CN100497426C - High solid content water polyurethane adhesive for non-absorbability base material and preparing method - Google Patents
High solid content water polyurethane adhesive for non-absorbability base material and preparing method Download PDFInfo
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- CN100497426C CN100497426C CNB2007100273117A CN200710027311A CN100497426C CN 100497426 C CN100497426 C CN 100497426C CN B2007100273117 A CNB2007100273117 A CN B2007100273117A CN 200710027311 A CN200710027311 A CN 200710027311A CN 100497426 C CN100497426 C CN 100497426C
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 41
- 239000004814 polyurethane Substances 0.000 title claims abstract description 41
- 239000000853 adhesive Substances 0.000 title claims abstract description 25
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 38
- 239000007787 solid Substances 0.000 title claims description 23
- 239000000463 material Substances 0.000 title claims description 21
- 238000000034 method Methods 0.000 title claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000000839 emulsion Substances 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 23
- 229910052731 fluorine Inorganic materials 0.000 claims description 23
- 239000011737 fluorine Substances 0.000 claims description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 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 13
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical group CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 8
- 238000004945 emulsification Methods 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000009775 high-speed stirring Methods 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- 238000009736 wetting Methods 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920005906 polyester polyol Polymers 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 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 5
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- UHAMPPWFPNXLIU-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)pentanoic acid Chemical compound CCCC(CO)(CO)C(O)=O UHAMPPWFPNXLIU-UHFFFAOYSA-N 0.000 claims description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229920003180 amino resin Polymers 0.000 claims description 2
- 150000001718 carbodiimides Chemical class 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 1
- 239000012975 dibutyltin dilaurate Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000002745 absorbent Effects 0.000 abstract 1
- 239000002250 absorbent Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- -1 tinsel Substances 0.000 description 9
- 239000010985 leather Substances 0.000 description 8
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 3
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920001610 polycaprolactone Polymers 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical class CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- MBVGJZDLUQNERS-UHFFFAOYSA-N 2-(trifluoromethyl)-1h-imidazole-4,5-dicarbonitrile Chemical compound FC(F)(F)C1=NC(C#N)=C(C#N)N1 MBVGJZDLUQNERS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920002799 BoPET Polymers 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical class CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Abstract
The invention discloses a high firm content of aquosity polyurethane adhesive of non-absorbent substrate and its preparation. In the invention, it firstly synthesizes polyurethane resin emulsion as the main agent. The synthesis technical is simple and consumes less organic solvent, and the firm content of polyurethane is 35~55%, the surface tension is 33~40mN/m, the diameter is 50~300 nm. Then, it adds curing agent to perpare the high firm content of aquosity polyurethane adhesive.
Description
Technical field
The present invention relates to fine polymer material field, relate in particular to a kind of high-solid content water-based polyurethane adhesive and preparation method who is used for non-absorbability base material.
Background technology
Bi-component polyurethane adhesive is a most important class in the polyurethane adhesive, is widely used for bonding various non-absorbability base material, as rubber, leather, plastics film, glass, tinsel, fiber etc.Conventional process is with coating machine, manual hairbrush or blade coating, and tackiness agent is uniformly coated on thin film or the sheet material by certain spread, allows solvent or moisture evaporation by heating then, fits together with another kind of film or sheet material again.
Water-based polyurethane adhesive is to be dispersion medium with water, have do not burn, smell is few, toxicity is little, advantage such as free from environmental pollution, easy for operation.The same with the solvent borne polyurethane tackiness agent, water-based polyurethane adhesive also has characteristics such as hardness is adjustable, low temperature resistant, snappiness is good, bonding strength is big, be other aqueous adhesive can not and.But concerning aqueous polyurethane, high solids content and low viscosity are a pair of contradiction.The emulsion for preparing high solids content, emulsion particle diameter need increase, and this certainly will cause that package stability descends.Though the adding small-molecular emulsifier can improve stability, easily bubbles during construction, make tackiness agent dry film water tolerance descend.
The Japanese Patent spy opens clear 53-26897 and proposes to utilize the ethylene oxide unit of nonionic hydrophilic segment in the polyether chain to prepare polyaminoester emulsion, and this particle size of emulsion is greater than 0.3 μ m, but the content of ethylene oxide unit is difficult to obtain uniform dispersion liquid more after a little while.On the other hand, emulsion viscosity also increased when its content increased, and this can reduce the bonding strength of base material and spreadability.
