CN117777936A - Dual-curing reaction type polyurethane hot melt adhesive and preparation method thereof - Google Patents
Dual-curing reaction type polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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- CN117777936A CN117777936A CN202311785588.1A CN202311785588A CN117777936A CN 117777936 A CN117777936 A CN 117777936A CN 202311785588 A CN202311785588 A CN 202311785588A CN 117777936 A CN117777936 A CN 117777936A
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 52
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 49
- 239000004814 polyurethane Substances 0.000 title claims abstract description 49
- 238000006757 chemical reactions by type Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 45
- 150000003077 polyols Chemical class 0.000 claims abstract description 34
- 229920005862 polyol Polymers 0.000 claims abstract description 33
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 26
- 229920000570 polyether Polymers 0.000 claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003381 stabilizer Substances 0.000 claims abstract description 17
- 239000013530 defoamer Substances 0.000 claims abstract description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- 230000000655 anti-hydrolysis Effects 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000003112 inhibitor Substances 0.000 claims description 18
- 239000004925 Acrylic resin Substances 0.000 claims description 14
- 229920000178 Acrylic resin Polymers 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 12
- 230000009977 dual effect Effects 0.000 claims description 11
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 10
- 230000001588 bifunctional effect Effects 0.000 claims description 9
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 7
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- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
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- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 3
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 claims description 2
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical group CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 19
- 230000001070 adhesive effect Effects 0.000 abstract description 19
- 229920000459 Nitrile rubber Polymers 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000004100 electronic packaging Methods 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 26
- 238000005286 illumination Methods 0.000 description 18
- 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 description 13
- 150000001718 carbodiimides Chemical group 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000084 colloidal system Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- -1 acrylic ester Chemical class 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 238000013008 moisture curing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002160 Celluloid Polymers 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
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- 238000007711 solidification Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- 244000226021 Anacardium occidentale Species 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
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- 239000012943 hotmelt Substances 0.000 description 1
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- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 238000007719 peel strength test Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
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- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 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 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to the technical field of reactive polyurethane hot melt adhesives, in particular to a dual-curing reactive polyurethane hot melt adhesive and a preparation method thereof, comprising the following components: 110-140 parts of acrylic prepolymer containing double bonds, 150-250 parts of crystalline polyester polyol, 250-320 parts of amorphous polyester polyol, 80-120 parts of amorphous polyether polyol, 0.1-2 parts of defoamer, 0.2-2 parts of anti-hydrolysis agent, 0.5-3 parts of stabilizer, 50-100 parts of diisocyanate, 0.05-4 parts of silane coupling agent, 0.05-2 parts of catalyst and 10-25 parts of photoinitiator. The UV and moisture dual-curing reaction type polyurethane hot melt adhesive has higher initial strength and final bonding strength for a nitrile rubber film; combines the characteristics of quick bonding and fixation of UV adhesive and high reliability of polyurethane hot melt adhesive, and meets the requirements of environmental protection, low odor, portable fixation and high bonding strength in the field of electronic packaging.
Description
Technical Field
The invention relates to the technical field of reactive polyurethane hot melt adhesives, in particular to a dual-curing reactive polyurethane hot melt adhesive and a preparation method thereof.
Background
As the modernization process accelerates, more and more enterprises begin to pay attention to the improvement of production efficiency, which requires some processes and flows to be performed quickly and stably. In the adhesive industry, the application proportion of the UV adhesive and the reactive polyurethane hot melt adhesive in electronic assembly is higher and higher due to the characteristics of rapid solidification and the like. UV glue can be cured rapidly by ultraviolet or visible light irradiation. The reactive polyurethane hot melt adhesive is in a solid state at room temperature, can be melted into a liquid or fluid state under the heating condition, can be applied with glue at the moment, can be contacted with a second bonding base material before being cooled, can form solid glue with certain bonding strength after being cooled, and can be distributed with water in air for crosslinking and solidification to finish final solidification, so that higher bonding strength can be obtained. The reactive polyurethane hot melt adhesive can generate adhesive lines with the thickness of less than 0.5mm, has no residue, and can be used for bonding small parts and precise parts.
