CN105176475A - Solvent-free polyurethane adhesive with high initial viscosity and preparation method thereof - Google Patents
Solvent-free polyurethane adhesive with high initial viscosity and preparation method thereof Download PDFInfo
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- CN105176475A CN105176475A CN201510587969.8A CN201510587969A CN105176475A CN 105176475 A CN105176475 A CN 105176475A CN 201510587969 A CN201510587969 A CN 201510587969A CN 105176475 A CN105176475 A CN 105176475A
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- component
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- polyol
- bonding strength
- high initial
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- 239000012940 solvent-free polyurethane adhesive Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 6
- 229920005862 polyol Polymers 0.000 claims abstract description 42
- 150000003077 polyols Chemical class 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 21
- 229920000570 polyether Polymers 0.000 claims abstract description 21
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 18
- 239000008158 vegetable oil Substances 0.000 claims abstract description 18
- 239000004814 polyurethane Substances 0.000 claims abstract description 15
- 229920002635 polyurethane Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- -1 isocyanate group compound Chemical class 0.000 claims abstract description 10
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 7
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000011127 biaxially oriented polypropylene Substances 0.000 claims description 13
- 229920006378 biaxially oriented polypropylene Polymers 0.000 claims description 13
- 239000012948 isocyanate Substances 0.000 claims description 13
- 150000002513 isocyanates Chemical class 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 12
- 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
- 150000002009 diols Chemical class 0.000 claims description 9
- 229920001451 polypropylene glycol Polymers 0.000 claims description 9
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 238000003851 corona treatment Methods 0.000 claims description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 235000019198 oils Nutrition 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 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 claims description 4
- 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 4
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000005030 aluminium foil Substances 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 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 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 235000005513 chalcones Nutrition 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229960002725 isoflurane Drugs 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 239000000853 adhesive Substances 0.000 abstract description 12
- 230000001070 adhesive effect Effects 0.000 abstract description 12
- 239000012790 adhesive layer Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 12
- 229920002799 BoPET Polymers 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- 239000003292 glue Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 5
- 238000005304 joining Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- AYEFIAVHMUFQPZ-UHFFFAOYSA-N propane-1,2-diol;prop-2-enoic acid Chemical class CC(O)CO.OC(=O)C=C AYEFIAVHMUFQPZ-UHFFFAOYSA-N 0.000 description 2
- JMWGZSWSTCGVLX-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical class CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CCC(CO)(CO)CO JMWGZSWSTCGVLX-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical class OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000005025 cast polypropylene Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000206 moulding compound Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a solvent-free bi-component polyurethane adhesive with high initial viscosity. The adhesive comprises a component A and a component B, wherein the component A is a blocked isocyanate group compound, the component B is a polyhydroxy compound, and the component A and the component B are mixed according to the molar ratio of NCO:OH of 1.1-1.5 so as to obtain the solvent-free polyurethane adhesive with high initial viscosity. The component A, namely the blocked isocyanate group compound, is formed by reaction of polyisocyanate and the polyhydroxy compound. The component B, namely the polyhydroxy compound, is composed of polyether polyol, or composed of polyether polyol and vegetable oil polyol, or composed of polyether polyol, vegetable oil polyol and tackifying resin. The viscosity of the solvent-free compound adhesive is reduced, and certain initial viscosity can be ensured. Particularly, good initial viscosity can be achieved by only applying a thin adhesive layer.
Description
Technical field
The present invention relates to a kind of no-solvent polyurethane composite adhesive being applicable to composite soft packaging field, be specifically related to a kind of high initial bonding strength solvent-free polyurethane adhesive and preparation method thereof.
Background technology
Solvent type polyurethane compound binder, through development for many years, is widely used at packaging industry.But owing to using a large amount of organic solvents, there is very large destruction for environment, there is the shortcomings such as inflammable, explosive, smell is large simultaneously.Therefore along with country is for the concern of environmental protection and the people care for the security of packaging, the solvent-free composite adhesive of environmental protection will become the trend of following packaging industry.
At present, less viscosity must be had because solvent-free process determines solvent-free composite adhesive, otherwise the operability of the mobility in production process and the coating of upper machine is all poor, easily causes quality accident, so the general feature of solvent-free products on market is that viscosity is low.Because adhesive viscosities is low, cause the molecular weight and molecular weight of the resin in tackiness agent, this change result in solvent-free composite adhesive compared to solvent borne polyurethane tackiness agent, and the tack after film forming is poor, usually needs to be regulated by equipment.
