TWI583713B - 冷接觸黏著劑 - Google Patents
冷接觸黏著劑 Download PDFInfo
- Publication number
- TWI583713B TWI583713B TW101137588A TW101137588A TWI583713B TW I583713 B TWI583713 B TW I583713B TW 101137588 A TW101137588 A TW 101137588A TW 101137588 A TW101137588 A TW 101137588A TW I583713 B TWI583713 B TW I583713B
- Authority
- TW
- Taiwan
- Prior art keywords
- dispersion
- din
- polyester polyol
- aii
- heating rate
- Prior art date
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- 239000004821 Contact adhesive Substances 0.000 title claims description 11
- 239000006185 dispersion Substances 0.000 claims description 50
- 229920005906 polyester polyol Polymers 0.000 claims description 38
- 239000000853 adhesive Substances 0.000 claims description 32
- 230000001070 adhesive effect Effects 0.000 claims description 32
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 26
- 238000002844 melting Methods 0.000 claims description 26
- 230000008018 melting Effects 0.000 claims description 26
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 229920005862 polyol Polymers 0.000 claims description 18
- 150000003077 polyols Chemical class 0.000 claims description 18
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 16
- 229920002635 polyurethane Polymers 0.000 claims description 16
- 239000004814 polyurethane Substances 0.000 claims description 16
- -1 aliphatic Isocyanate Chemical class 0.000 claims description 15
- 125000001931 aliphatic group Chemical group 0.000 claims description 14
- 239000001361 adipic acid Substances 0.000 claims description 13
- 235000011037 adipic acid Nutrition 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 9
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 7
- 239000004800 polyvinyl chloride Substances 0.000 claims description 7
- 239000004970 Chain extender Substances 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- IVGRSQBDVIJNDA-UHFFFAOYSA-N 2-(2-aminoethylamino)ethanesulfonic acid Chemical compound NCCNCCS(O)(=O)=O IVGRSQBDVIJNDA-UHFFFAOYSA-N 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 4
- 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 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 3