U.S. Pat 4870129, US5432228, US6191214B1 disclose and have adopted hydrophilic carboxylic acid type or/and the preparation method of the polyester type aqueous polyurethane emulsion of sulfonate type chain extension.By the tackiness agent that this emulsion makes, though particle diameter is less, solid content reaches 40～50%, but this patent is used quadrol base sodium sulfonate, needs to carry out chain extending reaction in a large amount of acetone solvents, and then is scattered in the water, this technology must be distilled and be reclaimed a large amount of acetone, complex process, power consumption.In addition, do not add substantial emulsifying agent when synthetic aqueous polyurethane emulsion, to open clear 53-26897 identical with the spy, and its surface tension is also bigger, exists problems such as base material wettability, spreadability and bonding strengths.
Bi-component polyurethane adhesive is made up of two components of first, second of independent packaging usually, and first component (host) is a hydroxy component, and second component (solidifying agent) is for containing the component of NCO.The host that also has is the base polyurethane prepolymer for use as of end group NCO, and solidifying agent is low molecular weight polyols or polyamine.First, second component is mixed the generation polyurethane adhesive by a certain percentage.The polyisocyanate curing agent of solvent borne polyurethane tackiness agent use in the market is difficult to directly be distributed in the water, must use hydrophilic solidifying agent (also claiming linking agent).
Summary of the invention
The objective of the invention is to solve problems of the prior art, provide a kind of good, good film-forming property, the high-solid content water-based polyurethane adhesive that bonding strength is high the non-absorbability base material wettability.
Another object of the present invention provides a kind of aqueous polyurethane resin emulsion and preparation method thereof.
A kind of preparation method of aqueous polyurethane resin emulsion comprises the steps:
(1) with polyester polyol (a1), polyether glycol (a2), binary fluorine alcohol (b1) and organic multiple isocyanate (c1) in the presence of dibutyl tin laurate (being abbreviated as DBTDL) catalyzer, reacted 2～4 hours in 70～80 ℃; Wherein the mol ratio of a1, a2 and c1 is c1:(a1+a2)=2.3～3.3:1, a2:a1=0～70:30～100, the quality of binary fluorine alcohol is 0.1～2% of a prepolymer total mass, the quality of dibutyl tin laurate is 0.01～0.1% of a prepolymer total mass;
(2) add then the hydrophilic component account for prepolymer total mass 3.0～6.5%, account for containing of prepolymer total mass 0～2.5% of polyhydric micromolecular compound and account for the acetone of prepolymer total mass 5～15%, in 65～70 ℃ of reactions 2 hours, make prepolymer;
When (3) cooling to 40 ℃ then, in the prepolymer that makes, add the triethylamine neutralization, control degree of neutralization 60～110%; Continue will neutralize after polyurethane prepolymer join in the deionized water and low molecule polyamines that accounts for aqueous polyurethane emulsion total mass 45～65%, high-speed stirring 0.5～1 hour is carried out emulsification and chain extending reaction simultaneously; The mole dosage of wherein low molecule polyamines is in the raw material-difference of NCO total mole number and-OH total mole number 60～120%.Decompression at last steams acetone, makes high solid content aqueous polyurethane emulsion.
Above-mentioned polyester polyol (a1) molecular weight is 600～5000, and preferred molecular weight 1000～3000 mainly contains these three types of polyester diol, polylactone two pure and mild polycarbonate diols.Preferred polyester polyvalent alcohol of the present invention is polyester diol or polylactone glycol, polyester diol can be passed through phthalic acid, m-phthalic acid, terephthalic acid, succsinic acid, tartrate, pentanedioic acid, hexanodioic acid, nonane diacid, the certain herbaceous plants with big flowers diacid, toxilic acid, 1, di-carboxylic acid such as 4 cyclohexyl dicarboxylic acid or acid anhydrides more than a kind and ethylene glycol, propylene glycol, 1,2 butyleneglycols, 1,3 butyleneglycols, 1,4 butyleneglycols, neopentyl glycol, 1,6 hexylene glycols, 1,8 ethohexadiols, 1,9 nonanediol, Diethylene Glycol, dipropylene glycol, dihydroxyphenyl propane, glycerine, TriMethylolPropane(TMP), the known method polycondensation of using more than a kind of low molecular polylols such as tetramethylolmethane etc. obtains.Cyclic ester monomers such as the 6-caprolactone that the polylactone glycol can replace by 6-caprolactone, alkyl, δ-Wu Neizhi use known method ring-opening polymerization to obtain.The present invention preferably poly-hexanodioic acid 1,4 butanediol ester (PBA), polyethylene glycol adipate (PEA) and poly-epsilon-caprolactone (PCL).
