CN104379642A - 热塑性淀粉和tpe的合金用于制备粘合性超薄防水透气薄膜的用途 - Google Patents
热塑性淀粉和tpe的合金用于制备粘合性超薄防水透气薄膜的用途 Download PDFInfo
- Publication number
- CN104379642A CN104379642A CN201380033737.7A CN201380033737A CN104379642A CN 104379642 A CN104379642 A CN 104379642A CN 201380033737 A CN201380033737 A CN 201380033737A CN 104379642 A CN104379642 A CN 104379642A
- Authority
- CN
- China
- Prior art keywords
- weight
- film
- tpe
- block
- alloy
- 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
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 32
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 32
- 229920008262 Thermoplastic starch Polymers 0.000 title claims abstract description 19
- 239000004628 starch-based polymer Substances 0.000 title claims abstract description 19
- 230000001070 adhesive effect Effects 0.000 title abstract description 10
- 239000000853 adhesive Substances 0.000 title abstract description 7
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000004753 textile Substances 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 73
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 44
- 239000004744 fabric Substances 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 39
- 229920002472 Starch Polymers 0.000 claims description 37
- 239000008107 starch Substances 0.000 claims description 37
- 235000019698 starch Nutrition 0.000 claims description 37
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 34
- 229920002614 Polyether block amide Polymers 0.000 claims description 24
- VPRUMANMDWQMNF-UHFFFAOYSA-N phenylethane boronic acid Chemical compound OB(O)CCC1=CC=CC=C1 VPRUMANMDWQMNF-UHFFFAOYSA-N 0.000 claims description 23
- 239000000835 fiber Substances 0.000 claims description 21
- -1 polyoxyethylene Polymers 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229920000728 polyester Polymers 0.000 claims description 13
- 238000009795 derivation Methods 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000007858 starting material Substances 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 229920000098 polyolefin Polymers 0.000 claims description 9