The present invention aims to provide a kind of high initial bonding strength solvent-free polyurethane adhesive, and it, while the viscosity reducing solvent-free composite adhesive, can ensure certain initial bonding strength again.Especially only execute the very thin one deck glue of Tu and just can reach good initial bonding strength, curing speed is also improved.This use range for expansion and popularization adhesive for solvent-free use has active effect.
Summary of the invention
The invention provides solvent-free polyurethane adhesive of a kind of high initial bonding strength and preparation method thereof, there is high initial bonding strength, high strength and low viscous solvent-free double-component polyurethane tackiness agent, may be used in the package compound film of food, medicine etc.
The present invention implements by the following technical programs:
The invention process invention provides a kind of solvent-free double-component polyurethane tackiness agent of high initial bonding strength, this tackiness agent comprises: component A and B component, wherein component A is isocyanate terminated based compound, B component is polyol, and component A and B component are that 1.1-1.5 carries out mixing and obtain high initial bonding strength solvent-free polyurethane adhesive according to NCO:OH mol ratio.
The isocyanate terminated based compound of described component A is reacted by polyisocyanates and polyol and forms, and wherein polyol is made up of polyether glycol, vegetable oil polyol and terminal hydroxy group acrylate resin.
Described B component polyol is made up of polyether glycol, or is made up of polyether glycol, vegetable oil polyol, or is made up of polyether glycol, vegetable oil polyol and tackifying resin.
Isocyanate content in isocyanate terminated compound in described component A is 8%-18%, and preferred isocyanate content is 13%-17%.
Polyether glycol in described component A accounts for the 10%-60% of polyol hydroxyl mole total amount, and vegetable oil polyol accounts for the 20%-80% of polyol hydroxyl mole total amount, and terminal hydroxy group acrylic resin accounts for the 5%-20% of polyol hydroxyl mole total amount.
Polyether glycol in described component A, its molecular weight ranges at 300-2500, by one or both mixtures formed in polyoxypropyleneglycol and polytetrahydrofuran diol.
Vegetable oil polyol in described component A is by the mixture that in Viscotrol C, epoxy soybean oil, plam oil, one or more form.
Terminal hydroxy group acrylic resin in described component A is the polymkeric substance formed after radical polymerization by the monomer of esters of acrylic acid.The acrylic ester monomer selected is made up of one or more in methyl acrylate, butyl acrylate, vinylformic acid, methyl methacrylate, methacrylic acid, hydroxyethyl methylacrylate, Rocryl 410, trimethylolpropane trimethacrylate.The initiator used is by one or more in Diisopropyl azodicarboxylate, benzoyl peroxide, 2,2'-Azobis(2,4-dimethylvaleronitrile), and usage quantity is the 0.5%-2% of acrylic ester monomer amount.
Polyisocyanates in described component A is by one or more mixtures formed in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), liquefied mdi, isoflurane chalcone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), two ring ethyl methane vulcabond (HMDI) etc.
Polyether glycol in described B component, its molecular weight ranges is at 300-2500, and by one or both mixtures formed in polyoxypropyleneglycol and polytetrahydrofuran diol, consumption accounts for the 10%-60% of B component total amount.
Vegetable oil polyol in described B component is by the mixture that in Viscotrol C, epoxy soybean oil, plam oil, one or more form, and consumption accounts for the 20%-50% of B component total amount.
Tackifying resin in described B component is by one or more mixtures formed in terpine resin, Gum Rosin, petroleum resinoid, and consumption accounts for the 1%-10% of B component total amount.
The preparation method of above-mentioned high initial bonding strength solvent-free polyurethane adhesive, comprises the steps:
1. the polyether glycol in component A and/or vegetable oil polyol are heated to 60 degree of-100 degree, drip the acrylic ester monomer solution being mixed with initiator, drip off in 2h-3h, insulation 1h-2h, mixture is heated to 110 degree of-120 degree, dewater 1.5h-2.5h under pressure <1.3KPa, by water content control below 0.1%, after cool to less than 70 degree, add polyisocyanates, under 80-90 degree, react the component A that 2-3h obtains isocyanate terminated compound.
2. polyether glycol in B component and/or vegetable oil polyol and/or tackifying resin are heated to 110-120 degree, dissolve 0.5h-1h, dewater 1.5h-2.5h under pressure <1.3KPa, and by water content control below 0.1%, discharging obtains the B component of polyol.