Above-mentioned polyether glycol (a2) molecular weight is 600～5000, preferred molecular weight 1000～3000, polyether glycol can be by employed low molecular polylol class in above-mentioned polyester polyol synthetic, quadrol, propylene diamine, tolylene diamine, mphenylenediamine, diphenylmethane diamine, having more than 2 of low molecule polyamines such as phenylenedimethylidyne diamines class etc., the compound of preferred 2～3 reactive hydrogens is as initiator, by such as propylene oxide, the alkylene oxides of propylene oxide etc., alkyl glycidyl ether classes such as methyl glycidyl ether, single or its mixture of cyclic ether monomers such as tetrahydrofuran (THF) uses known method addition polymerization to obtain.Preferred polyoxypropyleneglycol of the present invention (PPG) and PTMG (PTMG).
Above-mentioned binary fluorine alcohol (b1) is by monobasic fluorine alcohol, TriMethylolPropane(TMP) and vulcabond preparation, it is characterized in that, with equimolar monobasic fluorine alcohol (as 2,3,3,4,5,5,6,7,7-nine fluorine-2,4,6-trichlorine enanthol) with equimolar vulcabond (optional isophorone diisocyanate, tolylene diisocyanate, 1, hexamethylene-diisocyanate, ditan-4, one or both mixture in 4 '-vulcabond) and the dibutyl tin laurate (DBTDL) of material total mass 0.01% add in the reactor, fill N
2, 80 ℃ of reactions 2 hours, add equimolar TriMethylolPropane(TMP) (TMP) again and continue reaction, measure the NCO group content by the Di-n-Butyl Amine method, when being 1.1%, nco value, obtains binary fluorine alcohol product (b1) as reaction end.
Above-mentioned organic multiple isocyanate (c1) is isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), 1, hexamethylene-diisocyanate (HDI), ditan-4, the mixture of one or more in 4 '-vulcabond (MDI), xylylene diisocyanate (XDI), poly methylene poly phenyl poly isocyanate (PAPI), the Methylcyclohexyl diisocyanate (HTDI).The mixture of one or both of the preferred IPDI of the present invention, TDI, HDI, MDI.
Above-mentioned hydrophilic component (d1) is 2,2-dihydroxymethyl acetate, 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid or 2,2-dihydroxymethyl valeric acid.The present invention is preferred 2,2-dimethylol propionic acid (DMPA).
Above-mentioned polyhydric micromolecular compound (d2) is TriMethylolPropane(TMP) (TMP), 1,4 butyleneglycol, ethylene glycol or 1,6 hexylene glycol.The TMP that contains three hydroxy functional groups is as linking agent, and di-alcohols is as chainextender.Preferred TriMethylolPropane(TMP) of the present invention (TMP) and 1,4 butyleneglycol (BDO).
Low molecule polyamines (e1) molecular weight of above-mentioned chain extension component is less than 300, and wherein representational have: quadrol (EDA), Ursol D, diethylenetriamine, triethylene tetramine, hexanediamine, hydrazine, isophorone diamine etc.The preferred quadrol of the present invention (EDA).
Aqueous polyurethane emulsion of the present invention both can use separately, also can add solidifying agent, and the adding of solidifying agent can improve stripping strength and thermotolerance significantly.
A kind of high-solid content water-based polyurethane adhesive that is used for non-absorbability base material, comprise host and solidifying agent, the weight of solidifying agent is 0.1～20% of host, host is above-mentioned aqueous polyurethane resin emulsion, and solidifying agent is wetting ability polymeric polyisocyanate, carbodiimide, aminoresin or epoxy compounds.Host and solidifying agent stir and get final product.