However, with the enhancement of environmental protection awareness and the increase of skin irritation reports of sensitization monomers contained in main acrylate type UV adhesives, the problems of heavy smell, high sensitization, no environmental protection and the like exist in the direct UV initiation by using the acrylic acid monomers, and the UV light curing by using the prepolymer becomes a preferential path. The current electronic consumption field gradually develops towards the reactive polyurethane hot melt adhesive due to the requirements of environmental protection, convenience, no residue and the like. Meanwhile, the UV adhesive can be quickly fixed by illumination, and although the environment-friendly and nontoxic reactive polyurethane hot melt adhesive can obtain certain strength by cooling crystalline substances or high-softening-point substances in the formula, the UV adhesive needs 10-20min for pressure maintaining and fixing, so that the production efficiency is reduced.
Therefore, a method is developed, which can quickly reach higher initial strength after illumination and meet the initial transportation requirement; further, the bonding strength is further improved through moisture rapid curing, and finally the requirements of high bonding and high reliability are met; meanwhile, the intensity can still be kept high in the area where illumination is not available; and the environment-friendly hot-melt adhesive without sensitization monomer has good market prospect and necessity.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a dual-curing reaction type polyurethane hot melt adhesive and a preparation method thereof.
The technical scheme for solving the technical problems is as follows:
the invention provides a dual-curing reaction type polyurethane hot melt adhesive, which comprises the following components in parts by weight:
110-140 parts of acrylic prepolymer containing double bonds, 150-250 parts of crystalline polyester polyol, 250-320 parts of amorphous polyester polyol, 80-120 parts of amorphous polyether polyol, 0.1-2 parts of defoamer, 0.2-2 parts of anti-hydrolysis agent, 0.5-3 parts of stabilizer, 50-100 parts of diisocyanate, 0.05-4 parts of silane coupling agent, 0.05-2 parts of catalyst and 10-25 parts of photoinitiator.
The dual-curing reaction type polyurethane hot melt adhesive is a UV (photosensitive polymer exposure) and moisture dual-curing reaction type polyurethane hot melt adhesive, and high bonding strength is obtained immediately after UV illumination, meanwhile, the bonding strength is continuously increased in the subsequent contact with moisture, so that the rapid bonding and fixing of the UV adhesive are met, and the dual-curing reaction type polyurethane hot melt adhesive has the characteristic of high reliability and high curing strength after curing under the dark condition.
Based on the technical scheme, the invention can also make the following improvements:
further, the double bond-containing acrylic acid prepolymer comprises the following components in parts by weight: 150-250 parts of non-crystalline double bond-containing difunctional polyester polyol, 150-250 parts of non-crystalline double bond-containing polyether polyol, 0.2-1 part of hydrolysis inhibitor, 0.5-3 parts of stabilizer, 0.2-1 part of defoamer, 140-170 parts of diisocyanate, 0.1-2 parts of polymerization inhibitor and 70-100 parts of monofunctional acrylic resin.
The beneficial effects of adopting the further scheme are as follows: the monofunctional acrylic resin and the noncrystalline bifunctional polyester polyol containing double bonds used in the synthesis of the acrylic prepolymer containing double bonds contain double bonds, so that the proportion of double bonds in the polymer can be increased, the photocuring efficiency can be improved, and the ultraviolet irradiation time can be shortened.
Further, the double bond-containing acrylic acid prepolymer is prepared by the following steps: dehydrating a mixture of a non-crystalline double-bond-containing bifunctional polyester polyol, a non-crystalline double-bond-containing bifunctional polyether polyol and a non-crystalline double-bond-containing bifunctional polyester polyol, heating the mixture with diisocyanate to react, then blocking the mixture by using a polymerization inhibitor, adding a monofunctional acrylic resin after the reaction is finished, and obtaining the double-bond-containing acrylic prepolymer, and placing the prepolymer in a closed container for moisture isolation for standby.
