CN114630878A - 粘合剂组合物 - Google Patents
粘合剂组合物 Download PDFInfo
- Publication number
- CN114630878A CN114630878A CN201980101920.3A CN201980101920A CN114630878A CN 114630878 A CN114630878 A CN 114630878A CN 201980101920 A CN201980101920 A CN 201980101920A CN 114630878 A CN114630878 A CN 114630878A
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- CN
- China
- Prior art keywords
- acid
- acrylate
- adhesive composition
- methacrylate
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 82
- 239000000853 adhesive Substances 0.000 title claims abstract description 30
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 60
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 26
- 239000000839 emulsion Substances 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 14
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 11
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 9
- 150000002763 monocarboxylic acids Chemical class 0.000 claims abstract description 9
- 239000004815 dispersion polymer Substances 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 27
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 16
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 16
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 14
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 239000004753 textile Substances 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 150000003440 styrenes Chemical class 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical class C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- ANFKICQAFDDROM-UHFFFAOYSA-N 2-(carboxymethyl)cyclopropane-1-carboxylic acid Chemical compound OC(=O)CC1CC1C(O)=O ANFKICQAFDDROM-UHFFFAOYSA-N 0.000 claims description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 2
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical class CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- 150000003926 acrylamides Chemical class 0.000 claims description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 150000002688 maleic acid derivatives Chemical class 0.000 claims description 2
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 2