- 239000004902 Softening Agent Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000004746 geotextile Substances 0.000 claims description 4
- 239000005445 natural material Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920006228 ethylene acrylate copolymer Polymers 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract 2
- 229920001223 polyethylene glycol Polymers 0.000 abstract 2
- 238000010276 construction Methods 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 52
- 229920000570 polyether Polymers 0.000 description 39
- 239000004721 Polyphenylene oxide Substances 0.000 description 35
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 16
- 238000009833 condensation Methods 0.000 description 16
- 230000005494 condensation Effects 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 150000004985 diamines Chemical class 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 150000001721 carbon Chemical group 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 150000001408 amides Chemical class 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 229920000856 Amylose Polymers 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 229920000945 Amylopectin Polymers 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- 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 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- KSMVBYPXNKCPAJ-UHFFFAOYSA-N 4-Methylcyclohexylamine Chemical compound CC1CCC(N)CC1 KSMVBYPXNKCPAJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 3
- 230000000155 isotopic effect Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 2
- VJHDPVWEDUCKRQ-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O.NCCCCCCCCCCCC(O)=O VJHDPVWEDUCKRQ-UHFFFAOYSA-N 0.000 description 2
- HWRRQRKPNKYPBW-UHFFFAOYSA-N 2,4-dimethylcyclohexan-1-amine Chemical compound CC1CCC(N)C(C)C1 HWRRQRKPNKYPBW-UHFFFAOYSA-N 0.000 description 2
- MSWZFWKMSRAUBD-UHFFFAOYSA-N 2-Amino-2-Deoxy-Hexose Chemical compound NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 2