The preparation of the acrylic prepolymer containing double bonds involves 2 reactions in which R represents the other structure than hydroxyl groups in the structure of the noncrystalline double bond-containing difunctional polyester polyol or the noncrystalline difunctional polyether polyol. The first step, the excessive isocyanate reacts with polyol to generate a terminal-NCO compound; the second step is then reacted with a monofunctional acrylic resin (for example hydroxyethyl methacrylate) to block the-NCO groups and produce a double bond containing acrylic prepolymer.
Equation 1
Equation 2
The beneficial effects of adopting the further scheme are as follows: the double-solidification reaction type polyurethane hot melt adhesive is added with the acrylic acid prepolymer component containing double bonds, and after illumination, the acrylic acid ester groups are added through double bonds to form a net chain structure, and meanwhile, the crystallized polyester polyol is crystallized and cooled, so that certain cohesive strength can be provided; as moisture curing proceeds, the large number of urethane groups and biuret structures formed by the glue increase the adhesive and cohesive strength; after the prepolymer with acrylic ester reacts with diisocyanate, the prepolymer can participate in light and moisture curing, so that the strength of the prepolymer is higher under the condition of no light.
Further, the molar ratio of isocyanate group content of the diisocyanate to hydroxyl group content of the difunctional polyol is 2.05:1 (R value 2.05), the molar ratio of isocyanate groups (NCO) content of the unreacted diisocyanate to the hydroxyl content of the monofunctional acrylic resin being 0.95:1 (R value 0.95).
The beneficial effects of adopting the further scheme are as follows: the specific functional group of the obtained acrylic prepolymer containing double bonds contains double bonds and a small amount of hydroxyl groups, and does not contain NCO groups.
Further, the noncrystalline double bond-containing difunctional polyester polyol is one or two selected from the group consisting of Hui technology HDPOL-6610DA, heda Croda Priplast 3190 and Yingzhang Dynacoll 7361; the noncrystalline bifunctional polyether polyol is one or two selected from the group consisting of Kadeli chemical NX-9212, lanxingdong chemical 330n, neutralized Cheng Tai PPG-2000 and an Hao Yi New P03G.
The beneficial effects of adopting the further scheme are as follows: the noncrystalline bifunctional polyether polyol adopted by the invention is a polyol taking a polyether structure as a main repeating chain unit, can provide flexibility, is soft due to the material of the nitrile rubber film, has lower modulus after colloid curing, and can be better attached to the nitrile rubber substrate, thereby generating good adhesive force.
Further, the polymerization inhibitor is N, N-diethyl hydroxylamine (DEHA) or polymerization inhibitor 590 (Easepi 590), and the monofunctional acrylic resin is one of hydroxyethyl methacrylate, hydroxybutyl methacrylate and hydroxybutyl acrylate.
Further, the anti-hydrolysis agent is carbodiimide, the stabilizer is one of phosphoric acid or antioxidant 1010, the antifoaming agent is one of BASF EFKA SI 2038 or De 5500, and the diisocyanate is one or two of diphenylmethane diisocyanate (MDI) or toluene diisocyanate (HDI).
Further, the crystalline polyester polyol is one or two of celluloid PCL230N, PCL, PCL230, jiaji chemical Priplast 3172 and Hui technology HDPOL-6650S, and the amorphous polyester polyol is two or three of BY3026, BY3037, BY3003, BY3038 and BY3032 of Bai source chemical industry.
Further, the silane coupling agent is selected from one or more of KH560, KH550, A-189, the catalyst is selected from one or two of dibutyl tin dilaurate, stannous octoate and triethylene diamine, and the photoinitiator is selected from one or more of a photoinitiator TPO (diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide), TPO-L (ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate), 184 (1-hydroxycyclohexyl phenyl ketone), 907 (2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone) or 819 (phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide).
The beneficial effects of adopting the further scheme are as follows: adding the catalyst to regulate the speed of the synthesis reaction and the final curing speed of the finished adhesive; the photoinitiator can be any photoinitiator with good compatibility, and can be any component which is stable under no illumination and absorbs energy to initiate free radical polymerization under illumination.