- 125000003010 ionic group Chemical group 0.000 claims description 3
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 3
- 239000011118 polyvinyl acetate Substances 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000701 coagulant Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical group 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 229920003051 synthetic elastomer Polymers 0.000 claims description 2
- 239000005061 synthetic rubber Substances 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims 2
- BJQAPWAEPRRBOZ-UHFFFAOYSA-N 1,4-diaminobutane-2-sulfonic acid Chemical compound NCCC(CN)S(O)(=O)=O BJQAPWAEPRRBOZ-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000005056 polyisocyanate Substances 0.000 description 7
- 229920001228 polyisocyanate Polymers 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 229920002396 Polyurea Polymers 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 229920003009 polyurethane dispersion Polymers 0.000 description 5
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 3
- 229920003226 polyurethane urea Polymers 0.000 description 3
- 229960004063 propylene glycol Drugs 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 2
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 2
- NNLRDVBAHRQMHK-UHFFFAOYSA-N 3-(2-aminoethylamino)propanoic acid Chemical compound NCCNCCC(O)=O NNLRDVBAHRQMHK-UHFFFAOYSA-N 0.000 description 2
- CDBAMNGURPMUTG-UHFFFAOYSA-N 4-[2-(4-hydroxycyclohexyl)propan-2-yl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1C(C)(C)C1CCC(O)CC1 CDBAMNGURPMUTG-UHFFFAOYSA-N 0.000 description 2
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000007942 carboxylates Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FBPFZTCFMRRESA-GUCUJZIJSA-N galactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-GUCUJZIJSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical group NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- 238000007725 thermal activation Methods 0.000 description 2
- XDLNRRRJZOJTRW-UHFFFAOYSA-N thiohypochlorous acid Chemical class ClS XDLNRRRJZOJTRW-UHFFFAOYSA-N 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- OZCRKDNRAAKDAN-HNQUOIGGSA-N (e)-but-1-ene-1,4-diol Chemical compound OCC\C=C\O OZCRKDNRAAKDAN-HNQUOIGGSA-N 0.000 description 1
