to 2000, which is initiated by using a low molecular compound having a hydroxyl group, an amino group or both of them as an initiator.
12. The polyurethane laminating adhesive of claim 1, wherein the functionality of the polyhydroxy compound in the a-component is two functionalities.
13. The polyurethane laminating adhesive of claim 12, wherein the polyol in the a-component is a difunctional polyether polyol.
14. The polyurethane laminating adhesive of claim 1, wherein the B component has a hydroxyl value of 80-200mg KOH/g.
15. The polyurethane laminating adhesive of claim 14, wherein the B component has a hydroxyl value of 100-150mg KOH/g and a viscosity of 300-700 mPa-s at 65 ℃.
16. The polyurethane laminating adhesive according to claim 1, wherein the polyether polyol in the component B is a hydroxyl-terminated oligomer with a main chain having an ether bond and a molecular weight of 400-2000, which is initiated by using a low molecular compound having a hydroxyl group, an amino group or both as an initiator.
17. The polyurethane laminating adhesive of claim 16, wherein the polyether polyol functionality in the B component is two functionalities.
18. The polyurethane laminating adhesive according to claim 1, wherein the polyester polyol in the B component comprises a polyester polyol 1 and a polyester polyol 2, and the mass ratio of the polyester polyol 1 in the B component is 20-60% and the mass ratio of the polyester polyol 2 in the B component is 10-30%.
19. The polyurethane laminating adhesive of claim 18, wherein the functionality of both polyester polyol 1 and polyester polyol 2 is difunctional.
20. The polyurethane laminating adhesive according to claim 1, wherein the molar content of the linear diol without side group in the diol synthesized with the polyester polyol 1 is more than 0.1 times of the total molar amount of the diol.
21. The polyurethane laminating adhesive according to claim 1, wherein the polyester polyol 1 has a crystallization temperature of less than 25 ℃.
22. The polyurethane laminating adhesive according to claim 1, wherein the molar content of diethylene glycol and 1, 4-cyclohexanedimethanol diol in the diol synthesized with the polyester polyol 1 is more than 0.3 times of the total molar amount of the diol.
23. The polyurethane laminating adhesive according to claim 1, wherein the polyester polyol 1 has a molecular weight of 400 to 5000.
24. The polyurethane laminating adhesive of claim 23, wherein the polyester polyol 1 has a molecular weight of 800 to 3000.
25. The polyurethane laminating adhesive according to claim 1, wherein the molar content of the aromatic dibasic acid/anhydride in the dibasic acid of the synthetic polyester polyol 1 is 5mol% or more of the total amount of the dibasic acid.
26. The polyurethane laminating adhesive according to claim 1, wherein the dibasic acid and/or anhydride synthesized by the polyester polyol 1 is one or more of adipic acid, isophthalic acid and terephthalic acid, and the dibasic alcohol synthesized by the polyester polyol 1 is one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 6-hexanediol and 1, 4-cyclohexanedimethanol.
27. The polyurethane laminating adhesive according to claim 1, wherein the diol of the synthetic polyester polyol 2 comprises a diol having a methyl structure in a side chain.
28. The polyurethane laminating adhesive according to claim 27, wherein the molar ratio of the diol having a methyl structure in the side chain to the total amount of the diol in the diol of the synthetic polyester polyol 2 is in the range of 0.3 to 0.8.
29. The polyurethane laminating adhesive according to claim 1, wherein the dibasic acid and/or anhydride containing benzene ring in the dibasic acid of the synthetic polyester polyol 2 accounts for 50% -90% of the total molar amount of the dibasic acid.
30. The polyurethane laminating adhesive according to claim 1, wherein the molecular weight of the polyester polyol 2 is 400-4000.
31. The polyurethane laminating adhesive of claim 30, wherein the polyester polyol 2 has a molecular weight of 800 to 3000.
32. The polyurethane laminating adhesive according to claim 1, wherein the dibasic acid and/or anhydride of the synthetic polyester polyol 2 is selected from adipic acid, isophthalic acid, phthalic anhydride.
33. The polyurethane laminating adhesive according to claim 1, wherein the modified butenediol is a product obtained by reacting 1, 4-butenediol with polymethylhydrosiloxane, and the preparation method comprises the following steps: in a nitrogen atmosphere, 1, 4-butylene glycol and polymethylhydrosiloxane are added into a reaction kettle in a molar ratio of 1:1-1.5, heating to 70-90 ℃, adding 0.01-0.1% chloroplatinic acid catalyst, stirring, preserving heat for 0.5-1h, continuously heating to 90-120 ℃ for reacting for 5-8h, and removing the residual polymethylhydrosiloxane by rotary evaporation to obtain the final product of the modified butenediol.
34. The polyurethane laminating adhesive of claim 33, wherein the molar amount of the modified butenediol in the polyester polyol 2 is less than 0.3 of the total moles of diols.
35. The polyurethane laminating adhesive of claim 34, wherein the molar amount of the modified butenediol is 0.05 to 0.2 based on the total molar amount of the diols.
36. The method for preparing the polyurethane laminating adhesive as claimed in any one of claims 1 to 35, comprising the steps of:
1) Uniformly mixing the polyhydroxy compound I and polyisocyanate, and reacting at 60-90 ℃ for 2-3 hours to obtain a component A;
2) Reacting the polyhydroxy compound II, an optional adhesion promoter and/or a leveling agent and/or a tackifier at 60-90 ℃ for 1-2h to obtain a component B;
3) The A component and the B component are mixed according to isocyanate groups (NCO) in the A component: and mixing the component B with the hydroxyl (OH) molar ratio of 1.5-2.2 to obtain the double-component solvent-free polyurethane laminating adhesive.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544880A (en) * | 2009-03-12 | 2009-09-30 | 中山市康和化工有限公司 | Adhesive for soft package compound and preparation method thereof |
| CN103897191A (en) * | 2014-02-20 | 2014-07-02 | 合肥市科天化工有限公司 | Preparation method of hydroxy-terminated polysiloxane polyol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544880A (en) * | 2009-03-12 | 2009-09-30 | 中山市康和化工有限公司 | Adhesive for soft package compound and preparation method thereof |
| CN103897191A (en) * | 2014-02-20 | 2014-07-02 | 合肥市科天化工有限公司 | Preparation method of hydroxy-terminated polysiloxane polyol |
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