Above-mentioned solidifying agent preferred hydrophilic polymeric polyisocyanate, as the HDI of Rhodia wetting ability tripolymer Rhodocoat WAT (standard level, solid content 100%, NCO content 19.0%, at 23 ℃ of following viscosity 4000mPa.s,) and Rhodocoat WAT-1 (low viscosity level, solid content 100%, NCO content 21.7%, at 23 ℃ of following viscosity 1400mPa.s), the HDI of Bayer A.G wetting ability tripolymer Bayhydur 3100 (solid content 100%, NCO content 17.4%, at 23 ℃ of following viscosity 3300mPa.s), Bayhydur XP2570 (solid content 100%, NCO content 20.5% is at 23 ℃ of following viscosity 3500mPa.s) and Bayhydur VPLS2319 (solid content 100%, NCO content 18.0%, at 23 ℃ of following viscosity 4500mPa.s), preferred Rhodocoat WAT of the present invention and Bayhydur 3100.
Tackiness agent provided by the invention is primarily aimed at non-absorbability base material, the surface tension of non-absorbability base material such as polypropylene, polyvinyl chloride, polyester mostly is 32～40mN/m greatly, and the surface tension of water is 72mN/m, and the surface tension of water-based polyurethane adhesive is big than base material, more difficult wetting base material.So need add organosilicon in water-based polyurethane adhesive or the organic fluorine tensio-active agent reduces its surface tension, and the wetting base material of ability is sprawled film forming.
Compared with prior art, the present invention has following beneficial effect:
In the synthetic method of aqueous polyurethane resin emulsion of the present invention, add a small amount of fluorochemicals and urethane copolymerization, improve its wettability and dry film water resisting property greatly non-absorbability base material.Synthesis technique of the present invention is simple, and consumption of organic solvent is few, and synthetic polyaminoester emulsion solid content is 35～55%, and surface tension is 33～40mN/m, and particle diameter is 50～300nm.
The tackiness agent that aqueous polyurethane resin emulsion of the present invention is made is good to non-absorbability base material wettabilitys such as plastics film, leather shoes material, tinsels, good film-forming property, the bonding strength height, be applicable to footwear glue and plastics, aluminum foil package compound glue, also can be used as the bonding of leather polish and fiber, paper, foams.It is particularly useful for the applying of the compound and footwear material (as corium, PVC leather, TPR, EVA etc.) of food product packing film (as plastics films such as BOPP, PET, PE, aluminium foil).
Embodiment
Characterize water-based polyurethane adhesive bonding strength of the present invention with the T-stripping strength.
The T-stripping strength: with the PVC leather be cut into 150mm * 25mm specification or BOPP, PE, PET, the AL film is cut into 200mm * 15mm specification, uses the acetone treatment surface contaminants, the equal gluing of two test pieces, in 70～80 ℃ oven for drying, the pressurization of fitting.After 24 hours, survey the T-stripping strength with the Hoursfield puller system, draw speed is 300mm/min.
Embodiment 1
In the reactor that has agitator, thermometer, water cooler and nitrogen-sealed pipe, adding 1000.0g molecular weight is 3000 PBA, in 100～120 ℃ of fusings down, at pressure less than vacuum hydro-extraction under the 0.67kPa 1 hour, sampling is surveyed moisture less than cooling in 0.1% o'clock, when temperature is about 70 ℃, add 6.3g binary fluorine alcohol (b1), 232.1g IPDI, stir, slowly add 0.3g DBTDL catalyzer, 75 ℃ of isothermal reactions 2 hours, adding 56.4g DMPA, the 3.2gTMP and the 120.0g acetone that continue, 70 ℃ of isothermal reactions 2 hours, make prepolymer; When prepolymer is cooled to 40 ℃, add in the 30.1g triethylamine and salify.Polyurethane prepolymer after will neutralizing again joins in 18.0g quadrol and the 1200.0g deionized water, and high-speed stirring 1 hour is carried out emulsification and chain extending reaction simultaneously.Decompression at last steams acetone, filters and obtains aqueous polyurethane emulsion APU-1.