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 description 1
- OHTRJOZKRSVAOX-UHFFFAOYSA-N 1,3-diisocyanato-2-methylcyclohexane Chemical compound CC1C(N=C=O)CCCC1N=C=O OHTRJOZKRSVAOX-UHFFFAOYSA-N 0.000 description 1
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- JMFCAIUTSABFDU-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O JMFCAIUTSABFDU-UHFFFAOYSA-N 0.000 description 1
- SERLAGPUMNYUCK-DCUALPFSSA-N 1-O-alpha-D-glucopyranosyl-D-mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O SERLAGPUMNYUCK-DCUALPFSSA-N 0.000 description 1
- FNVNVQAFYMEIES-UHFFFAOYSA-N 2-(3-aminopropylamino)ethanesulfonic acid Chemical compound NCCCNCCS(O)(=O)=O FNVNVQAFYMEIES-UHFFFAOYSA-N 0.000 description 1
- SZSSMFVYZRQGIM-UHFFFAOYSA-N 2-(hydroxymethyl)-2-propylpropane-1,3-diol Chemical compound CCCC(CO)(CO)CO SZSSMFVYZRQGIM-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- HYFFNAVAMIJUIP-UHFFFAOYSA-N 2-ethylpropane-1,3-diol Chemical compound CCC(CO)CO HYFFNAVAMIJUIP-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- PWNRAOSPRYHYPT-UHFFFAOYSA-N 3-(3-aminopropylamino)propane-1-sulfonic acid Chemical compound NCCCNCCCS(O)(=O)=O PWNRAOSPRYHYPT-UHFFFAOYSA-N 0.000 description 1
- DCZHZRHYJMLWCD-UHFFFAOYSA-N 3-(3-aminopropylamino)propanoic acid Chemical compound NCCCNCCC(O)=O DCZHZRHYJMLWCD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NAZDYUSPKMNQKK-UHFFFAOYSA-N 4-(2-aminopropylamino)butanoic acid Chemical compound CC(N)CNCCCC(O)=O NAZDYUSPKMNQKK-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004358 Butane-1, 3-diol Substances 0.000 description 1
- FSTLABGYTNGMRJ-UHFFFAOYSA-N CN.N=C=O.N=C=O Chemical compound CN.N=C=O.N=C=O FSTLABGYTNGMRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- UNXHWFMMPAWVPI-QWWZWVQMSA-N D-threitol Chemical compound OC[C@@H](O)[C@H](O)CO UNXHWFMMPAWVPI-QWWZWVQMSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 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
- JUBNBYBUFCFLHB-UHFFFAOYSA-N Isoputreanine Chemical compound NCCCNCCCC(O)=O JUBNBYBUFCFLHB-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Description