The invention also provides a preparation method of the dual-curing reaction type polyurethane hot melt adhesive, which is characterized by comprising the following steps:
dehydrating the crystalline polyester polyol, the amorphous polyether polyol, the defoamer, the anti-hydrolysis agent and the stabilizer for 1.5 to 3 hours under the conditions that the temperature is 110 to 150 ℃ and the vacuum degree is-0.09 Mpa to-0.1 Mpa, after dehydration, reducing the temperature to 90 to 110 ℃, adding diisocyanate, heating to 110 to 120 ℃ for continuous reaction for 0.5 to 1 hour, then adding the silane coupling agent, the catalyst, the photoinitiator and the acrylic acid prepolymer containing double bonds for continuous stirring for 0.5 to 3 hours, breaking vacuum, discharging, and sealing and packaging to obtain the dual-curing reaction polyurethane hot melt adhesive.
Compared with the prior art, the invention has the following technical effects:
the UV and moisture dual-curing reaction type polyurethane hot melt adhesive prepared by the invention contains a plurality of double bond groups from acrylic acid and polyalcohol, and double bonds among acrylate groups are added to form a network chain structure after short illumination; meanwhile, the crystallized polyester polyol is crystallized and cooled, and certain cohesive strength can be provided; in the subsequent contact with moisture, as the moisture solidifies, the glue forms a plurality of urethane groups and biuret structures, improving the adhesive and cohesive strength, and the strength continues to increase; the dual-curing reaction type polyurethane hot melt adhesive prepared by the invention has excellent initial and final bonding strength. After the reaction of the polyol with acrylic ester and the polyisocyanate, the polyol with acrylic ester can participate in light and moisture curing, so that the strength is still higher under the condition of no light. The UV and moisture dual-curing reaction type polyurethane hot melt adhesive has the characteristics of rapid adhesion and fixation of UV adhesive and high reliability of polyurethane hot melt adhesive, can be cured under the dark condition, has higher curing strength, and particularly has higher adhesive strength on nitrile rubber.
Drawings
FIG. 1 shows an infrared spectrum of a prepolymer A1 of example 1 of the present invention.
Detailed Description
Further advantages and effects of the present invention will become apparent to those skilled in the art from the disclosure of the present specification, by describing the embodiments of the present invention with specific examples. While the description of the invention will be described in connection with the preferred embodiments, it is not intended to limit the inventive features to the implementation. Rather, the purpose of the invention described in connection with the embodiments is to cover other alternatives or modifications, which may be extended by the claims based on the invention. The following description contains many specific details for the purpose of providing a thorough understanding of the present invention. The invention may be practiced without these specific details. Furthermore, some specific details are omitted from the description in order to avoid obscuring the invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
Example 1
Preparation of acrylic acid prepolymer containing double bond:
200g of noncrystalline double bond-containing difunctional polyester polyol (sink technology HDPOL-6610 DA), 200g of noncrystalline difunctional polyether polyol (Kadeli chemical NX-9212), 2g of stabilizer (antioxidant 1010), 1g of defoamer (De 5500) and 1g of anti-hydrolysis agent (carbodiimide) are added into a reaction bottle and dehydrated for 2 hours at 130 ℃ in advance for standby, cooled to 80 ℃, 152g of MDI (diphenyl-methane-diisocyanate) and 0.1g of polymerization inhibitor 590 are added into the reaction bottle, heated to 120 ℃, the reaction is continued for 60 minutes, 81g of monofunctional acrylic resin (hydroxyethyl methacrylate) is added for reaction for 60 minutes, nitrogen is broken, vacuum is filled into a closed container for isolating moisture for standby, and the prepolymer A1 is obtained.
Comparative example 1
Preparation of acrylic acid prepolymer containing double bond:
200G of noncrystalline double bond-containing difunctional polyester polyol (sink technology HDPOL-6610 DA), 200G of noncrystalline difunctional polyether polyol (novel material P03G), 2G of stabilizer (antioxidant 1010), 1G of defoamer (pretty 5500) and 1G of anti-hydrolysis agent (carbodiimide) are added into a reaction bottle and dehydrated for 2 hours at 130 ℃ in advance for standby, cooled to 80 ℃, 152G of MDI (diphenyl-methane-diisocyanate) and 0.1G of polymerization inhibitor 590 are added into the reaction bottle, heated to 120 ℃ for continuous reaction for 60 minutes, 81G of monofunctional acrylic resin (hydroxyethyl methacrylate) is added for reaction for 60 minutes, and then the reaction bottle is subjected to vacuum breaking by nitrogen and filled into a closed container for isolating moisture to be used as prepolymer A2.