- KNIBGFJYGWBIIV-UHFFFAOYSA-N 2-methyl-4-propylcyclohexan-1-amine Chemical compound CCCC1CCC(N)C(C)C1 KNIBGFJYGWBIIV-UHFFFAOYSA-N 0.000 description 2
- CKDSFRWKHBYHHT-UHFFFAOYSA-N 4-bicyclo[2.2.1]heptanylmethanamine Chemical compound C1CC2CCC1(CN)C2 CKDSFRWKHBYHHT-UHFFFAOYSA-N 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 2
- GLBHAWAMATUOBB-UHFFFAOYSA-N 6,6-dimethylheptane-1,1-diamine Chemical compound CC(C)(C)CCCCC(N)N GLBHAWAMATUOBB-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- YMUAXKYTHNCMAS-UHFFFAOYSA-N [butyl(nitroso)amino]methyl acetate Chemical compound CCCCN(N=O)COC(C)=O YMUAXKYTHNCMAS-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000009940 knitting Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- PBLZLIFKVPJDCO-UHFFFAOYSA-N omega-Aminododecanoic acid Natural products NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YMZUNDOYNOLDEC-UHFFFAOYSA-N 2-[2-(2-carboxy-5-hydroxyphenyl)ethyl]-4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1CCC1=CC(O)=CC=C1C(O)=O YMZUNDOYNOLDEC-UHFFFAOYSA-N 0.000 description 1
- HASUJDLTAYUWCO-UHFFFAOYSA-N 2-aminoundecanoic acid Chemical compound CCCCCCCCCC(N)C(O)=O HASUJDLTAYUWCO-UHFFFAOYSA-N 0.000 description 1
- WECIKJKLCDCIMY-UHFFFAOYSA-N 2-chloro-n-(2-cyanoethyl)acetamide Chemical compound ClCC(=O)NCCC#N WECIKJKLCDCIMY-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000024675 Eruca sativa Species 0.000 description 1
- 235000014755 Eruca sativa Nutrition 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 229920006099 Vestamid® Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011173 biocomposite Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 210000004534 cecum Anatomy 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000007278 cyanoethylation reaction Methods 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- HRIZJUDKZZJVBC-UHFFFAOYSA-N ethane-1,1-diol;ethane-1,2-diol Chemical compound CC(O)O.OCCO HRIZJUDKZZJVBC-UHFFFAOYSA-N 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/0015—Making