本發明係關於一種水性聚胺甲酸酯分散體、含此聚胺甲酸酯分散體之冷接觸黏著劑、產生黏合的方法及此冷接觸黏著劑用於產生黏合的用途。
以水性聚胺甲酸酯分散體為基質的黏著劑在世界各地已經建立高要求的工業應用,例如在鞋類的生產、汽車內飾或織物基材或層合膠膜的連接部份。水性聚胺甲酸酯或聚胺甲酸酯-聚脲分散體之生產也是普遍已知於此項技藝中。
當使用水性聚胺甲酸酯或聚胺甲酸酯-聚脲分散體作為黏著劑時,通常使用熱活化過程。在此過程中,將黏著劑施加至基材上,並將水完全蒸發後,經由熱將黏著劑層活化,例如使用紅外線燈。此轉移黏著劑成為黏性狀態。所需的溫度通常稱為活化溫度。
合適於熱活化過程的以水性聚胺甲酸酯或聚胺甲酸酯-聚脲分散體為基質的黏著劑是陳述例如在US 4,870,129。此專利係關於一種黏著劑,其實質上是由含有化學上摻混羧酸酯基及
/或磺酸酯基的聚胺甲酸酯之水溶液或分散體所組成。該聚胺甲酸酯是從至少兩種(環)-脂族二異氰酸酯及以(i)己二酸及(ii)丁二醇、己二醇或這些醇類的混合物為主的選擇聚酯二醇類之混合物製備。已揭示此水性溶液與相同物質或與其他物質用於在任何基材特別是在皮革、塑膠、橡膠材料及/或含塑化劑的聚氯乙烯上形成黏合之用途。
此黏著劑的缺點是其在室溫下無法用於結合物件,據此不合適於許多基材。
WO 2010/054761 A1陳述一種含有具下式結構單元的聚胺甲酸酯脲聚合物之水性聚胺甲酸酯脲分散體:-O-C(=O)-NH-Aromat-NH-C(=O)-NH-Aromat-NH-C(=O)-O-
其中Aromat代表化合物選自由伸苯基、伸甲苯基、伸二甲苯基、四甲基伸二甲苯基、及伸二苯基甲烷所組成群組,且其中聚胺甲酸酯脲是得自包括A)至少一種芳族二異氰酸酯,B)至少一種聚醚多元醇、其數量平均分子量從300克/莫耳至1500克/莫耳,C)至少一種化合物、其含有一或兩個異氰酸酯-反應性基及至少一個離子生成基,D)至少一種多元醇、其數量平均分子量從60克/莫耳至499克/莫耳,及E)水之成份,其中化合物B)至D)的平均總官能度是從1.85至2.2且其中芳族脲基的量及胺甲酸酯基的量之總和是每公斤聚胺甲酸酯脲聚合物中2700至5000毫莫耳。
以這些聚合物為基質的黏著劑可以在室溫使用但是不能
作為接觸黏著劑,因為黏著劑固化過程中需要機械固定。而且,光解作用的老化導致變黃,例如由於UV或螢光。
聚氯丁二烯分散體例如Dispercoll® C(Bayer MaterialScience)經常作為冷接觸黏著劑使用。其優點是連接前不需要將水蒸發且其可以用在溼式(wet-in-wet)製程。缺點是其在光暴露下容易變黃並在軟質PVC等級中的性能差。
本發明因此有個目的以提供一種水性聚胺甲酸酯分散體,其合適作為冷接觸黏著劑使用,其在長時間UV光暴露下不會顯現變黃且可以在例如軟質PVC基材上使用。
此目的在本發明中藉由含有至少一種熔化溫度範圍在30℃至50℃的聚胺甲酸酯聚合物之水性分散體而達成,其係藉由差式掃描量熱法根據DIN 65467在20K/分鐘的加熱速率下測量,該聚胺甲酸酯聚合物可以得自反應混合物包括:AI)至少一種聚酯多元醇其數量平均分子量範圍是400克/莫耳至5000克/莫耳且熔化溫度範圍是40℃至80℃,藉由差式掃描量熱法根據DIN 65467在20K/分鐘的加熱速率下測量;AII)至少一種聚酯多元醇其數量平均分子量範圍是400克/莫耳至5000克/莫耳且熔化溫度範圍是5℃至35℃,藉由差式掃描量熱計法根據DIN 65467在20K/分鐘的加熱速率下測量;B)任意地,至少一種二官能基的多元醇成份;
C)至少一種脂族二異氰酸酯;及D)至少一種含有至少一個離子或潛在離子基的胺系鏈延伸劑;其中莫耳比例AI):AII)的範圍是7:3至3:7。
訝異地發現此聚胺甲酸酯分散體合適在溼式製程及凝聚製程中作為冷接觸黏著劑且抵抗長時間光暴露後的變黃。這些黏著劑較佳在UV光暴露300天後不會變黃,更佳600天且尤其較佳900天。
該分散體的固體含量(DIN EN ISO 3251)範圍是20重量-%至70重量-%,較佳從30重量-%至65重量-%且更佳從32重量-%至62重量-%。
在本發明之內文中,「聚胺甲酸酯聚合物」一詞係指也包括聚胺甲酸酯-聚脲聚合物。
該聚酯多元醇AI)及AII)可以得自二羧酸與多元醇的聚縮合。這些多元醇較佳具有分子量是62克/莫耳至399克/莫耳,含有2至12個C原子,支鏈或直鏈,二官能基並含有一級或二級OH基。
較佳的聚酯多元醇AI)是晶質的且脂族。合適的聚酯多元醇AI)包括此多元醇其係基於直鏈二羧酸及/或其衍生物例如酸酐、酯或醯基氯及脂族或環脂族、直鏈或支鏈多元醇類。合適的二羧酸包括己二酸、琥珀酸、癸二酸及十二烷二羧酸。較佳是己二酸。這些酸的使用量是至少90莫耳-%,較佳是95莫耳-%至100莫耳-%,相對於全部羧酸的總量。如果需要時,也可以使用其他脂族、環脂族或芳族二羧酸。此種酸之實例包