Comparative example 2
Preparation of acrylic acid prepolymer containing double bond:
200g of noncrystalline double bond-containing difunctional polyester polyol (sink technology HDPOL-6610 DA), 200g of noncrystalline difunctional polyether polyol (Kadeli chemical NX-9212), 2g of stabilizer (antioxidant 1010), 1g of defoamer (De 5500) and 1g of anti-hydrolysis agent (carbodiimide) are added into a reaction bottle and dehydrated for 2 hours at 130 ℃ in advance for standby, cooled to 80 ℃, 152g of MDI (diphenyl-methane-diisocyanate) and 0.1g of polymerization inhibitor 590 are added into the reaction bottle, heated to 120 ℃ for continuous reaction for 60 minutes, 90g of monofunctional acrylic resin (hydroxybutyl acrylate) is added for reaction for 60 minutes, and then the reaction bottle is filled with nitrogen for vacuum breaking and isolated from moisture for standby, and is marked as a prepolymer A3.
Comparative example 3
Preparation of acrylic acid prepolymer containing double bond:
200g of saturated amorphous polyester polyol (Asahi chemical FLP 2000N) and 200g of amorphous polyether polyol (Kadeli chemical NX-9212), 2g of stabilizer (antioxidant 1010), 1g of defoamer (Demodit 5500) and 1g of hydrolytic inhibitor (carbodiimide) are added into a reaction bottle and dehydrated for 2 hours at 130 ℃ in advance for standby, cooled to 80 ℃, 103 MDI (methylene diphenyl oxide) and 0.1g of polymerization inhibitor 590 are added into the reaction bottle, heated to 120 ℃ for continuous reaction for 60 minutes, 55g of monofunctional acrylic resin (hydroxyethyl methacrylate) is added for reaction for 60 minutes, nitrogen is broken into vacuum, and the mixture is poured into a closed container for moisture isolation standby, and is marked as a prepolymer A4.
The acrylic prepolymers prepared in example 1 and comparative examples 1 to 3 were used to prepare dual curing reactive polyurethane hot melt adhesives by the procedure of example 2, respectively.
Example 2
Preparation of dual-curing reaction type polyurethane hot melt adhesive:
200g of crystalline polyester polyol (large xylonite PCL 230N), 50g of amorphous polyester polyol (Bai Yu chemical BY 3026), 100g of amorphous polyester polyol (Bai Yu chemical BY 3037), 110g of amorphous polyester polyol (Bai Yu chemical BY 3038), 100g of amorphous polyether polyol (Cardel-crafts NX-9212), 2g of hydrolysis inhibitor (carbodiimide), 3g of stabilizer (antioxidant 1010), 2g of defoamer (De-lumen 5500) are dehydrated for 2h under the conditions of 140 ℃ and minus 0.098Mpa, the dehydration is completed, then the temperature is reduced to 90 ℃, 82.4g of MDI is added, the temperature is raised to 120 ℃ for continuous reaction for 1h, then 4g of silane coupling agent (KH 550), 1g of catalyst (triethylenediamine), 25g of photoinitiator (TPO-L) and 120g of acrylic acid prepolymers (A1-A4) are added, stirring is continued for 1h, vacuum breaking is carried out, and the materials are discharged, and sealed package is carried out, so that the double-reaction type polyurethane is obtained.
The prepolymer used and the corresponding dual cure reactive polyurethane hot melt adhesive codes are shown in table 1.