articles of indefinite length, e.g. corrugated tubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/024—Woven fabric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2003/00—Use of starch or derivatives as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/02—Cellular or porous
- B32B2305/026—Porous
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2437/00—Clothing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2471/00—Floor coverings
- B32B2471/02—Carpets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2479/00—Furniture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/12—Polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249982—With component specified as adhesive or bonding agent
- Y10T428/249983—As outermost component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
- Y10T442/3854—Woven fabric with a preformed polymeric film or sheet
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/674—Nonwoven fabric with a preformed polymeric film or sheet
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Woven Fabrics (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明涉及热塑性淀粉用于制备粘合性超薄防水-透气薄膜的用途,所述热塑性淀粉以与亲水TPE的合金的形式存在,该亲水TPE包含至少10%重量,优选地至少20%重量,优选地至少30%重量,优选地至少40%重量,优选地至少50%重量的聚乙二醇(PEG),相对于TPE的重量。该薄膜可以用于药物领域、卫生学、行李业、制衣业、服装业、家庭或者家用设备、家具、绒头织物、汽车和工业、特别地工业过滤,农业和/或建筑物中。
Description
技术领域
本发明涉及的技术领域为在织物领域中使用的防水透气薄膜的领域。
这种防水透气薄膜同时地是可透水汽的和不透水的。
背景技术
存在许多要求具有改善并且延长的防水透气性质的织物的技术领域。特别地可以提及的药物领域、医疗设备、手术袍、地毯、床垫、包扎带、防护衣;农业、农用膜;包裹、包装;军事设备、海上设备,特别地船舶覆盖物;运输、航空、汽车;运动;休闲活动;信息、电子学、家具;装饰;用于婴儿或者用于儿童的设备;外部设备;建筑物墙壁的隔离、屋顶下薄膜。
防水-透气薄膜是挠性薄膜,其一方面起防止外界要素,如粉尘,花粉,沙,雨和雪,渗透穿过该织物的作用,和另一方面起防止产生的水汽,例如由人活动产生的水汽在该织物中积累。这种薄膜允许水汽从织物中排出。防水-透气薄膜的使用允许具有能呼吸的织物并因此对于使用它的用户是健康的织物。
透水汽性使用参数MVTR(水汽渗透率)进行评价。特别地,合意的是,防水-透气薄膜具有在24小时期间在23℃在50%的相对湿度时和对25微米的薄膜厚度至少70g/m2的通过标准ASTM E96进行测量的MVTR值。对于上述的应用,特别地合意的是,当使用的薄膜在织物表面上粘附时,最小渗透性在相同的测量条件下为至少350g/m2。还合意的是,该薄膜在织物上的粘合作用在使用该织物时不受到有害地改变,特别地当放出的水汽量在温度显著提高的情况下是更大的时候更是如此。换句话说,寻找不容易被长期暴露于湿气引起的劣化的防水-透气纺织产品。此外,防水-透气性质和该薄膜在织物上的粘合作用的增强不应该以牺牲该织物的柔韧性或者薄度(厚度)为代价而产生。因此寻找一种防水-透气纺织产品(在下文中,经处理织物或者层压制品),其具有强透水汽性和优良的寿命,以保证其持久性,同时具有“裸露”织物的外观而不需要特殊处理。