括戊二酸、壬二酸、1,4-、1,3-或1,2-環己二羧酸、對苯二甲酸或間苯二甲酸。這些酸的使用總量是不超過5莫耳-%,較佳是0莫耳-%至5莫耳-%,相對於羧酸的總量。
用於聚酯多元醇AI)的較佳多元醇成份是乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、新戊二醇或1,6-己二醇。較佳是1,6-己二醇及1,4-丁二醇,特別較佳是1,4-丁二醇。該聚酯多元醇AI)可以得自一或多種多元醇,較佳是只從一種多元醇。
該聚酯多元醇AI)的數量平均分子量Mn較佳的範圍是400克/莫耳至4000克/莫耳,特別較佳是1000克/莫耳至3000克/莫耳,更特別較佳是1500克/莫耳至2500克/莫耳且最佳是1800克/莫耳至2400克/莫耳。
較佳的聚酯多元醇AII)是晶質的且脂族。合適的晶質或半晶質聚酯多元醇AII)包括此多元醇其係基於直鏈二羧酸及/或其衍生物例如酸酐、酯或醯基氯及脂族或環脂族、直鏈或支鏈多元醇類。合適的二羧酸包括己二酸、琥珀酸、癸二酸及十二烷二羧酸。較佳是己二酸。這些酸的使用量是至少90莫耳-%,較佳是95莫耳-%至100莫耳-%,相對於全部羧酸的總量。如果需要時,也可以使用其他脂族、環脂族或芳族二羧酸。此種酸之實例包括戊二酸、壬二酸、1,4-、1,3-或1,2-環己二羧酸、對苯二甲酸或間苯二甲酸。這些酸的使用總量是不超過5莫耳-%,較佳是0莫耳-%至5莫耳-%,相對於羧酸的總量。
一般來說,用於聚酯多元醇AI)的相同多元醇成份也合適用於聚酯多元醇AII)。對於AII),較佳是至少兩種多元醇的混合物。特別較佳是1,4-丁二醇與新戊二醇、以及1,6-己二醇與
新戊二醇之混合物。後者混合物是最佳。如果是使用多元醇的混合物時,主要成份較佳組成至少各20莫耳-%,較佳至少各30莫耳-%且更佳至少各40莫耳-%之所使用的多元醇之總量。
該聚酯多元醇AII)的數量平均分子量Mn較佳的範圍是400克/莫耳至4000克/莫耳,特別較佳是1000克/莫耳至3000克/莫耳,更特別較佳是1500克/莫耳至2300克/莫耳且最佳是1500克/莫耳至1900克/莫耳。
被理解是不同於AI)及AII)的任意至少一種二官能基多元醇之實例包括乙-1,2-二醇、丙-1,2-二醇、丙-1,3-二醇、丁-1,2-二醇、丁-1,3-二醇、丁-1,4-二醇、丁烯-1,4-二醇、丁炔-1,4-二醇、戊-1,5-二醇及其位置異構物、己-1,6-二醇、辛-1,8-二醇、1,4-雙羥基甲基環己烷、2,2-雙(4-羥基環己基)丙烷、2-甲基-1,3-丙二醇、甘油、三羥甲基丙烷、三羥甲基乙烷、己-1,2,6-三醇、丁-1,2,4-三醇、二甘醇、三甘醇、四甘醇、低分子量聚乙二醇、聚-1,2-丙二醇、聚-1,3-丙二醇或聚THF,以及多元醇類例如三羥甲基丁烷、三羥甲基丙烷、三羥甲基乙烷、新戊二醇、羥基三甲基乙酸新戊二醇酯、新戊四醇、2-乙基-1,3-丙二醇、2-甲基-1,3-丙二醇、2-乙基-1,3-己二醇、甘油、二三羥甲基丙烷、二新戊四醇、氫醌、雙酚A、雙酚F、雙酚B、雙酚S、2,2-雙(4-羥基環己基)丙烷、1,1-、1,2-、1,3-及1,4-環己烷二甲醇、1,2-、1,3-或1,4-環己二醇或糖醇例如山梨糖醇、甘露醇、二甘油、蘇糖醇(threitol)、赤蘚糖醇、核糖醇(adonitol)(側金盞花醇(ribitol))、***糖醇(arabitol)(lyxitol)、木糖醇、半乳糖醇(dulcitol)(半乳糖醇(galactitol))、麥芽糖醇或異麥芽糖醇。較佳
是使用直鏈1,ω-二羥基烷類,更佳是丁-1,4-二醇及己-1,6-二醇。
脂族二異氰酸酯C)較佳是含有4至20個碳原子之異氰酸酯。典型的二異氰酸酯之實例是脂族二異氰酸酯例如四亞甲基二異氰酸酯、五亞甲基1,5-二異氰酸酯、六亞甲基二異氰酸酯(1,6-二異氰酸基己烷)、八亞甲基二異氰酸酯、十亞甲基二異氰酸酯、十二亞甲基二異氰酸酯、十四亞甲基二異氰酸酯、離胺酸二異氰酸酯之衍生物(例如離胺酸甲酯二異氰酸酯、離胺酸乙酯二異氰酸酯)、三甲基己烷二異氰酸酯或四甲基己烷二異氰酸酯、環脂族二異氰酸酯例如1,4-、1,3-或1,2-二異氰酸基環己烷、4,4'-或2,4'-二-(異氰酸基環己基)甲烷、1-異氰酸基-3,3,5-三甲基-5-(異氰酸基甲基)-環己烷(異佛酮二異氰酸酯)、1,3-或1,4-雙(異氰酸基甲基)環己烷或2,4-或2,6-二異氰酸基-1-甲基環己烷、以及3(或4),8(或9)-雙-(異氰酸基甲基)三環[5.2.1.02,6]癸烷異構物混合物。
合適的胺系鏈延伸劑D)是二胺與單胺以及其混合物。在本發明之內文中,「鏈延伸劑」一詞也包括導致鏈終止之單胺類。
單胺類的實例包括脂族及/或非脂族一級及/或二級單胺類例如乙胺、二乙胺、異構性丙胺及丁胺、高直鏈脂族單胺及環脂族單胺例如環己胺。其他實例包括胺基醇類,也就是在一個分子內含有胺基及羥基之化合物,例如乙醇胺、N-甲基乙醇胺、二乙醇胺或2-丙醇胺。也包括含磺酸及/或羧酸基的單胺基化合物,例如牛磺酸、甘胺酸或丙胺酸。