TABLE 1 number of prepolymers used in colloids and corresponding hot melts obtained
| Prepolymer | A1 | A2 | A3 | A4 |
| The obtained hot melt adhesive | B1 | B2 | B3 | B4 |
FIG. 1 is an infrared spectrum of a prepolymer A1. Wherein 3336cm -1 The peak corresponds to the peak of-OH, the prepolymer is slightly higher in the amount of-OH and is 2270cm in order to ensure complete consumption of-NCO groups -1 There is no obvious peak intensity, which proves that the-NCO group in the prepolymer is completely consumed; 1731cm -1 The strong peak is the characteristic peak of esters (polyester polyol, technology HDPOL-6610DA is obtained); 1535cm -1 And 2930cm -1 The strong peak is the corresponding peak of benzene ring (Cardely chemical NX-9212 is cashew shell polyether polyol containing benzene ring); 1600cm -1 The strong peak corresponds to the characteristic peak of C=C double bond (the sink technology HDPOL-6610DA is polyester polyol containing carbon-carbon double bond, and the hydroxyethyl methacrylate also contains carbon-carbon double bond).
Comparative example 4
Preparation of dual-curing reaction type polyurethane hot melt adhesive:
200g of crystalline polyester polyol (Priplast 3172 in Jiaji chemical industry), 50g of amorphous polyester polyol (BY 3026 in Bai Yu chemical industry), 100g of amorphous polyester polyol (BY 3037 in Bai Yu chemical industry), 110g of amorphous polyester polyol (BY 3037 in Bai Yu chemical industry), 100g of amorphous polyether polyol (NX-9212 in Kadeli chemical industry), 2g of hydrolysis inhibitor (carbodiimide), 3g of stabilizer (antioxidant 1010), 2g of defoamer (De Qing 5500) are dehydrated for 2 hours under 140 ℃ and-0.098 Mpa, the dehydration is completed, then the temperature is reduced to 90 ℃, 82.4g of MDI is added, the temperature is raised to 120 ℃ for continuous reaction for 1 hour, then 4g of silane coupling agent (KH 550), 1g of catalyst (triethylene diamine), 25g of photoinitiator (TPO-L) and 120g of prepolymer A1 in the above example 1 are added, stirring is continued for 1 hour, vacuum breaking, discharging and sealing packaging is carried out, and the double reaction type polyurethane B5 is obtained.
Comparative example 5
Preparation of dual-curing reaction type polyurethane hot melt adhesive:
200g of crystalline polyester polyol (sink technology HDPOL-6650S), 50g of amorphous polyester polyol (Bai Yu chemical, BY 3026), 100g of amorphous polyester polyol (Bai Yu chemical, BY 3037), 110g of amorphous polyester polyol (Bai Yu chemical, BY 3038), 100g of amorphous bifunctional polyether polyol (Kad Lai chemical NX-9212), 2g of hydrolysis inhibitor (carbodiimide), 3g of stabilizer (antioxidant 1010), 2g of defoamer (De 5500) are dehydrated in vacuum for 2h under 140 ℃ and-0.098 Mpa, the dehydration is completed, then the temperature is reduced to 90 ℃, 94.1g of MDI is added, the temperature is increased to 120 ℃ for continuous reaction for 1h, then 4g of silane coupling agent (KH 550), 1g of catalyst (triethylene diamine), 25g of photoinitiator (L) and 120g of prepolymer A1 in the above examples are added for continuous stirring for 1h, vacuum breaking, discharging and sealing packaging, thus obtaining the double-reaction type polyurethane B6.
Comparative example 6
Preparation of polyurethane hot melt adhesive:
200g of crystalline polyester polyol (large xylonite, PCL 230N), 50g of amorphous polyester polyol (Bai Yuan chemical, BY 3026), 100g of amorphous polyester polyol (Bai Yuan chemical, BY 3037), 110g of amorphous polyester polyol (Bai Yuan chemical, BY 3038), 100g of amorphous bifunctional polyether polyol (Carley chemical NX-9212), 2g of carbodiimide, 3g of stabilizer (antioxidant 1010), 2g of defoamer (De-pretty 5500) are dehydrated for 2 hours under the conditions of 140 ℃ and-0.098 Mpa, the dehydration is completed, then the temperature is reduced to 90 ℃, 82.4g of MDI is added, the temperature is raised to 120 ℃ for continuous reaction for 1 hour, then 4g of silane coupling agent (KH 550) and 1g of catalyst (triethylene diamine) are added, stirring is continued for 1 hour, vacuum breaking is carried out, discharging is carried out, and the sealed package is recorded as B7.