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 13
- 239000000835 fiber Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- -1 for example Chemical class 0.000 description 12
- 238000009472 formulation Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 239000004816 latex Substances 0.000 description 7
- 229920000126 latex Polymers 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000008365 aqueous carrier Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical class CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229920000742 Cotton Polymers 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-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
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920000057 Mannan Polymers 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920005822 acrylic binder Polymers 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical class N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical class OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
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Abstract
提供了一种粘合剂组合物。所述粘合剂组合物包含以下组分:(a)多元酸聚合物水性分散体,其中所述多元酸聚合物包含50重量%~100重量%的一种或多种烯键式不饱和一元或二元羧酸/酸酐;(b)含羟基丙烯酸共聚物乳液,其中所述含羟基丙烯酸共聚物通过使含有0.1‑10%含羟基单体、0.1至20重量%不饱和羧酸和30%‑90%丙烯酸单体的单体混合物聚合来获得,其中基于所述上述组分(a)和(b)的固体,所述组分(a)和(b)的固体重量比为0.1∶100至10∶100。
Description
技术领域
本公开涉及一种粘合剂组合物,特别是一种包含多元酸聚合物水性分散体和聚丙烯酸酯乳液的粘合剂组合物。
背景技术
用于纺织品和非织造布应用的传统粘结剂含有N-羟甲基丙烯酰胺(NMA)作为功能单体,这为粘结剂提供了出色的耐水性(湿强度)和耐溶剂性(异丙醇强度)。然而,含有NMA的粘结剂在加热时会释放甲醛。
近年来,无甲醛交联技术的研究工作很多。这些交联技术在固化后实现了良好的耐水性和耐溶剂性,但仍无法与含NMA的粘结剂竞争。
预期将开发一种具有适中固化温度以实现更好性能的新型制剂。
发明内容
本发明提供一种具有适中固化温度以获得更好性能的粘合剂组合物,特别是不含NMA单体。
在本发明的第一方面,本发明提供了一种粘合剂组合物,其包含以下组分:
(a)多元酸聚合物水性分散体,其中所述多元酸聚合物含有50重量%~100重量%的一种或多种烯键式不饱和一元或二元羧酸/酸酐;
(b)含羟基丙烯酸共聚物乳液,其中含羟基丙烯酸共聚物通过使含有0.1-10%含羟基单体、0.1%至20重量%不饱和羧酸和30%-90%丙烯酸单体的单体混合物聚合来获得,
其中基于所述上述组分(a)和(b)的固体,所述组分(a)和(b)的固体重量比为0.1∶100至10∶100。
在本公开的第二方面,本公开提供了一种由根据本公开的粘合剂组合物制备的制品。
在本公开的第三方面,本公开提供了本公开的粘合剂组合物用于纺织品/非织造织物的用途。
在本公开中,在含羟基的丙烯酸粘结剂体系中引入多元酸聚合物水性分散体,可固化成网状并带来优异的性能。在150℃下,自交联体系表现出优异的湿强度和IPA强度。根据本公开的制剂显示出非常好的储存稳定性。在50℃烘箱中加速热老化30天后,性能没有下降。因此,根据本公开的制剂可以是单组分制剂并易于处理。
应当理解,前面的一般性描述和以下的详细描述均仅为示例性和解释性的,而非对如所要求保护的本发明的限制。
具体实施方式