The binary fluorine alcohol (b1) that above-mentioned reaction is used can be synthetic by following prescription and technology.In the reactor that has agitator, thermometer, water cooler and nitrogen-sealed pipe, add 381.5g 2,3,3,4,5,5,6,7,7-nine fluorine-2,4,6-trichlorine enanthol, 222.3gIPDI and 0.07g DBTDL fill N
2, 80 ℃ of isothermal reactions 2 hours, add 134.0gTMP again and continue reaction, measure the NCO group content by the Di-n-Butyl Amine method, when being 1.1%, nco value, obtains binary fluorine alcohol product (b1) as reaction end.
The solid content of APU-1 is 51.0%, appearance milky white, and the pH value is 6.7, and at 25 ℃ of following viscosity 620mPa.s, median size is 245nm, and surface tension is 39.0mN/m.
Embodiment 2
In the reactor that has agitator, thermometer, water cooler and nitrogen-sealed pipe, adding 1000.0g molecular weight is 3000 PBA, in 100～120 ℃ of fusings down, at pressure less than vacuum hydro-extraction under the 0.67kPa 1 hour, sampling is surveyed moisture less than cooling in 0.1% o'clock, when temperature is about 70 ℃, add 12.4g binary fluorine alcohol (b1), 74.1g IPDI, 112.0gHDI, stir, slowly add 0.4g DBTDL catalyzer, 75 ℃ of isothermal reactions 2 hours, adding 52.5g DMPA that continues and 120.0g acetone, 70 ℃ of isothermal reactions 2 hours, make prepolymer; When prepolymer is cooled to 40 ℃, add in the 26.1g triethylamine and salify.Polyurethane prepolymer after will neutralizing again joins in 18.1g quadrol and the 1240.0g deionized water, and high-speed stirring 1 hour is carried out emulsification and chain extending reaction simultaneously.Decompression at last steams acetone, filters and obtains aqueous polyurethane emulsion APU-2.
Used binary fluorine alcohol (b1) preparation method of above-mentioned reaction is with embodiment 1.The solid content of APU-2 is 51.2%, appearance milky white, and the pH value is 6.6, and at 25 ℃ of following viscosity 490mPa.s, median size is 289nm, and surface tension is 37.2mN/m.
Embodiment 3
Having agitator, thermometer, in the reactor of water cooler and nitrogen-sealed pipe, adding 800.0g molecular weight is 2000 PBA, 200.0g molecular weight is 2000 PCL, in 100～120 ℃ of fusings down, at pressure less than vacuum hydro-extraction under the 0.67kPa 1 hour, sampling is surveyed moisture less than cooling in 0.1% o'clock, when temperature is about 70 ℃, add 10.0g binary fluorine alcohol (b1), 175.6g IPDI, 132.7g HDI, stir, slowly add the 0.4gDBTDL catalyzer, 75 ℃ of isothermal reactions 2 hours, the adding 60.3g DMPA that continues, 27.2gBDO and 120.0g acetone, 70 ℃ of isothermal reactions 2 hours, make prepolymer; When prepolymer is cooled to 40 ℃, add in the 39.2g triethylamine and salify.Polyurethane prepolymer after will neutralizing again joins in 21.0g quadrol and the 1466.0g deionized water, and high-speed stirring 1 hour is carried out emulsification and chain extending reaction simultaneously.Decompression at last steams acetone, filters and obtains aqueous polyurethane emulsion APU-3.
Used binary fluorine alcohol (b1) preparation method of above-mentioned reaction is with embodiment 1.The solid content of APU-3 is 50.1%, appearance milky white, and the pH value is 6.8, and at 25 ℃ of following viscosity 591mPa.s, median size is 253nm, and surface tension is 38.7mN/m.