The polyurethane hot melt adhesive of the invention is subjected to the following performance test:
1. sample, base material and curing condition
The substrate selected: nitrile rubber film 0.1mm+1mm vs PC;
peel strength test: dots of 3mm diameter;
colloid thickness: 0.15mm;
stretching speed: 10mm/min;
curing conditions: curing at 25℃with 50% humidity for 1min,5min,24h;
UV light curing: 365nm (800 mw 5s,10 s);
testing ambient temperature: 25 ℃.
2. Intensity test
Illumination intensity: and (3) adding a gap piece with the diameter of 0.15mm to the surface of the substrate at the adhesive point with the diameter of 3mm, pressing the second piece, pressing for 10s by using a 1kg weight, irradiating for 5s by using a UV lamp with the wavelength of 365nm, and maintaining the pressure for a fixed time after 10 s. (determination of starting hardening of colloid for adjusting illumination time)
No illumination intensity: and (3) adding a gap piece with the diameter of 3mm to the surface of the base material, pressing a second piece, pressing for 10s by using a weight of 1kg, and maintaining the pressure for a fixed time.
The hot melt adhesive obtained in example 5 was tested and the results are shown in Table 2.
TABLE 2 illumination time and initial peel force test results for hot melt adhesives
| Hot melt adhesive numbering | B1 | B2 | B3 | B4 |
| Duration/s of illumination | 5 | 5 | 5 | 10 |
| Initial peel force/N | 2.12 | 1.73 | 1.65 | 1.74 |
As can be seen from the detection results in Table 2, in the invention, the addition of the unsaturated polyester polyol shortens the time required for the UV curing illumination of the colloid by comparing the data of the illumination time periods; compared with the data of B1 and B3, the acrylate with methyl can obviously improve the colloid activity and enhance the initial strength after UV illumination; meanwhile, the low-polarity polyether polyol (NX-9212) has higher bonding strength than the polyether polyol with higher polarity due to the fact that the low-polarity polyether polyol is close to the polarity of the nitrile rubber. In the invention, the reactive polyurethane hot melt adhesive is prepared by adopting the A1 prepolymer continuously in the follow-up process because the comprehensive performance of the B1 is good.
The test results of the light irradiation time and the initial peel force of the hot melt adhesives of B1, B5 and B6 and comparative example 1 are shown in Table 3.
TABLE 3 results of the light time and initial peel force tests for the examples and comparative examples
As can be seen from the test results in Table 3, in the invention, the used polyol in B1 and B5 has low polarity, so that the adhesive strength to the nitrile rubber film is comprehensively higher, and the adhesive strength in the non-illuminated area is still higher.
The UV-moisture dual-curing reactive polyurethane hot melt adhesive prepared by the invention can participate in illumination and moisture curing, so that the strength is higher under the condition of no illumination; the UV adhesive has the characteristics of quick adhesion and fixation of UV adhesive and high reliability of polyurethane hot melt adhesive. In addition, the requirements of environmental protection, low odor and quick fixing and bonding in the field of electronic packaging can be met.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The double-curing reaction type polyurethane hot melt adhesive is characterized by comprising the following components in parts by weight:
110-140 parts of acrylic prepolymer containing double bonds, 150-250 parts of crystalline polyester polyol, 250-320 parts of amorphous polyester polyol, 80-120 parts of amorphous polyether polyol, 0.1-2 parts of defoamer, 0.2-2 parts of anti-hydrolysis agent, 0.5-3 parts of stabilizer, 50-100 parts of diisocyanate, 0.05-4 parts of silane coupling agent, 0.05-2 parts of catalyst and 10-25 parts of photoinitiator.