除非另外定义,否则本文所用的所有技术和科学术语具有与本发明所属领域中的普通技术人员通常所理解相同的含义。此外,本文所提及的所有公开案、专利申请、专利以及其他参考文献均以引用的方式并入。
如本文所公开,“和/或”意指“和、或作为替代方案”。除非另外指示,否则所有范围均包含端点。
如本文所公开,术语“组合物”、“配制品”或“混合物”是指不同组分的物理共混物,其是通过用物理方式简单地混合不同组分来获得。
如本文所公开,术语“玻璃化转变温度”或“Tg”通过差示扫描量热法(DSC)测定。
除非另有说明,否则如本文所公开,本文提及的所有百分比均按重量计,并且温度以℃为单位。
如本文中所公开的,术语“烷基”或“烷氧基”是指具有1到20个碳原子、优选地1-10个碳原子、更优选地1-8个碳原子的烷基或烷氧基。
如本文所用,术语“(甲基)丙烯酸酯”是指丙烯酸酯或甲基丙烯酸酯。
如本文所用,术语“苯乙烯单体”意指被芳族基团取代的烯键式不饱和单体,优选地苯乙烯(Sty)和取代的苯乙烯,例如α-甲基苯乙烯(AMS)。
如本文所用,术语“溶液”是指可通过常规聚合技术(例如像通过溶液聚合)制备的水溶性聚合物的分散体。
如本文所用,术语“乳液”、“胶乳”或“胶乳组合物”是指可通过常规聚合技术(例如像通过乳液聚合)制备的水不溶性聚合物的分散体。
在本发明的第一方面,本发明提供了一种粘合剂组合物,其包含以下组分:
(a)多元酸聚合物水性分散体,其中所述多元酸聚合物含有50重量%~100重量%的一种或多种烯键式不饱和一元或二元羧酸/酸酐;
(b)含羟基丙烯酸共聚物乳液,其中含羟基丙烯酸共聚物通过使含有0.1-10%含羟基单体、0.1%至20重量%不饱和羧酸和30%-90%丙烯酸单体的单体混合物聚合来获得,
其中基于所述上述组分(a)和(b)的固体,所述组分(a)和(b)的固体重量比为0.1∶100至10∶100。
粘合剂组合物是水性的,并且优选地不含溶剂,也就是说,按粘合剂组合物的总干重计,粘合剂组合物包含小于4干重%、优选地小于2干重%、并且更优选地小于1干重%的有机溶剂。
多元酸聚合物水性分散体
多元酸聚合物含有50重量%-100重量%、优选地60重量%-100重量%、更优选地70重量%-100重量%、最优选地80重量%-100重量%的一种或多种烯键式不饱和一元或二元羧酸/酸酐。合适的烯键式不饱和一元或二元羧酸/酸酐包括例如烯键式不饱和羧酸单体,例如像甲基丙烯酸、丙烯酸、巴豆酸、富马酸、马来酸、2-甲基马来酸、衣康酸、2-甲基衣康酸、α,β-亚甲基戊二酸、马来酸单烷基酯和富马酸单烷基酯;烯键式不饱和酸酐,例如像马来酸酐、衣康酸酐、丙烯酸酐和甲基丙烯酸酐;及其盐类。在本发明的一个优选实施方案中,羧基单体可以是丙烯酸或甲基丙烯酸或衣康酸/酸酐或马来酸/酸酐。
一种或多种烯键式不饱和一元或二元羧酸/酸酐可以与任何合适的单体共聚。在本公开的一个实施方案中,一种或多种烯键式不饱和一元或二元羧酸/酸酐与至少一种烯键式不饱和单体例如丙烯酸酯单体共聚。合适的丙烯酸酯单体包括例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、丙烯酸癸酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸异癸酯、丙烯酸羟乙酯、甲基丙烯酸羟乙酯和甲基丙烯酸羟丙酯;(甲基)丙烯酰胺或取代的(甲基)丙烯酰胺;苯乙烯或取代的苯乙烯;丁二烯;乙酸乙烯酯或其他乙烯基酯;丙烯腈或甲基丙烯腈;等。
多元酸聚合物含有0重量%-50重量%、优选地0重量%-40重量%、更优选地0重量%-30重量%、最优选地0重量%-20重量%的至少一种烯键式不饱和单体。
多元酸聚合物水性分散体具有不小于40%、优选地40%至60%、更优选地45%至55%的总固体重量。
在一个实施方案中,多元酸聚合物具有2,000至1,000,000、优选地5,000至750,000、最优选地10,000至600,000的重均分子量。
多元酸聚合物水性分散体可通过任何常规溶液聚合制备,所述溶液方法为本领域普通技术人员所熟知的。
在溶液聚合过程中,可以在聚合混合物中使用链转移剂如硫醇、聚硫醇和卤素化合物,以便调节多元酸聚合物的分子量。通常,基于多元酸聚合物的重量,可以使用0重量%至10重量%的C4-C20烷基硫醇、巯基丙酸或巯基丙酸酯。
含羟基丙烯酸共聚物乳液
含羟基丙烯酸共聚物乳液是一种胶乳,它是烯键式不饱和单体聚合物颗粒的基于水的分散体。含羟基丙烯酸共聚物通过使含有0.1-10%的含羟基单体、0.1-20%重量的不饱和羧酸和30%-90%的丙烯酸单体的单体混合物聚合来获得。胶乳在25℃下的粘度范围通常将为约10至1000cps并且更优选地在25℃下为20至500cps。胶乳中的固体含量可以在5%至95%的范围内。更优选其在20至80%、还优选地30至70%以及甚至还优选地40至60%的范围内。在一个实施方案中,胶乳聚合物的重均分子量为5000与2,000,000之间并且更优选地在100,000与2,000,000之间。