已知的薄膜由合成的聚合物制成。事实上,合成的聚合物由非可再生的原材料制成。寻求限制它们在防水-透气薄膜的制备中的量。因此研究一种至少部分地从天然的(或者生物来源化的)原材料获得的并且具有至少与从合成的聚合物获得的薄膜同样好的渗透性的薄膜。特别地,寻求至少部分地从天然原材料获得的并且满足如上所指出的渗透性要求的薄膜。
最后,现有技术的薄膜通过使包含不同的因为它们的防水-透气性质而已知的聚合物的共混物成型而获得。该成型可以根据任何已知的挤出方法进行实施,如扁平模头挤出压延(extrusion
calandrage à plat)、挤出丙烯酸树脂涂层(extrusion
plaxage)或者挤出-吹塑。通常,尽管高的加热功率,不可能获得具有低于25微米的厚度的薄膜。因此寻求一种防水-透气薄膜,其可以容易地使用传统的用于制备热塑性薄膜的装置并且在100℃至300℃,优选地150℃至250℃范围中的加热或者挤出温度进行制备。
发明简述
本发明因此涉及热塑性淀粉用于制备粘合性超薄防水-透气薄膜,特别地在至少一种纺织材料的表面上的粘合性超薄防水-透气薄膜的用途,所述热塑性淀粉以与亲水TPE的合金的形式存在,该亲水TPE包含至少10%重量,优选地至少20%重量,优选地至少30%重量,优选地至少40%重量,优选地至少50%重量的聚乙二醇(PEG),相对于TPE的重量。
该可用于根据本发明的合金中的热塑性弹性体聚合物(在本说明书称为TPE)可以选自(a)包含聚酯嵌段和聚醚嵌段的共聚物(在下文中,COPE或者共聚醚酯),(b)包含聚氨酯嵌段和聚醚或者聚酯嵌段的共聚物(亦被称为TPU,是热塑性聚氨酯的缩写),和(c)包含聚酰胺嵌段和聚醚嵌段的共聚物(根据IUPAC亦被称为PEBA)。
“亲水TPE”理解为表示包含至少10%重量,优选地至少20%重量,优选地至少30%重量,优选地至少40%重量,优选地至少50%重量的聚乙二醇(PEG)的TPE,相对于该TPE的重量。
(a)关于COPE或者共聚醚酯,这为包含聚酯嵌段和聚醚嵌段的共聚物。它们由产生自聚醚二醇的柔性聚醚嵌段和由至少一种二羧酸与至少一种扩链的短二醇单元反应产生的刚性聚酯嵌段组成。该聚酯嵌段和该聚醚嵌段经由酯键连接,该酯键产生自该二羧酸的酸官能团与该聚醚二醇的OH官能团的反应。聚醚和二酸的连接形成柔性嵌段而乙二醇或者丁二醇与二酸的连接形成该共聚醚酯的刚性嵌段。该扩链短二醇可以选自新戊二醇,环己烷二甲醇和式HO(CH2)nOH的脂族二醇,其中n为具有2至10的值的整数。
有利地,该二酸为具有8至14个碳原子的芳香族二羧酸。最高50mol%的芳族二羧酸可以用至少一种具有8至14个碳原子的其它芳族二羧酸替换,最高20mol%可以用具有2至14个碳原子的脂族二羧酸替换。
作为芳香族二羧酸的实例,可以提到对苯二酸、间苯二酸、联苯甲酸、萘二酸、4,4’-联苯二甲酸、双(对-羧基苯基)甲烷酸、亚乙基双(对-苯甲酸)、1,4-四亚甲基双(对-羟基苯甲酸)、亚乙基双(对-羟基苯甲酸)或者1,3-三亚甲基双(对-羟基苯甲酸)。
作为二醇的实例,可以提到乙二醇、1,3-三亚甲基二醇、1,4-丁二醇、1,6-己二醇、1,3-丙二醇、1,8-辛二醇、1,10-十亚甲基二醇和1,4-环己二甲醇。该包含聚酯嵌段和聚醚嵌段的共聚物为例如具有由聚醚二醇得来的聚醚单元,如聚乙二醇(PEG)、聚丙二醇(PPG)、聚三亚甲基二醇(PO3G)或者聚丁二醇(PTMG),二羧酸单元,如对苯二酸,和乙二醇(乙烷二醇)或者1,4-丁二醇单元的共聚物。这种共聚醚酯描述在专利EP402883和EP405227中。这些聚醚酯为热塑性弹性体。它们可以包含增塑剂。
(b)关于TPU,可以提到产生自为聚醚二醇的柔性聚醚嵌段和产生自至少一种二异氰酸酯与至少一种短二醇的反应的刚性聚氨酯嵌段的聚醚氨酯嵌段的缩合,该二异氰酸酯可以选自芳族二异氰酸酯(例如:MDI、TDI)和脂族二异氰酸酯(例如:HDI或者己撑二异氰酸酯)。该扩链短二醇可以选自如上面在该共聚醚酯的描述中所提及的二醇。该聚氨酯嵌段和该聚醚嵌段通过由异氰酸酯官能团与聚醚二醇的OH官能团反应产生的键而连接。
还可以提及聚酯氨酯,其产生自柔性聚酯嵌段(其为聚酯二醇)和刚性聚氨酯嵌段(产生自至少一种二异氰酸酯与至少一种短二醇的反应)的缩合。该聚酯二醇产生自二羧酸(有利地选自具有2至14个碳原子的脂族二羧酸)和二醇(其为扩链短二醇)的缩合,该扩链短二醇选自如上面在共聚醚酯的描述中所提及的二醇。它们可以包含增塑剂。
(c)关于"PEBA"或者包含聚醚嵌段和聚酰胺嵌段的共聚物,它们由包含反应性端基的聚酰胺嵌段与包含反应性端基的聚醚嵌段的缩聚反应产生,尤其如:
1)包含二胺链端的聚酰胺嵌段与包含二羧基链端的聚氧化烯嵌段;
2)包含二羧基链端的聚酰胺嵌段与包含二胺链端的聚氧化烯嵌段,其通过脂族α,ω-二羟基化聚氧化烯嵌段(被称为聚醚二醇)的氰乙基化和氢化获得;
3)具有二羟基链端的聚酰胺嵌段与聚醚二醇,该获得的产品在此特定情况下是聚醚酯酰胺。
包含二羟基链端的聚酰胺嵌段例如来源于在链限制二羧酸存在时由聚酰胺的前体的缩合。包含胺链端的聚酰胺嵌段例如来源于在链限制二胺存在时由聚酰胺的前体的缩合。
聚酰胺嵌段的数均摩尔质量Mn为400至20000g/mol,优选地500至10000g/mol。
包含聚酰胺嵌段和聚醚嵌段的聚合物还可以包含随机分布的单元。
有利地可以使用三种类型聚酰胺嵌段。
根据第一种类型,聚酰胺嵌段来源于二羧酸(特别地具有4至20个碳原子,优选地具有6至18个碳原子的那些)和脂族或者芳族二胺(特别地具有2至20个碳原子,优选地具有6至14个碳原子的那些)的缩合获得。
作为二羧酸的实例,可以提到1,4-环己基二甲酸,丁二酸,己二酸,壬二酸,辛二酸,癸二酸,十二烷二酸和十八烷二酸和对苯二酸和间苯二酸,以及二聚脂肪酸。
作为二胺的实例,可以提到四亚甲基二胺,己二胺,1,10-癸二胺,十二烷二胺,三甲基己二胺,双(4-氨基环己基)甲烷(BACM)的异构体,双(3-甲基-4-氨基环己基)甲烷(BMACM),和2,2-双(3-甲基-4-氨基环己基)丙烷(BMACP),和二(对氨基环己基)甲烷(PACM),和异佛尔酮二胺(IPDA),2,6-双(氨甲基)降冰片烷(BAMN)和哌嗪(Pip)。
有利地存在以下嵌段:PA4.12、PA4.14、PA4.18、PA6.10、PA6.12、PA6.14、PA6.18、PA9.12、PA10.10、PA10.12、PA10.14和PA10.18,第一个数字指出二胺的碳原子的数目和第二个数字指出羧酸的碳原子的数目。
根据第二种类型,该聚酰胺嵌段产生自一种或多种α,ω-氨基羧酸和/或一种或多种内酰胺(它们具有6至12个碳原子)在二羧酸(具有4至12碳原子)或者二胺存在时的缩合。作为内酰胺的实例,可以提到己内酰胺、庚内酰胺和十二碳内酰胺。作为α,ω-氨基羧酸的实例,可以提到氨基己酸,7-氨基庚酸,11-氨基十一烷酸和12-氨基十二烷酸。
有利地,第二种类型的聚酰胺嵌段为聚酰胺11、聚酰胺12或者聚酰胺6。
根据第三种类型,该聚酰胺嵌段产生自至少一种α,ω-氨基羧酸(或者内酰胺),至少一种二胺和至少一种二羧酸的缩合。
在这种情况下,聚酰胺PA嵌段通过以下化合物的缩聚反应进行制备:
-具有X个碳原子的线性脂族或者芳族二胺;
-一种或多种具有Y个碳原子的二羧酸;和
-一种或多种共聚单体{Z},其选自具有Z个碳原子的内酰胺和α,ω-氨基羧酸和至少一种具有X1个碳原子的二胺和至少一种具有Y1个碳原子的二羧酸的等摩尔混合物,其中(X1,Y1)与(X,Y)不同。
-相对于聚酰胺前体单体的整体,将所述一种或多种共聚单体{Z}以最高至50%,优选地最高至20%,更有利地最高至10%的重量比引入;
-在选自二羧酸的链限制试剂存在时。
作为链限制剂,有利地使用具有Y个碳原子的二羧酸,其以相对于所述一种或多种二胺的化学计量过量地被引入。
根据该第三种类型的替代形式,聚酰胺嵌段产生自在任选存在链限制试剂时,至少两种α,ω-氨基羧酸或者至少两种具有6至12个碳原子的内酰胺或者具有不相同碳原子数的内酰胺和氨基羧酸的缩合。作为α,ω-氨基羧酸的实例,可以提到氨基己酸,7-氨基庚酸,11-氨基十一烷酸和12-氨基十二烷酸。作为内酰胺的实例,可以提到己内酰胺、庚内酰胺和十二碳内酰胺。作为脂族二胺的实例,可以提到己二胺、十二烷二胺和三甲基己二胺。作为脂环族二酸的实例,可以提到1,4-环己基二甲酸。作为脂族二酸的实例,可以提到丁二酸、己二酸、壬二酸、辛二酸、癸二酸和十二烷二甲酸,二聚脂肪酸(这些二聚脂肪酸优选地具有至少98%的二聚物含量;优选地,它们进行氢化;它们以Pripol®商标由Unichema公司或者以Empol®商标由Henkel公司销售,和聚氧化烯-α,ω二酸。作为芳族二酸的实例,可以提到对苯二酸(T)和间苯二酸(I)。作为脂环族二胺的实例,可以提到双(4-氨基环己基)甲烷(BACM)的异构体,双(3-甲基-4-氨基环己基)甲烷(BMACM),和2,2-双(3-甲基-4-氨基环己基)丙烷(BMACP),和二(对氨基环已基)甲烷(PACM)。其它通常使用的二胺可以是异佛尔酮二胺(IPDA)、2,6-双(氨甲基)降冰片烷(BAMN)和哌嗪。
作为第三种类型的聚酰胺嵌段的实例,可以提到以下:
- 6.6/6,其中6.6表示与己二酸缩合的己二胺单元,6表示产生自己内酰胺缩合的单元;