二胺基化合物的實例包括1,2-乙二胺、1,6-己二胺、1-胺基-3,3,5-三甲基-5-胺基甲基-環己烷(異佛酮二胺)、哌、1,4-二胺基環己烷或雙-(4-胺基環己基)-甲烷。也合適是A己二酸二肼、肼或肼水合物。也可以使用多胺類例如二乙三胺代替二胺基化合物。
其他實例包括二胺基醇類例如1,3-二胺基-2-丙醇、N-(2-羥基乙基)-乙二胺或N,N-雙(2-羥基乙基)-乙二胺。
含有離子或潛在離子基的二胺基化合物之實例,特別是含磺酸酯及/或羧酸酯基,包括N-(2-胺基乙基)-2-胺基乙磺酸、N-(2-胺基乙基)-2-胺基乙烷羧酸、N-(3-胺基丙基)-2-胺基乙磺酸、N-(3-胺基丙基)-2-胺基乙烷羧酸、N-(3-胺基丙基)-3-胺基丙磺酸、N-(3-胺基丙基)-3-胺基丙烷羧酸、N-(2-胺基丙基)-3-胺基丙磺酸及N-(2-胺基丙基)-3-胺基丙烷羧酸之鈉或鉀鹽。較佳是N-(2-胺基乙基)-2-胺基乙磺酸及N-(2-胺基乙基)-2-胺基乙烷羧酸之鈉鹽,前者特別較佳。
先前技藝已知的全部方法可以用於製備根據本發明之分散體,例如乳化劑/剪切力、丙酮、預聚合物混合、熔融乳化、酮亞胺及固體自動分散法或其衍生方法。這些方法之總結可見於Methoden der organischen Chemie(Houben-Weyl,Erweiterungs-und Folgebände zur 4.Auflage,Volume E20,H.Bartl and J.Falbe,Stuttgart,New York,Thieme 1987,p.1671-1682)。熔融乳化及丙酮法較佳。丙酮法特別較佳。關於此點,參見DE 1570 602 A1、DE 1570 615 A1及DE 1694 062 A1。
以下將陳述本發明之特定具體實施例及其他態樣。除非文中另外指出,該具體實施例可以自由組合。
在根據本發明的分散體之一個具體實施例中,該聚胺甲酸酯聚合物之玻璃轉化溫度範圍是-60℃至-10℃,其係藉由差式掃描量熱法根據DIN 65467在20K/分鐘的加熱速率下測量。較佳該玻璃轉化溫度範圍是-50℃至-20℃。
在根據本發明的分散體之另一個具體實施例中,該聚胺甲酸酯聚合物之熔化溫度範圍是30℃至50℃,其係藉由差式掃描量熱法根據DIN 65467在20K/分鐘的加熱速率下測量。較佳該熔化溫度範圍是40℃至45℃。
在根據本發明的分散體之另一個具體實施例中,該聚酯多元醇AI)之熔化溫度範圍是40℃至60℃,其係藉由差式掃描量熱法根據DIN 65467在20K/分鐘的加熱速率下測量。較佳該熔化溫度範圍是45℃至55℃。
在根據本發明的分散體之另一個具體實施例中,該聚酯多元醇AII)之熔化溫度範圍是15℃至30℃,其係藉由差式掃描量熱法根據DIN 65467在20K/分鐘的加熱速率下測量。較佳該熔化溫度範圍是20℃至28℃。
在根據本發明的分散體之另一個具體實施例中,莫耳比例AI):AII)的範圍是6:4至4:6。較佳該莫耳比例的範圍是1.1:1至1:1.1。
在根據本發明的分散體之另一個具體實施例中,該聚酯多元醇AI)之熔融焓(enthalpy of fusion)的範圍是65焦耳/克至90焦耳/克,其係藉由差式掃描量熱法根據DIN 65467在20K/分
鐘的加熱速率下測量。較佳該熔融焓的範圍是75焦耳/克至85焦耳/克。
在根據本發明的分散體之另一個具體實施例中,該聚酯多元醇AII)之熔融焓的範圍是30焦耳/克至70焦耳/克,其係藉由差式掃描量熱法根據DIN 65467在20K/分鐘的加熱速率下測量。較佳該熔融焓的範圍是40焦耳/克至60焦耳/克。
在根據本發明的分散體之另一個具體實施例中,該聚酯多元醇AI)及AII)是脂族的。
在根據本發明的分散體之另一個具體實施例中,該聚酯多元醇AI)是得自含己二酸及1,4-丁二醇或1,6-己二醇之反應混合物。特別較佳的聚酯多元醇AI)是以己二酸及1,4-丁二醇為基質之聚酯。
在根據本發明的分散體之另一個具體實施例中,該聚酯多元醇AII)是得自含己二酸、1,6-己二醇及新戊二醇之反應混合物或自含己二酸、1,4-丁二醇及新戊二醇之反應混合物。前者混合物特別較佳。
在根據本發明的分散體之另一個具體實施例中,該脂族二異氰酸酯C)包括六亞甲基1,6-二異氰酸酯、1,3-及/或1,4-雙(異氰酸基甲基)環己烷、異佛酮二異氰酸酯及/或4,4'-或2,4'-二(異氰酸基環己基)甲烷。
在根據本發明的分散體之另一個具體實施例中,該胺系鏈延伸劑D)包括N-(2-胺基乙基)-2-胺基乙磺酸之鈉鹽與二乙醇胺之混合物或包括N-(2-胺基乙基)-2-胺基乙磺酸之鈉鹽、二乙醇胺與N-(2-羥基乙基)-乙二胺之混合物。
根據本發明的分散體可以單獨或與塗料及黏著劑技藝中已知的黏合劑(binder)、輔劑物質及添加劑使用,特別是乳化劑及光安定劑例如UV吸收劑及位阻胺類(HALS),以及抗氧化劑、填充劑及輔劑例如抗沈著劑、去泡沫劑及/或溼化劑、流動控制劑、反應性稀釋劑(thinner)、塑化劑、中和劑、觸媒、輔助溶劑及/或增稠劑、及添加劑例如顏料、染料或消光劑。也可以添加增黏劑。
在正要處理之前,可以將添加劑添加至根據本發明之產物中。然而,在預聚合物分散前或分散期間,也可能添加至少一部份添加劑。