在一个实施方案中,含羟基单体的合适实施例包括但不限于(甲基)丙烯酸羟烷基酯,优选地(甲基)丙烯酸C2-C8羟烷基酯,优选地(甲基)丙烯酸C2-C4羟烷基酯,优选地(甲基)丙烯酸C2-C3羟烷基酯。在另一个实施方案中,含羟基单体包括甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟乙酯(HEA)、甲基丙烯酸羟丙酯(HPMA)和丙烯酸羟丙酯。
基于单体混合物的重量,单体混合物包含0.1-10%、优选地0.5-8%、更优选地0.5-5%、最优选地0.5-2%的含羟基单体。
在一个实施方案中,不饱和羧酸包含一种或多种α,β-烯键式不饱和羧酸。合适的α,β烯键式不饱和羧酸的实施例包括但不限于:含酸单体,诸如(甲基)丙烯酸、衣康酸或富马酸;或含有酸形成基团的单体,其产生或随后可转化为此类酸基团(诸如酸酐、(甲基)丙烯酸酐或马来酸酐);或其混合物。
基于单体混合物的重量,单体混合物包含0.1-20%、优选地1-15%、更优选地1.5-10%、最优选地1.5-8%的不饱和羧酸。
在一个实施方案中,丙烯酸单体的合适实施例包括但不限于(甲基)丙烯酸酯,例如(甲基)丙烯酸烷基酯。(甲基)丙烯酸烷基酯的实施例是但不限于丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸缩水甘油酯、丙烯酸2-乙基己酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯和甲基丙烯酸2-乙基己酯和其组合。
基于单体混合物的重量,单体混合物包含30-90%、优选地35-85%、更优选地40-85%、最优选地45-85%的丙烯酸单体。
单体混合物还可包含一种或多种附加单体,例如苯乙烯单体和乙烯基单体。苯乙烯单体的实施例可包括例如苯乙烯、取代的苯乙烯或其混合物。取代的苯乙烯可包括例如丙烯酸苄酯、丙烯酸2-苯氧基乙酯、丁基苯乙烯、甲基苯乙烯、对甲氧基苯乙烯或其混合物。优选的苯乙烯单体是苯乙烯。乙烯基单体的实施例可包括例如烯烃,诸如乙烯、丙烯和丁二烯;乙烯基酯,例如乙酸乙烯酯;乙烯醇;丙烯腈;卤代烯烃,诸如氯乙烯;及其混合物。
单体混合物可包含按单体混合物的重量计5%或更多、10%或更多、13%或更多以及同时60%或更少、50%或更少的苯乙烯单体。
应当理解,可根据需要在本公开的粘合剂组合物中使用表面活性剂(例如,用于乳液或分散聚合)以提供稳定性以及控制粒度。常规的表面活性剂包括阴离子或非离子乳化剂或它们的组合。典型的阴离子乳化剂包括但不限于烷基硫酸碱或铵、烷基醚硫酸碱或铵、烷基芳基醚硫酸碱或铵、烷基磺酸盐、脂肪酸盐、磺基琥珀酸盐的酯、烷基二苯醚二磺酸盐和复合有机磷酸酯的盐或游离酸。典型的非离子乳化剂包括但不限于聚醚,例如环氧乙烷和环氧丙烷缩合物,其包括直链和支链烷基和烷基芳基聚乙二醇和聚丙二醇醚和硫醚、烷基基团含有约7至约18个碳原子并具有约4至约100个乙烯氧基单元的烷基苯氧基聚(乙烯氧基)乙醇以及己糖醇的聚氧化烯衍生物,包括山梨糖醇、山梨糖醇酐、甘露聚糖和甘露糖醇酐。基于最终组合物的总重量,表面活性剂可用于本发明的聚合物组合物中的水平为0.1至3重量%或更高。
丙烯酸乳液具有-80℃至100℃、优选地-50℃至80℃、更优选地-45℃至60℃、最优选地-40℃至50℃的Tg。
基于多元酸聚合物水性分散体和含羟基丙烯酸共聚物乳液的固体,多元酸聚合物水分散液与含羟基丙烯酸共聚物乳液的固体重量比为0.1∶100至10∶100、优选地0.5∶100至8∶100、更优选地1∶100至8∶100、最优选地2∶100至7∶100。
本公开的粘合剂组合物的其他任选组分包括但不限于选自共溶剂、聚结剂、颜料或其他着色剂、填料、增强剂(例如纤维)、分散剂、润湿剂、蜡、催化剂、发泡剂、消泡剂、紫外线吸收剂、阻燃剂、粘合促进剂、抗氧化剂、杀生物剂、聚结剂或稳定剂的试剂。这些任选组分(根据需要)可以以任何不引起组分之间不相容的添加顺序添加。不溶于水性载体的组分(例如颜料和填料)可以使用混合器(任选地高剪切混合器)分散在胶乳或水性载体或共溶剂中。可以通过在搅拌下添加酸或碱来调节组合物的pH。碱的实施例包括但不限于氨、二乙胺、三乙胺、二甲基乙醇胺、三乙醇胺、氢氧化钠、氢氧化钾和乙酸钠。酸的实施例包括但不限于乙酸、甲酸、盐酸、硝酸和甲苯磺酸。
本公开的粘合剂组合物可用于任何目的。优选的用途是作为纺织品/非织造织物的粘结剂。例如,可例如通过浸渍、计量、喷涂或其他方法使一批单根纤维(即尚未纺成线的纤维)与本公开的组合物接触;将本公开的组合物中的水蒸发或允许其蒸发,以产生纺织品/非织造垫。可在蒸发水之前或期间加热或不加热所得纺织品/非织造垫(即,暴露于高于40℃的温度)。预期连续体积的聚合物将粘附到多于一根纤维上,因此聚合物将用于将纤维粘结在一起。
粘结剂的有效性的一个量度是纺织品/非织造垫的拉伸强度,特别是当已将垫暴露于水或有机溶剂时。较高的拉伸强度是期望的。