Embodiment 4
In the reactor that has agitator, thermometer, water cooler and nitrogen-sealed pipe, add the 800.0g molecular weight and be 2000 PEA, 200.0g molecular weight and be 1000 PPG, in 100～120 ℃ of following vacuum hydro-extractions 1 hour, sampling is surveyed moisture less than cooling in 0.1% o'clock, when temperature is about 70 ℃, add 13.0g binary fluorine alcohol (b1), 257.0gTDI, stir, slowly add 0.3g DBTDL catalyzer, 75 ℃ of isothermal reactions 2 hours, adding 62.5g DMPA that continues and 100.0g acetone 70 ℃ of isothermal reactions 2 hours, make prepolymer; Prepolymer is cooled to 40 ℃, add in the 44.7g triethylamine and salify.Polyurethane prepolymer after will neutralizing again joins in 23.3g quadrol and the 2590.0g deionized water, and high-speed stirring 1 hour is carried out emulsification and chain extending reaction simultaneously.Decompression at last steams acetone, filters and obtains aqueous polyurethane emulsion APU-4.
Used binary fluorine alcohol (b1) preparation method of above-mentioned reaction is with embodiment 1.The solid content of APU-4 is 35.1%, appearance milky white, and the pH value is 7.0, and at 25 ℃ of following viscosity 60mPa.s, median size is 96nm, and surface tension is 36.9mN/m.
Embodiment 5
Having agitator, thermometer, in the reactor of water cooler and nitrogen-sealed pipe, adding 700.0g molecular weight is 2000 PEA, 200.0g molecular weight is 1000 PPG, 100.0g molecular weight is 2000 PTMG, in 100～120 ℃ of following vacuum hydro-extractions 1 hour, sampling is surveyed moisture less than cooling in 0.1% o'clock, when temperature is about 70 ℃, add 11.5g binary fluorine alcohol (b1), 327.0g IPDI, stir, slowly add 0.3g DBTDL catalyzer, 75 ℃ of isothermal reactions 2 hours, adding 57.6g DMPA that continues and 100.0g acetone, 70 ℃ of isothermal reactions 2 hours, make prepolymer; When prepolymer is cooled to 40 ℃, add in the 36.2g triethylamine and salify.Polyurethane prepolymer after will neutralizing again joins in 29.8g quadrol and the 2622.0g deionized water, and high-speed stirring 1 hour is carried out emulsification and chain extending reaction simultaneously.Decompression at last steams acetone, filters and obtains aqueous polyurethane emulsion APU-5.
Used binary fluorine alcohol (b1) preparation method of above-mentioned reaction is with embodiment 1.The solid content of APU-5 is 35.9%, appearance milky white, and the pH value is 6.8, and at 25 ℃ of following viscosity 54mPa.s, median size is 120nm, and surface tension is 38.0mN/m.
The water-based polyurethane adhesive of embodiment 1～3 gained is particularly useful for footwear glue, and embodiment 4～5 is particularly useful for the plastic flexible package composite gum, because footwear glue is different with composite gum test bars specification, its stripping strength unit representation method is had any different.The prescription and the test result of all tackiness agent are listed in table 1.
Embodiment 6
With 96.0gAPU-1 host and 4.0g Rhodocoat WAT solidifying agent, stir, make water-based polyurethane adhesive, the T-stripping strength that records the PVC leather is 99.0N/25mm.
Embodiment 7
With 96.0gAPU-2 host and 4.0g Rhodocoat WAT solidifying agent, stir, make water-based polyurethane adhesive, the T-stripping strength that records the PVC leather is 115.0N/25mm.
Embodiment 8
With 96.0gAPU-3 host and 4.0g Rhodocoat WAT solidifying agent, stir, make water-based polyurethane adhesive, the T-stripping strength that records the PVC leather is 106.0N/25mm.
Embodiment 9
With 98.0gAPU-4 agent and 2.0g Bayhydur 3100 solidifying agent, stir, make water-based polyurethane adhesive, recording its T-stripping strength at BOPP film and PE film is 3.1N/15mm.
Embodiment 10
With 98.0gAPU-5 agent and 2.0g Bayhydur 3100 solidifying agent, stir, make water-based polyurethane adhesive, recording it is 2.9N/15mm in the T-of PET film and aluminium foil stripping strength.