這些物質所要使用的選擇及量(其可以添加至個別的成份及/或至完整的混合物)原則上是從事此項技藝者已知且可以藉由針對特定應用的簡單初步實驗,不需不必要的花費而決定。
根據上述,本發明的另一個態樣是一種黏著劑,其含有至少一種根據本發明之分散體。在一個具體實施例中,該黏著劑是冷接觸黏著劑。在本發明內文中的冷接觸黏著劑係應理解為一種可以在不需額外加熱下在接觸黏合製程中使用之黏著劑。
該黏著劑的固體含量範圍(DIN EN ISO 3251)可以在20重量-%至70重量-%,較佳從30重量-%至65重量-%且更佳從32重量-%至62重量-%。
根據本發明之黏著劑也可能進一步含有聚異氰酸酯化合物。此聚異氰酸酯則作為交聯劑。該交聯劑可以在使用前加入(2K處理)。在此情形中,較佳的聚異氰酸酯化合物是可以在
水中乳化的。這些是例如陳述在EP 0 206 059 A1、DE 31 12 117 A1或DE 100 24 624 A1中的化合物。該聚異氰酸酯化合物的用量是從0.1重量-%至20重量-%,較佳從0.5重量-%至10重量-%,特別較佳從1.5重量-%至6重量-%,以水性分散體為基準。
根據本發明之黏著劑組成物也合適於使用凝聚劑例如CaCl2鹽溶液之溼式製程。關於溼式(wet-in-wet)製程,明確地考慮噴霧-混合法及雙向法。多孔或水蒸汽可穿透的基材例如織物、皮革、羊毛或發泡體可以不需事先乾燥而黏合。或者是,根據本發明之黏著劑組成物也可以在加熱活化製程中使用。
根據本發明之黏著劑組成物合適黏合多種基材,例如紙、紙板、木材、織物、金屬、皮革或礦物材料。根據本發明之黏著劑組成物特別合適用於黏合橡膠材料例如天然或合成橡膠、多種塑膠材料例如聚胺甲酸酯、聚醋酸乙烯酯、聚氯乙烯、特別是塑化的聚氯乙烯。其特別較佳用於將用這些材料製成的鞋底,較佳是以聚氯乙烯特別是塑化的聚氯乙烯為基質、或以聚醋酸乙基乙烯酯或聚胺甲酸酯彈性發泡體為基質者、黏合至皮革或人造皮革的鞋筒(shoe shafts)。根據本發明之黏著劑組成物也特別合適用於將以聚氯乙烯或塑化的聚氯乙烯為基質的膜黏合至木材。
根據本發明之黏著劑組成物也合適作為底漆使用。
本發明申請案也提供黏著性複合物其含有使用根據發明之分散體黏著性黏合的基材。
根據本發明之黏著性複合物是藉由黏著劑技術中已知關
於處理水性分散體黏著劑的方法處理。
本發明將參照下面的實施例進一步陳述,但不受其限制。
玻璃轉化溫度是根據DIN 65467使用Perkin Elmer DSC-7裝置測定,其經由使用銦及鉛的熔化起始而校正。在各情形中,在溫度範圍從-100℃至+150℃測量10毫克的固體物質。加熱速率是20K/分鐘。總共進行三個加熱循環。在DSC圖(DIN 51005)中,使用切線法(DIN 65467中的方法A)評估玻璃轉化溫度。使用在第三次加熱操作的玻璃轉化之高度一半的溫度。聚合物的熔化溫度對應至最高溫度(在曲線的最大溫度)且熔融焓(熔化焓(melting enthalpy))對應至曲線及基線之間的積分。如果結晶緩慢使得結晶作用在20K/分鐘的冷卻速率下沒有開始,則使用從第一次加熱操作之對應數據。
分散體之固體含量是根據DIN EN ISO 3251測定且數量平均分子量Mn是根據末端基分析(根據DIN 53240的OH數量)而計算。
在應用測試中的黏合強度及剝離強度是根據DIN EN 1392測定。
聚酯多元醇1
此聚酯多元醇對應至本發明文中的AI)。其可以描述為以己二酸及1,4-丁二醇為基質的部份結晶、雙官能基的聚酯多元醇,其數量平均分子量Mn是2250克/莫耳(OH數50毫克KOH/克)。玻璃轉化溫度是-61℃,熔化溫度是49℃且熔融焓是80焦耳/克。
聚酯多元醇2
此聚酯多元醇對應至本發明文中的AII)。其可以描述為以己二酸、1,6-己二醇及新戊二醇(1,6-己二醇對新戊二醇的莫耳比例=3:2)為基質的部份結晶、雙官能基的聚酯多元醇,其數量平均分子量Mn是1700克/莫耳(OH數66毫克KOH/克)。玻璃轉化溫度是-63℃,熔化溫度是26℃且熔合焓是55焦耳/克。
將196克聚酯多元醇1(0.087莫耳)及148克聚酯多元醇2(0.087莫耳)之混合物在100℃及15毫巴的壓力下乾燥1小時。在60℃加入6.62克1,4-丁二醇,隨後加入77.1克異佛酮二異氰酸酯(IPDI)。將混合物在90℃攪拌直到到達穩定的異氰酸酯含量是1.89%。冷卻至60℃後,將混合物再攪拌20分鐘後,溶解在642克丙酮中並冷卻至50℃。在激烈攪拌下,將7.79克Na-二胺基磺酸鹽(H2N-CH2-CH2-NH-CH2-CH2-SO3Na)及3.79克二乙醇胺在100克水中的溶液添加至均勻溶液中。經15分鐘後,經由加入715克水而製備分散體。經由蒸餾將丙酮移除,導致無溶劑的水性聚胺甲酸酯-聚脲分散體,固體
含量是35.1重量-%。
乾燥後的分散體之玻璃轉化溫度是-41℃,熔化溫度是43℃且熔融焓是25焦耳/克。
以實施例1的分散體為基質之黏著劑以二成份(two-component)冷接觸黏著劑與額外3重量-%以HDI為基質之親水性脂族聚異氰酸酯(Desmodur® DN,Bayer MaterialScience)在不同基材上測試。樣本在23℃乾燥1小時並在4巴壓力下黏合30秒。結果總結如下。