Above-mentioned solvent-free polyurethane adhesive can be applied to compound in BOPP, CPP, PE, PET, PA, aluminium foil and aluminium plating film between any two kinds of materials (film surface must through corona treatment), and is applicable to high speed compound.
Usefulness of the present invention is:
1, solvent-free polyurethane adhesive of the present invention is while the viscosity (initial viscosity after joining glue is 500CP) reducing solvent-free composite adhesive, can ensure certain initial bonding strength again; Especially only execute the very thin one deck glue (15mm) of Tu and just can reach good initial bonding strength.
2, solvent-free polyurethane adhesive curing speed of the present invention is also improved, can also water boiling resistance, and this has active effect for the use range expanded and promote adhesive for solvent-free use.
Embodiment
embodiment 1:
The synthesis of A-0
Be the polyoxypropyleneglycol of 1000 by 50 parts of molecular weight, the Viscotrol C of 100 parts, load in reaction vessel, temperature of reaction rises to 110 degree, and dewater 2h under pressure <1.3KPa, by water content control below 0.1%, after cool to less than 70 degree, add 252 parts of diphenylmethanediisocyanates (MDI), under 85 degree, reaction 2.5h, filters discharging and obtains component A.
embodiment 2:
The synthesis of A-1
Be the polyoxypropyleneglycol of 1000 by 50 parts of molecular weight, the Viscotrol C of 100 parts, load in reaction vessel, be warmed up to 60 degree, drip containing 0.2 part of Diisopropyl azodicarboxylate, 15 parts of butyl acrylates, the mixing solutions of 5 parts of methyl methacrylates, dropwise in 2h, insulation 1.5h, temperature of reaction is risen to 110 degree, dewater 2h under pressure <1.3KPa, by water content control below 0.1%, after cool to less than 70 degree, add 252 parts of diphenylmethanediisocyanates (MDI), under 85 degree, reaction 2.5h, filter discharging and obtain component A.
embodiment 3:
The synthesis of A-2
Be the polyoxypropyleneglycol of 1000 by 50 parts of molecular weight, the Viscotrol C of 100 parts, load in reaction vessel, be warmed up to 900 degree, drip containing 0.2 part of benzoyl peroxide, 10 parts of butyl acrylates, 5 parts of methyl methacrylates, the mixing solutions of 5 parts of Hydroxyethyl acrylates, dropwise in 2h, insulation 1.5h, temperature of reaction is risen to 110 degree, dewater 2h under pressure <1.3KPa, by water content control below 0.1%, after cool to less than 70 degree, add 252 parts of diphenylmethanediisocyanates (MDI), under 85 degree, reaction 2.5h, filter discharging and obtain component A.
embodiment 4:
The synthesis of A-3
Be the polyoxypropyleneglycol of 400 by 50 parts of molecular weight, the Viscotrol C of 100 parts, load in reaction vessel, be warmed up to 60 degree, drip containing 0.2 part of 2,2'-Azobis(2,4-dimethylvaleronitrile), 10 parts of butyl acrylates, 5 parts of methyl methacrylates, the mixing solutions of 5 parts of Propylene glycol monoacrylates, dropwise in 2h, insulation 1.5h, temperature of reaction is risen to 110 degree, dewater 2h under pressure <1.3KPa, by water content control below 0.1%, after cool to less than 70 degree, add 273 parts of diphenylmethanediisocyanates (MDI), under 85 degree, reaction 2.5h, filter discharging and obtain component A.
embodiment 5:
The synthesis of A-4
Be the polyoxypropyleneglycol of 400 by 50 parts of molecular weight, the Viscotrol C of 100 parts, load in reaction vessel, be warmed up to 60 degree, drip containing 0.2 part of Diisopropyl azodicarboxylate, 10 parts of butyl acrylates, 5 parts of trimethylolpropane trimethacrylates, the mixing solutions of 5 parts of Propylene glycol monoacrylates, dropwise in 2h, insulation 1.5h, temperature of reaction is risen to 110 degree, dewater 2h under pressure <1.3KPa, by water content control below 0.1%, after cool to less than 70 degree, add 273 parts of diphenylmethanediisocyanates (MDI), under 85 degree, reaction 2.5h, filter discharging and obtain component A.