Table 1 water-based polyurethane adhesive
Claims (8)
1, a kind of preparation method of aqueous polyurethane resin emulsion is characterized in that comprising the steps:
(1) with polyester polyol a1, polyether glycol a2, binary fluorine alcohol b1 and organic multiple isocyanate c1 in the presence of dibutyltin dilaurate catalyst, reacted 2～4 hours in 70～80 ℃; Wherein the mol ratio of a1, a2 and c1 is c1:(a1+a2)=2.3～3.3:1, a2:a1=0～70:30～100, the quality of binary fluorine alcohol is 0.1～2% of a prepolymer total mass, the quality of dibutyl tin laurate is 0.01～0.1% of a prepolymer total mass;
(2) add then the hydrophilic component account for prepolymer total mass 3.0～6.5%, account for containing of prepolymer total mass 0～2.5% of polyhydric micromolecular compound and account for the acetone of prepolymer total mass 5～15%, in 65～70 ℃ of reactions 2 hours, make prepolymer;
When (3) cooling to 40 ℃ then, in the prepolymer that makes, add the triethylamine neutralization, control degree of neutralization 60～110%; Continue will neutralize after polyurethane prepolymer join in the deionized water and low molecule polyamines that accounts for aqueous polyurethane emulsion total mass 45～65%, high-speed stirring 0.5～1 hour is carried out emulsification and chain extending reaction simultaneously; The mole dosage of wherein low molecule polyamines is in the raw material-difference of NCO total mole number and-OH total mole number 60～120%, decompression at last steams acetone, makes solid content and be 35～55% aqueous polyurethane emulsion;
Described hydrophilic component is 2,2-dihydroxymethyl acetate, 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid or 2,2-dihydroxymethyl valeric acid;
Described polyhydric micromolecular compound is a TriMethylolPropane(TMP), 1,4-butyleneglycol, ethylene glycol or 1,6-hexylene glycol;
Described low molecule polyamines molecular weight is quadrol, Ursol D, diethylenetriamine, triethylene tetramine, hexanediamine, hydrazine or isophorone diamine less than 300.
2, preparation method as claimed in claim 1 is characterized in that described polyester polyol is polyester diol, polylactone glycol or polycarbonate diol, and molecular weight is 600～5000.
3, preparation method as claimed in claim 1 is characterized in that described polyether glycol is polyoxypropyleneglycol or PTMG, and molecular weight is 600～5000.
4, preparation method as claimed in claim 1 is characterized in that described binary fluorine alcohol is prepared from by following method: equimolar monobasic fluorine alcohol and equimolar vulcabond and the dibutyl tin laurate that accounts for total mass 0.01% are added in the reactor, fill N
2, 80 ℃ of reactions 2 hours, add equimolar TriMethylolPropane(TMP) again and continue reaction, measure the NCO group content by the Di-n-Butyl Amine method, when being 1.1%, nco value, obtains binary fluorine alcohol product as reaction end.
5, preparation method as claimed in claim 1, it is characterized in that described organic multiple isocyanate is isophorone diisocyanate, tolylene diisocyanate, 1, hexamethylene-diisocyanate, ditan-4, the mixture of one or both in 4 '-vulcabond.
6, a kind of aqueous polyurethane resin emulsion is characterized in that being prepared from by the described method of claim 1.
7, a kind of high-solid content water-based polyurethane adhesive that is used for non-absorbability base material, it is characterized in that comprising host and solidifying agent, the weight of solidifying agent is 0.1～20% of host, host is the described aqueous polyurethane resin emulsion of claim 1, and solidifying agent is wetting ability polymeric polyisocyanate, carbodiimide, aminoresin or epoxy compounds.
8, high-solid content water-based polyurethane adhesive as claimed in claim 7 is characterized in that described solidifying agent is the wetting ability polymeric polyisocyanate.
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| CN101033287A (en) | 2007-09-12 |
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Assignee: GUANGZHOU HENGYUAN PRINTING Co.,Ltd. Assignor: Sun Yat-sen University Contract record no.: 2010440000748 Denomination of invention: High solid content water polyurethane adhesive for non-absorbability base material and preparing method Granted publication date: 20090610 License type: Exclusive License Open date: 20070912 Record date: 20100612 |
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Effective date of registration: 20170405 Address after: 353400 Fujian City, Nanping Rong industrial cluster of synthetic leather industrial park, block No. 25, Huashan Patentee after: Fujian Jiegao resin Co.,Ltd. Address before: 510275 Xingang West Road, Guangdong, China, No. 135, No. Patentee before: Sun Yat-sen University |
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