以實施例1的分散體為基質之黏著劑及在二成份之情形中,額外3重量-%以HDI為基質之親水性脂族聚異氰酸酯(Desmodur® DN,Bayer MaterialScience)在單-及二-成份熱活化黏合中測試。結果總結如下。
以實施例1的分散體為基質之黏著劑及在二成份之情形中,額外3重量-%以HDI為基質之親水性脂族聚異氰酸酯(Desmodur® DN,Bayer MaterialScience)在單-及二-成份加熱活化黏合中測試。結果總結如下。
Claims (16)
- 一種水性分散體,其含有至少一種熔化溫度範圍在30℃至50℃的聚胺甲酸酯,其係藉由差式掃描量熱法根據DIN 65467在20K/分鐘的加熱速率下測量,該聚胺甲酸酯聚合物可以得自反應混合物包括:AI)至少一種聚酯多元醇,其數量平均分子量範圍是400克/莫耳至5000克/莫耳且熔化溫度範圍是40℃至80℃,藉由差式掃描量熱法根據DIN 65467在20K/分鐘的加熱速率下測量;AII)至少一種聚酯多元醇其數量平均分子量範圍是400克/莫耳至5000克/莫耳且熔化溫度範圍是5℃至35℃,藉由差式掃描量熱法根據DIN 65467在20K/分鐘的加熱速率下測量;B)任意地,至少一種二官能基的多元醇成份;C)至少一種脂族二異氰酸酯;及D)至少一種含有至少一個離子或潛在離子基的胺系鏈延伸劑;其特徵是莫耳比例AI):AII)的範圍是7:3至3:7。
- 根據申請專利範圍第1項之分散體,其中該聚胺甲酸酯聚合物之玻璃轉化溫度範圍是-60℃至-10℃,其係藉由差式掃描量熱法根據DIN 65467在20K/分鐘的加熱速率下測量。
- 根據申請專利範圍第1項之分散體,其中該聚酯多元醇AI)的熔化溫度範圍是40℃至60℃,其係藉由差式掃描量熱法根據DIN 65467在20K/分鐘的加熱速率下測量。
- 根據申請專利範圍第1項之分散體,其中該聚酯多元醇AII)的熔化溫度範圍是15℃至30℃,其係藉由差式掃描量熱法根據DIN 65467在20K/分鐘的加熱速率下測量。
- 根據申請專利範圍第1項之分散體,其中該莫耳比例AI):AII)的範圍是6:4至4:6。
- 根據申請專利範圍第1項之分散體,其中該聚酯多元醇AI)的熔融焓(enthalpy of fusion)範圍是65焦耳/克至90焦耳/克,其係藉由差式掃描量熱法根據DIN 65467在20K/分鐘的加熱速率下測量。
- 根據申請專利範圍第1項之分散體,其中該聚酯多元醇AII)的熔融焓範圍是30焦耳/克至70焦耳/克,其係藉由差式掃描量熱法根據DIN 65467在20K/分鐘的加熱速率下測量。
- 根據申請專利範圍第1項之分散體,其中該聚酯多元醇AI)及AII)是脂族的。
- 根據申請專利範圍第1項之分散體,其中該聚酯多元醇AI)是從含己二酸及1,4-丁二醇或1,6-己二醇之反應混合物獲得。
- 根據申請專利範圍第1項之分散體,其中該聚酯多元醇AII)是從含己二酸、1,6-己二醇及新戊二醇之反應混合物或從含己二酸、1,4-丁二醇及新戊二醇之反應混合物獲得。
- 根據申請專利範圍第1項之分散體,其中該脂族二異氰酸酯C)包括六亞甲基1,6-二異氰酸酯、1,3-及/或1,4-雙(異氰酸基甲基)環己烷、異佛酮二異氰酸酯及/或4,4’-或2,4’-二(異 氰酸基環己基)甲烷。
- 根據申請專利範圍第1項之分散體,其中該胺系鏈延伸劑D)包括N-(2-胺基乙基)-2-胺基乙磺酸之鈉鹽與二乙醇胺之混合物或包括N-(2-胺基乙基)-2-胺基乙磺酸之鈉鹽、二乙醇胺與N-(2-羥基乙基)-乙二胺之混合物。
- 一種黏著劑,其含有至少一種根據申請專利範圍第1至12項中一或多項之分散體。
- 根據申請專利範圍第13項之黏著劑,其中該黏著劑是一種冷接觸黏著劑。
- 一種根據申請專利範圍第1項之分散體之用途,係用於黏合選自由天然及人造橡膠、聚胺甲酸酯、聚醋酸乙烯酯及聚氯乙烯所組成群組的橡膠材料。
- 一種根據申請專利範圍第1項之分散體之用途,係使用凝聚劑藉由溼式(wet-in-wet)處理而用於黏合多孔或水蒸汽可穿透性基材。
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CN112079989A (zh) * | 2019-06-13 | 2020-12-15 | 科思创德国股份有限公司 | 水性聚氨酯分散体 |
CN114206963A (zh) * | 2019-06-13 | 2022-03-18 | 科思创知识产权两合公司 | 水性聚氨酯分散体 |
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CN112442164B (zh) * | 2019-09-03 | 2023-03-31 | 万华化学(广东)有限公司 | 聚氨酯或聚氨酯脲的水分散体、其制备方法和用途 |
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