embodiment 6:
The synthesis of B-0
Be the polytetrahydrofuran diol of 400 by 200 parts of molecular weight, the Viscotrol C of 150 parts loads in reaction vessel, is heated to 115 degree, dissolve 0.5h, dewater 2h under pressure <1.3KPa, and by water content control below 0.1%, discharging obtains the B component of polyol.
embodiment 7:
The synthesis of B-1
Be the polytetrahydrofuran diol of 400 by 200 parts of molecular weight, the Viscotrol C of 150 parts, 20g terpine resin loads in reaction vessel, be heated to 115 degree, dissolve 0.5h, dewater 2h under pressure <1.3KPa, and by water content control below 0.1%, discharging obtains the B component of polyol.
embodiment 8:
The synthesis of B-2
Be the polytetrahydrofuran diol of 400 by 200 parts of molecular weight, the Viscotrol C of 150 parts, the epoxy soybean oil of 20 parts, 20g Gum Rosin loads in reaction vessel, be heated to 115 degree, dissolve 0.5h, dewater 2h under pressure <1.3KPa, by water content control below 0.1%, discharging obtains the B component of polyol.
embodiment 9:
The synthesis of B-3
Be the polytetrahydrofuran diol of 400 by 200 parts of molecular weight, the Viscotrol C of 150 parts, the plam oil of 20 parts, 20g terpine resin loads in reaction vessel, be heated to 115 degree, dissolve 0.5h, dewater 2h under pressure <1.3KPa, by water content control below 0.1%, discharging obtains the B component of polyol.
embodiment 10:
The synthesis of B-4
Be the polytetrahydrofuran diol of 400 by 200 parts of molecular weight, the Viscotrol C of 150 parts, the plam oil of 20 parts, 20g petroleum-type C5 resin loads in reaction vessel, be heated to 115 degree, dissolve 0.5h, dewater 2h under pressure <1.3KPa, by water content control below 0.1%, discharging obtains the B component of polyol.
embodiment 11:
(simultaneous test)
Fully mixed at normal temperature 25 DEG C with 80 parts of B-0 by 100 parts of A-0, carry out at being coated with and being compounded in normal temperature 25 DEG C, matrix material uses BOPP and PET film, film through corona treatment, spread 1.0-2.0g/m
2, recombination velocity at 200m/min, under the thin-film material that compound is good machine test initial bonding strength, after under 45-55 degree slaking 24h, test its final stripping strength.
Initial bonding strength between BOPP/PET film is 0.01N/15mm, and final stripping strength is 4.23N/15mm.
embodiment 12:
Fully mixed at normal temperature 25 DEG C with 82 parts of B-1 by 100 parts of A-1, carry out at being coated with and being compounded in normal temperature 25 DEG C, matrix material uses BOPP and PET film, film through corona treatment, spread 1.0-2.0g/m
2, recombination velocity at 200m/min, under the thin-film material that compound is good machine test initial bonding strength, after under 45-55 degree slaking 24h, test its final stripping strength.
Joining the initial viscosity after glue is 500P.
Stripping strength between PET/Al paper tinsel is 8.1N/15mm; 100 DEG C of boiling water boilings after 5 hours stripping strength be 7.5N/15mm.
Initial bonding strength between OPP/PET film is 0.15N/15mm, and final stripping strength is 4.62N/15mm.
embodiment 13:
Fully mixed at normal temperature 25 DEG C with 86 parts of B-2 by 100 parts of A-2, carry out at being coated with and being compounded in normal temperature 25 DEG C, matrix material uses BOPP and PET film, film through corona treatment, spread 1.0-2.0g/m
2, recombination velocity at 200m/min, under the thin-film material that compound is good machine test initial bonding strength, after under 45-55 degree slaking 24h, test its final stripping strength.
Joining the initial viscosity after glue is 500P.
Stripping strength between PET/Al paper tinsel is 8.2N/15mm; 100 DEG C of boiling water boilings after 5 hours stripping strength be 7.9N/15mm.
Initial bonding strength between BOPP/PET film is 0.23N/15mm, and final stripping strength is 4.51N/15mm.
embodiment 14:
Fully mixed at normal temperature 25 DEG C with 84 parts of B-3 by 100 parts of A-3, carry out at being coated with and being compounded in normal temperature 25 DEG C, matrix material uses BOPP and PET film, film through corona treatment, spread 1.0-2.0g/m
2, recombination velocity at 200m/min, under the thin-film material that compound is good machine test initial bonding strength, after under 45-55 degree slaking 24h, test its final stripping strength.