通过本公开的组合物粘结在一起的纤维可由任何材料制成。纤维可以是矿物纤维或有机纤维。有机纤维可以是天然的或人造的。一些合适的天然有机纤维由例如纤维素、纤维素衍生物、棉、亚麻和羊毛制成。一些合适的人造有机纤维由例如人造丝、尼龙、聚酯、丙烯酸类聚合物和聚烯烃制成。在本发明的实践中,纤维可以是合适纤维的混合物。
在本公开的第二方面,本公开提供了一种由根据本公开的粘合剂组合物制备的制品。
在本公开的第三方面,本公开提供了本公开的粘合剂组合物用于纺织品/非织造织物的用途。
在一个实施方案中,本公开的粘合剂组合物可用于增加非织造垫的拉伸强度,尤其是当已将垫暴露于水或有机溶剂时。
实施例
现将在以下实施例中描述本发明的一些实施方案,其中除非另外说明,否则所有份数和百分比均以重量计。然而,本公开的范围当然不限于这些实施例中所述的配制品。相反,实施例仅仅是本公开的说明。
原材料:
所用的缩写:DI水=去离子水;CD=横向;SC=固体含量;BA=丙烯酸丁酯;Sty=苯乙烯;IA=衣康酸;AA=丙烯酸;HEMA=甲基丙烯酸羟乙酯;MA=马来酸酐
A:多元酸聚合物水性分散体(即用型商品,来自陶氏化学(DOW Chemical)):
A1:Acusol 479N,AA/MA共聚物,40%的固体;
A2:Acusol 505N,AA/MA共聚物,35%的固体;
A3:Acusol 465,AA/MA共聚物,40%的固体
A4:Leukotan 8090,AA均聚物,40%的固体
DS-4:RHODACAL DS-4,表面活性剂,来自苏威化学(Solvay Chemical);
IA:衣康酸,来自国药化学试剂(Sinopharm Chemical Reagent);
HEMA:甲基丙烯酸羟乙酯,来自东京化学工业(Tokyo Chemical Industry);
AA:丙烯酸,来自国药化学试剂;
BA:丙烯酸丁酯,来自国药化学试剂;
Sty:苯乙烯,来自国药化学试剂;
APS:过硫酸氨,来自国药化学试剂;
SBS:亚硫酸氢钠,来自国药化学试剂;
t-BHP:叔丁基过氧化氢,70%水溶液,来自东京化学工业;
FF6:Bruggolite FF6,来自布鲁格曼化工(Brüggmann Chemical);
TRITON X-100:表面活性剂,来自陶氏化学。
IPA=异丙醇,来自国药化学试剂。
WHATMAN#4纸:沃特曼公司(Whatman Ltd.)的产品。
实施例1:含有羟基的丙烯酸共聚物乳液(B)的制备
B-I-1:
将5.77g DS-4溶解在475g去离子水(DI水)中。在搅拌下通过向溶液中缓慢添加以下原材料来制备乳化单体混合物:6.84g IA、13.7g HEMA、34.2g AA、1107.4g BA、177.7gSty。
将含有50.42g DS4和370g去离子水的溶液进料到配备有热电偶、冷却冷凝器和搅拌器的5颈3升圆底烧瓶中,并在氮气下加热至70℃。将255g 60℃DI水中的27.4g衣康酸(IA)装入烧瓶中。然后将82.8g乳化单体混合物装入烧瓶中。然后将25g DI水中的3.72g过硫酸氨(APS)和20g DI水中的1.86g亚硫酸氢钠(SBS)装入烧瓶中。当放热峰出现并且温度为70℃时,在120分钟内进料剩余的乳化单体混合物、APS溶液(50g DI水中的2.48g)和SBS溶液(50g DI水中的1.24g)。聚合反应温度保持在69-71℃下。在完成添加后,用90g DI水冲洗含有乳化单体混合物的容器和连接至烧瓶的进料管,并将冲洗液添加回到烧瓶中。然后将烧瓶保持在70℃下15分钟。然后,装入t-BHP(70%,5g DI水中的1.05g)和FF6(0.9g)于5gDI水中的溶液。15分钟后,在60分钟内逐渐添加t-BHP(70%,38g DI水中的3.98g)和FF6(42g DI水中的3.38g)的溶液,并且然后将反应物冷却至室温。添加15g氨溶液,以将pH值调节至6.5-7.5。固体含量为45%。
制备乳液B-I-1,其基于共聚物的干重按重量计包含81重量%BA、13重量%Sty、2.5重量%AA、2.5重量%IA、1重量%HEMA。Tg=-25℃。
B-I-2:乳液B-I-2根据与乳液B-I-1相同的制备方法制备,除了将5.77g DS-4溶解于475g去离子水(DI水)中,并且在搅拌下通过向溶液中添加以下原材料来制备乳化单体混合物:6.84g IA、34.2g AA、615.2g丙烯酸丁酯、670g苯乙烯。Tg=30℃。
B-I-3:乳液B-I-3根据与乳液B-I-1相同的制备方法制备,除了将5.77g DS-4溶解于475g去离子水(DI水)中,并且在搅拌下通过向溶液中添加以下原材料来制备乳化单体混合物:6.84g IA、34.2g AA、806.6g丙烯酸丁酯、478.5g苯乙烯。Tg=0℃。
B-C-1:乳液B-C-1根据与乳液B-I-1相同的制备方法制备,除了将5.77g DS-4溶解于475g去离子水(DI水)中,并且在搅拌下通过向溶液中添加以下原材料来制备乳化单体混合物:6.84g IA、34.2g冰丙烯酸、1107.4g丙烯酸丁酯、191.4g苯乙烯。未添加HEMA。Tg=-25℃。