2. The dual curing reactive polyurethane hot melt adhesive of claim 1, wherein the double bond-containing acrylic prepolymer comprises the following components in parts by weight:
150-250 parts of non-crystalline double bond-containing difunctional polyester polyol, 150-250 parts of non-crystalline double bond-containing polyether polyol, 0.2-1 part of hydrolysis inhibitor, 0.5-3 parts of stabilizer, 0.2-1 part of defoamer, 140-170 parts of diisocyanate, 0.1-2 parts of polymerization inhibitor and 70-100 parts of monofunctional acrylic resin.
3. The dual curing reactive polyurethane hot melt adhesive of claim 2, wherein the double bond-containing acrylic prepolymer is prepared by: dehydrating a mixture of a non-crystalline double-bond-containing difunctional polyester polyol and a non-crystalline double-bond-containing difunctional polyether polyol, reacting with diisocyanate in a heating manner, blocking by using a polymerization inhibitor, and adding a monofunctional acrylic resin to obtain the double-bond-containing acrylic prepolymer.
4. A dual cure reactive polyurethane hot melt adhesive according to claim 2 or 3, wherein the molar ratio of isocyanate group content of the diisocyanate to hydroxyl content of the difunctional polyol is 2.05:1, the molar ratio of the isocyanate group content of the unreacted diisocyanate to the hydroxyl group content of the monofunctional acrylic resin was 0.95:1.
5. the dual curing reactive polyurethane hot melt adhesive of claim 2 or 3, wherein the non-crystalline double bond-containing difunctional polyester polyol is selected from one or two of the technologies HDPOL-6610DA, croda Priplast 3190, winning Dynacol 7361; the noncrystalline bifunctional polyether polyol is one or two selected from the group consisting of Kadeli chemical NX-9212, lanxingdong chemical 330n, neutralized Cheng Tai PPG-2000 and an Hao Yi New P03G.
6. A dual cure reactive polyurethane hot melt adhesive as claimed in claim 2 or 3, wherein the polymerization inhibitor is N, N-Diethylhydroxylamine (DEHA) or polymerization inhibitor 590 (Easepi 590), and the monofunctional acrylic resin is one of hydroxyethyl methacrylate, hydroxybutyl methacrylate, and hydroxybutyl acrylate.
7. The dual cure reactive polyurethane hot melt adhesive of claim 1 or 2, wherein the anti-hydrolysis agent is carbodiimide, the stabilizer is one of phosphoric acid or antioxidant 1010, the defoamer is one of BASF EFKA SI 2038 or deya 5500, and the diisocyanate is one or both of MDI or HDI.
8. The dual cure reactive polyurethane hot melt adhesive of claim 1, wherein the crystalline polyester polyol is one or two of macrocellulite PCL230N, PCL, PCL230, jia chemical Priplast 3172, sink technology HDPOL-6650S, and the amorphous polyester polyol is two or three of BY3026, BY3037, BY3003, BY3038, BY3032 of the herborist chemical industry.
9. The dual curing reactive polyurethane hot melt adhesive of claim 1, wherein the silane coupling agent is selected from one or more of KH560, KH550, a-189, the catalyst is selected from one or two of dibutyltin dilaurate, stannous octoate, and triethylenediamine, and the photoinitiator is selected from one or more of photoinitiators TPO, TPO-L, 184, 907, or 819.
10. A method for preparing the dual curing reaction type polyurethane hot melt adhesive as claimed in any one of claims 1 to 9, comprising the steps of:
dehydrating the crystalline polyester polyol, the amorphous polyether polyol, the defoamer, the anti-hydrolysis agent and the stabilizer for 1.5 to 3 hours under the conditions that the temperature is 110 to 150 ℃ and the vacuum degree is-0.09 Mpa to-0.1 Mpa, after dehydration, reducing the temperature to 90 to 110 ℃, adding diisocyanate, heating to 110 to 120 ℃ for continuous reaction for 0.5 to 1 hour, then adding the silane coupling agent, the catalyst, the photoinitiator and the acrylic acid prepolymer containing double bonds for continuous stirring for 0.5 to 3 hours, breaking vacuum, discharging, and sealing and packaging to obtain the dual-curing reaction polyurethane hot melt adhesive.
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