Joining the initial viscosity after glue is 500P.
Stripping strength between PET/Al paper tinsel is 8.3N/15mm; 100 DEG C of boiling water boilings after 5 hours stripping strength be 8.2N/15mm.
Initial bonding strength between BOPP/PET film is 0.38N/15mm, and final stripping strength is 4.76N/15mm.
embodiment 15:
Fully mixed at normal temperature 25 DEG C with 84 parts of B-4 by 100 parts of A-4, carry out at being coated with and being compounded in normal temperature 25 DEG C, matrix material uses BOPP and PET film, film through corona treatment, spread 1.0-2.0g/m
2, recombination velocity at 200m/min, under the thin-film material that compound is good machine test initial bonding strength, after under 45-55 degree slaking 24h, test its final stripping strength.
Joining the initial viscosity after glue is 500P.
Stripping strength between PET/Al paper tinsel is 8.2N/15mm; 100 DEG C of boiling water boilings after 5 hours stripping strength be 7.9N/15mm.
Initial bonding strength between BOPP/PET film is 0.45N/15mm, and final stripping strength is 4.68N/15mm.
Multiple film glue of the present invention be mainly used in moulding compound (refer to can be applicable to CPP, BOPP, PE, PET, etc. the soft compound in plastics film between any two kinds of base materials), plastic-aluminum combined (comprising the soft compound between the plastics film such as aluminium foil and CPP, BOPP, PE, PET, PA).
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not limited by the examples; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the solvent-free double-component polyurethane tackiness agent of a high initial bonding strength, this tackiness agent comprises: component A and B component, wherein component A is isocyanate terminated based compound, B component is polyol, and component A and B component are that 1.1-1.5 carries out mixing and obtain high initial bonding strength solvent-free polyurethane adhesive according to NCO:OH mol ratio.
2. the solvent-free double-component polyurethane tackiness agent of high initial bonding strength according to claim 1, is characterized in that:
The isocyanate terminated based compound of described component A is reacted by polyisocyanates and polyol and forms, and wherein polyol is made up of polyether glycol, vegetable oil polyol and terminal hydroxy group acrylate resin;
Described B component polyol is made up of polyether glycol, or is made up of polyether glycol, vegetable oil polyol, or is made up of polyether glycol, vegetable oil polyol and tackifying resin.
3. the solvent-free double-component polyurethane tackiness agent of the high initial bonding strength described in claim 1-2, is characterized in that:
Isocyanate content in isocyanate terminated compound in described component A is 8%-18%, and preferred isocyanate content is 13%-17%;
Polyether glycol in described component A accounts for the 10%-60% of polyol hydroxyl mole total amount, and vegetable oil polyol accounts for the 20%-80% of polyol hydroxyl mole total amount, and terminal hydroxy group acrylic resin accounts for the 5%-20% of polyol hydroxyl mole total amount.
4. the solvent-free double-component polyurethane tackiness agent of high initial bonding strength according to claim 3, is characterized in that:
Isocyanate content is 13%-17%.
5. the solvent-free double-component polyurethane tackiness agent of the high initial bonding strength described in claim 1-2, is characterized in that:
Polyether glycol in described component A, its molecular weight ranges at 300-2500, by one or both mixtures formed in polyoxypropyleneglycol and polytetrahydrofuran diol;
Vegetable oil polyol in described component A is by the mixture that in Viscotrol C, epoxy soybean oil, plam oil, one or more form.
6. the solvent-free double-component polyurethane tackiness agent of the high initial bonding strength described in claim 1-2, is characterized in that:
Terminal hydroxy group acrylic resin in described component A is the polymkeric substance formed after radical polymerization by the monomer of esters of acrylic acid, and the acrylic ester monomer selected is made up of one or more in methyl acrylate, butyl acrylate, vinylformic acid, methyl methacrylate, methacrylic acid, hydroxyethyl methylacrylate, Rocryl 410, trimethylolpropane trimethacrylate; The initiator used is by one or more in Diisopropyl azodicarboxylate, benzoyl peroxide, 2,2'-Azobis(2,4-dimethylvaleronitrile), and usage quantity is the 0.5%-2% of acrylic ester monomer amount;
Polyisocyanates in described component A is by one or more mixtures formed in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), liquefied mdi, isoflurane chalcone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), two ring ethyl methane vulcabond (HMDI) etc.