- 6.6/6.10/11/12,其中6.6表示与己二酸缩合的己二胺,6.10表示与癸二酸缩合的己二胺,11表示产生自氨基十一烷酸缩合的单元和12表示产生自十二碳内酰胺缩合的单元。
优选地,该聚合物包含1%至80%重量的聚醚嵌段和20%至99%重量的聚酰胺嵌段,优选地4%至80%重量的聚醚嵌段和20%至96%重量的聚酰胺嵌段,更优选地30%至60%重量的聚醚嵌段和40%至70%重量的聚酰胺嵌段。聚醚嵌段的质量Mn为100至6000g/mol,优选地200至3000g/mol。
聚醚嵌段由烯化氧单元组成。这些单元可以是例如环氧乙烷单元、环氧丙烷单元或者四氢呋喃单元(其产生聚丁二醇链)。因此,因此使用:PEG(聚乙二醇)嵌段,即由环氧乙烷单元组成的那些,PPG(聚丙二醇)嵌段,即由环氧丙烷单元组成的那些,PO3G(聚三亚甲基二醇)嵌段,即,由聚三亚甲基二醇醚单元组成的那些(这种具有聚三亚甲基醚嵌段的共聚物描述在文献US6590065中),和PTMG嵌段,即由丁二醇单元组成的那些,也被称为聚四氢呋喃嵌段。PEBA共聚物可以在它们的链中包含数种类型聚醚,该共聚多醚可以是嵌段的或者无规的共聚多醚。PEBA共聚物的透水汽性随着聚醚嵌段的量而提高并且随着这些嵌段的种类而变化。优选地使用允许获得具有良好透水汽性的PEBA的聚乙二醇的聚醚嵌段。
聚醚嵌段还可以由乙氧基化伯胺组成。作为乙氧基化伯胺的实例,可以提到下式的产物:
其中m和n为1至20和x为8和18。这些产品可以以Noramox®商标从CECA公司和以Genamin®商标从Clariant公司商业获得。
该柔性聚醚嵌段可以包括含NH2链端的聚氧化烯嵌段,这种嵌段可以通过脂族的α,ω-二羟基化聚氧化烯嵌段(称为聚醚二醇)的氰基乙酰化获得。更特别地,可以使用Jeffamines(例如Jeffamine® D400、D2000、ED2003或者XTJ 542,来自Huntsman公司的销售产品,其还描述在专利文件JP2004346274、JP2004352794和EP1482011中)。
聚醚二醇嵌段或者原样进行使用并且与包含羧基端基的聚酰胺嵌段共缩聚合,或者它们进行胺化以被转化为聚醚二胺并且与包含羧基端基的聚酰胺嵌段缩合。用于两步制备在PA嵌段和PE嵌段之间具有酯键的PEBA共聚物的一般方法是已知的并且描述在例如法国专利FR2846332中。用于制备在PA嵌段和PE嵌段之间具有酰胺键的本发明的PEBA共聚物的一般方法是已知的并且描述在例如欧洲专利EP1482011中。聚醚嵌段还可以与聚酰胺前体和链限制性二酸混合以制备具有随机分布的单元的包含聚酰胺嵌段和聚醚嵌段的聚合物(一步法)。
当然,在本说明书中的名称PEBA还涉及由Arkema销售的PEBAX®产品,涉及由Evonik®销售的Vestamid®产品,涉及由EMS销售的Grilamid®产品,和涉及由DSM销售的Kellaflex®产品或者涉及任何其它来自其它供应商的PEBA。
有利地,PEBA共聚物具有由PA6、PA11、PA12、PA6.12、PA6.6/6、PA10.10和/或PA6.14产生的PA嵌段、优选地PA11和/或PA12嵌段;由PTMG、PPG和/或PO3G产生的PE嵌段。主要地由PEG组成的基于PE嵌段的PEBA被列入亲水PEBA范围内。主要地由PTMG组成的基于PE嵌段的PEBA被列入疏水PEBA范围内。
有利地,在根据本发明的组合物中使用的所述PEBA由至少部分地来自生物来源化的原材料获得。可再生来源的原材料或者生物来源化的原材料理解为表示包含生物来源化的碳或者可再生来源的碳的物质。事实上,与产生自化石材料的物质不同,由可再生原材料组成的物质包含14C。“可再生来源的碳含量”或者"生物来源化的碳含量”通过应用ASTM
D 6866 (ASTM D 6866-06)和ASTM D 7026(ASTM
D 7026-04)的标准进行测定。举例来说,基于聚酰胺11的PEBA至少部分地来源于生物来源化的原材料并且具有至少1%的生物来源化碳含量,其对应于至少1.2×10-14的12C/14C同位素比。优选地,根据本发明的PEBA包含相对于碳总重量至少50%重量的生物来源化的碳,其对应于至少0.6×10-12的12C/14C同位素比。这种含量有利地是更高的,特别地最高至100%,其对应于1.2×10-12的12C/14C同位素比,在包含PA11嵌段和PE嵌段(包含产生自可再生来源的原材料的PO3G、PTMG和/或PPG)的PEBA情况下。
根据本发明的有利实施方案,该亲水TPE包含:
- 1%至100%,优选地50%至100%的包含聚氨酯嵌段和PEG嵌段的共聚物(TPU),和
- 99%至0%,优选地50%至0%的至少一种其它亲水TPE,其选自包含聚酰胺嵌段和PEG嵌段的共聚物(PEBA),包含聚酯嵌段和PEG嵌段的共聚物(COPE)和它们的共混物,