B-C-2:乳液B-C-2为即用型商品(ECONEXT 919,来自陶氏化学),Tg=-25℃,不含HEMA
发明性实施例和比较实施例
上述原材料根据下表1配制。将原材料搅拌15分钟以获得可固化的水性组合物。
将28cm×46cm的WHATMAN纸片浸入在300mL配制的组合物中。将处理过的纸用Mathis拉轧机进行拉轧,然后在150℃下干燥和固化3分钟。聚合物在纸上的添加量控制在14-16%之间。将固化后的纸切成1英寸×4英寸的片,其中4英寸方向是纸的横向(CD)方向。在Instron拉伸试验机上在干燥(未处理)、湿润(在0.1%Triton X-100/水溶液中浸渍30分钟后)和IPA(在异丙醇中浸渍30分钟后)处理下测试样品的拉伸强度:。湿强度反映耐水性,并且IPA强度反映耐溶剂性。结果示出在下表2中。
表1:样品的制剂。
*括号()中的数值为制剂中的固体比率
**样品为发明性3-3,在50℃烘箱中老化30天。
表3:样品的应用测试。
*Δ意指制剂中组分B的湿强度/IPA强度的改善。
与比较实施例1至3相比,制剂中含有组分A的发明性1-1至3-4显示出湿强度改善10%-25%并且IPA强度改善40-90%。通过将比较实施例1与比较实施例4或5、发明性1-1与比较实施例4-1或5-1相比较,当组分B含有含羟基单体时,湿强度和IPA强度均增加。将发明性3-3与发明性3-3-a比较,发现本发明制剂在50℃热老化30天后保持稳定性能。
玻璃化转变温度(Tg)
将聚合物的干燥样品放入到铝坩埚中,并且然后通过TA仪器公司的DSC Q2000在此程序上对样品进行测试:
1.将温度以20℃/min的速度从-80℃升高到120℃以擦除热历史;
2.冷却至-80℃;
3.将温度以10℃/min的速度从-80℃升高到120℃。
半高转变点被确定为玻璃化转变温度(Tg)。
Claims (10)
1.一种粘合剂组合物,其包含以下组分:
(a)多元酸聚合物水性分散体,其中所述多元酸聚合物含有50重量%~100重量%的一种或多种烯键式不饱和一元或二元羧酸/酸酐;
(b)含羟基丙烯酸共聚物乳液,其中含羟基丙烯酸共聚物通过使含有0.1-10%含羟基单体、0.1%至20重量%不饱和羧酸和30%-90%丙烯酸单体的单体混合物聚合来获得,
其中基于所述上述组分(a)和(b)的固体,所述组分(a)和(b)的固体重量比为0.1∶100至10∶100。
2.根据权利要求1所述的粘合剂组合物,其中所述烯键式不饱和一元或二元羧酸/酸酐包括甲基丙烯酸、丙烯酸、巴豆酸、富马酸、马来酸、2-甲基马来酸、衣康酸、2-甲基衣康酸、α,β-亚甲基戊二酸、马来酸单烷基酯、富马酸单烷基酯、马来酸酐、衣康酸酐、丙烯酸酐、甲基丙烯酸酐;及其盐类。
3.根据权利要求1所述的粘合剂组合物,其中所述一种或多种烯键式不饱和一元或二元羧酸/酸酐与以下各项共聚:丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、丙烯酸癸酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸异癸酯、丙烯酸羟乙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、(甲基)丙烯酰胺、取代的(甲基)丙烯酰胺、苯乙烯、取代的苯乙烯、丁二烯、乙酸乙烯酯、丙烯腈和/或甲基丙烯腈。
4.根据权利要求1所述的粘合剂组合物,其中所述含羟基单体包括(甲基)丙烯酸羟烷基酯。
5.根据权利要求1所述的粘合剂组合物,其中所述含羟基单体包括甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟乙酯(HEA)、甲基丙烯酸羟丙酯(HPMA)和丙烯酸羟丙酯。
6.根据权利要求1所述的粘合剂组合物,其中所述不饱和羧酸包括(甲基)丙烯酸、衣康酸、富马酸、(甲基)丙烯酸酐、马来酸酐)或其混合物。
7.根据权利要求1所述的粘合剂组合物,其中所述丙烯酸单体包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸缩水甘油酯、丙烯酸2-乙基己酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸2-乙基己酯及其组合。
8.根据权利要求1所述的粘合剂组合物,其中所述单体混合物包括苯乙烯单体或乙烯基单体。
9.一种制品,其通过根据权利要求1所述的粘合剂组合物制备。
10.根据权利要求1所述的粘合剂组合物用于纺织品/非织造织物的用途。
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US20120172477A1 (en) * | 2010-12-31 | 2012-07-05 | Chi-Yu Huang | Photocurable adhesive composition |
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