7. the solvent-free double-component polyurethane tackiness agent of high initial bonding strength according to claim 6, is characterized in that:
Polyether glycol in described B component, its molecular weight ranges is at 300-2500, and by one or both mixtures formed in polyoxypropyleneglycol and polytetrahydrofuran diol, consumption accounts for the 10%-60% of B component total amount;
Vegetable oil polyol in described B component is by the mixture that in Viscotrol C, epoxy soybean oil, plam oil, one or more form, and consumption accounts for the 20%-50% of B component total amount;
Tackifying resin in described B component is by one or more mixtures formed in terpine resin, Gum Rosin, petroleum resinoid, and consumption accounts for the 1%-10% of B component total amount.
8. the preparation method of the solvent-free double-component polyurethane tackiness agent of the high initial bonding strength described in claim 1-7:
(1) polyether glycol in component A and/or vegetable oil polyol are heated to 60 degree of-100 degree, drip the acrylic ester monomer solution being mixed with initiator, drip off in 2h-3h, insulation 1h-2h, mixture is heated to 110 degree of-120 degree, dewater 1.5h-2.5h under pressure <1.3KPa, by water content control below 0.1%, after cool to less than 70 degree, add polyisocyanates, under 80-90 degree, react the component A that 2-3h obtains isocyanate terminated compound;
(2) polyether glycol in B component and/or vegetable oil polyol and/or tackifying resin are heated to 110-120 degree, dissolve 0.5h-1h, dewater 1.5h-2.5h under pressure <1.3KPa, and by water content control below 0.1%, discharging obtains the B component of polyol.
9. the solvent-free double-component polyurethane tackiness agent of the high initial bonding strength described in the claim 1-7 application in following: be applied to the compound between any two kinds of materials in BOPP, CPP, PE, PET, PA, aluminium foil and aluminium plating film as solvent-free polyurethane adhesive, and be applicable to high speed compound.
10. application according to claim 9, is characterized in that: film surface must through corona treatment.
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| CN106147689B (en) * | 2016-07-27 | 2019-01-01 | 江门市蓬江区盈通塑胶制品有限公司 | A kind of shoes high-flexibility, high-adhesive-strength two-component polyurethane adhesive and its preparation method and application |
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| CN106393749A (en) * | 2016-08-31 | 2017-02-15 | 河北洋浦包装材料有限公司 | Compound film being high in peel strength and preparation method of compound film |
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| US11267929B2 (en) | 2017-01-12 | 2022-03-08 | Basf Se | Physical property improvement of polyurethanes |
| CN110167985A (en) * | 2017-01-12 | 2019-08-23 | 巴斯夫欧洲公司 | The physical property of polyurethane is improved |
| JP2020504218A (en) * | 2017-01-12 | 2020-02-06 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Improvement of physical properties of polyurethane |
| CN106928444A (en) * | 2017-05-08 | 2017-07-07 | 万华化学集团股份有限公司 | Modified acrylate dispersion of a kind of epoxidized soybean oil and preparation method thereof |
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| CN108250935A (en) * | 2018-01-11 | 2018-07-06 | 山东扬名新材料技术有限公司 | Zero solvent polyurethane sealing bottom coating agent |
| CN108250935B (en) * | 2018-01-11 | 2020-10-09 | 山东扬名新材料技术有限公司 | Zero-solvent polyurethane sealing primer |
| CN110437743A (en) * | 2019-08-07 | 2019-11-12 | 德庆明亮树脂有限公司 | A kind of production technology and its application of water-white tackifying resins |
| CN110484191A (en) * | 2019-08-16 | 2019-11-22 | 无锡庄周新材料科技有限公司 | A kind of dual-component polyurethane adhesive and preparation method thereof |
| CN110790890A (en) * | 2019-11-22 | 2020-02-14 | 大连理工大学 | A kind of polyurethane elastomer for metal composite sandwich panel core material and using method thereof |
| CN113648451A (en) * | 2021-08-19 | 2021-11-16 | 青岛大学 | Novel alpha-cyanoacrylate medical adhesive and preparation method thereof |
| CN115181535A (en) * | 2022-08-11 | 2022-10-14 | 苏州合邦鑫材科技有限公司 | Ultraviolet light-moisture dual-curing polyurethane hot melt adhesive and preparation method thereof |
| CN115181535B (en) * | 2022-08-11 | 2024-01-12 | 苏州合邦鑫材科技有限公司 | Ultraviolet light-moisture dual-curing polyurethane hot melt adhesive and preparation method thereof |
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