相对于该亲水TPE的重量。
根据一种有利的实施方案,在本发明中使用的合金包含至少一种这种TPE,任选地与至少一种官能化聚烯烃共混。根据一种特定的实施方案,根据本发明的合金和随后的薄膜,另外包含官能化聚烯烃,即包含用选自以下的单体接枝的聚烯烃:不饱和羧酸,不饱和羧酸酐,乙烯类单体,丙烯酸类单体和它们的混合物。优选地,该(官能化的)聚烯烃选自乙烯-丙烯酸酯共聚物,乙烯-丙烯酸酯-马来酸酐共聚物和乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯共聚物,这些共聚物如上所述进行接枝/官能化。有利地,该使用的官能化聚烯烃选自在专利申请FR2959939A1中描述和要求保护的那些。
热塑性淀粉,在下文被称为“TPS”,理解为表示在少量水存在时通过增塑作用被转化为可加工的材料的天然淀粉。增塑化淀粉(被称为“热塑性淀粉”)特别地使用非挥发性增塑剂,如丙三醇而获得。这种材料具有许多优点,如它的价格,它的生物可降解性质和它产生自丰富的可再生资源的来源。它可以使用塑料工业的传统装置进行加工。增塑化淀粉使人遗憾地具有一些显著的限制,如与传统的热塑性塑料相比较,它对于水的高灵敏度,有限的机械性质和粘合性质,和在其加工之后在它的性质稳定(退化或者致密化的现象)之前的非常长的老化。它以根据本发明的合金的形式的使用借助于淀粉与其它化合物的配制和使用根据本发明的方法而允许克服这些缺点。根据优选的实施方案,热塑性淀粉在该使用的合金中的百分比占该合金重量的10%-90%,优选地30%-80%,更优选地40%-70%,更优选地该合金重量的50%-70%。
任何类型淀粉可用于本发明中。它可以是玉米、马铃薯、小麦、木薯粉或者豌豆淀粉。淀粉可以通过接枝化学基团进行改性。它可以以以下不同的形式进行使用:
-天然的(未改性的)淀粉:该淀粉颗粒是该两种组分聚合物(它们是直链淀粉和支链淀粉)的半结晶组织化的位点。直链淀粉的聚合度和比例根据淀粉的植物来源而不同。
-糊化(gélatinisé)淀粉:在水介质中在约80℃的加热期间,淀粉水化并且膨胀。直链淀粉部分然后支链淀 粉部分溶入溶液(浆化)。悬浮液这时变得粘性的并且淀粉变得更容易水解。
-胶凝化淀粉–回生淀粉:当水溶液的温度降低时,体系变得胶凝化然后重组织为半结晶结构(退化)。这些重组织的分子由直链淀粉、支链淀粉和混合直链淀粉-支链淀粉晶体形成。
-解构淀粉(amidon destructuré),在该形式中,直链淀粉和支链淀粉聚合物进行分散。
除了使用为天然材料的淀粉之外,使用至少部分地由生物来源化的聚酰胺和/或聚醚嵌段制备的PEBA聚合物也允许进一步提高在根据本发明的薄膜中的天然材料的量。
根据本发明的合金可以通过任何允许获得紧密或者均匀的包含热塑性淀粉和所述至少一种根据本发明的亲水TPE和任选的一种或多种添加剂和/或一种或多种相容剂的共混物的方法(如熔融混合、挤出、压实或者辊式捏合机)进行制备。
更特别地,根据本发明的合金通过在"直接"方法中熔融共混所有的成分(淀粉,增塑剂,水,TPE和任选的一种或多种相容剂和一种或多种添加剂)进行制备。还可以根据两步法制备该合金,第一步骤在于制备淀粉、增塑剂和水的浓缩共混物,以形成TPS基质,然后第二步在于通过与TPE基质共混来稀释TPS。
有利地使用热塑性塑料工业的用于混合和捏合的通常装置,如挤出机、双螺杆型挤出机,特别地自清洁啮合同向旋转的双螺杆挤出机,和捏合机,例如Buss商标的共-捏合机或者密炼机。在这种方法中,成分可以进行干混和并且被引入进料斗中或亲水TPE可以经由侧部加料被引入在TPS中或者在预先熔化的淀粉+增塑剂+水共混物中。
推荐的是,本发明的合金的制备(配混)和它们的加工在尽可能温和的温度和剪切速率的条件下进行实施。为了做到这一点,可以参考以下参考文献:O.Schacker,Plastics Additives and Compounding,April 2002,第28-33页。
根据本发明的合金具有对于获得新型防水-透气材料的优异的性能/成本比率。根据使用的TPE/TPS比率获得不同性能。为了改善该共混物的相容性,加入相容剂。后者在本发明中是优选的。
与通过增塑化淀粉和热塑性聚合物的共挤出进行制备的多层相反,根据本发明的合金不具有特别地由于存在于模具中的材料的化学性质和流变学性质的差异而引起的界面不稳定性的问题。此外,根据本发明的合金不具有生物复合材料通常遇到的亲水性质降低的问题。这是因为,将木质纤维素纤维引入到生物聚酯中或者到增塑化淀粉基质中引起与存在更疏水的纤维相关的亲水性质的降低。
本发明的另一个主题是粘合性超薄防水-透气薄膜,特征在于它包含热塑性淀粉和亲水TPE的合金,所述TPE包含至少10%重量,优选地至少20%重量,优选地至少30%重量,优选地至少40%重量,优选地至少50%重量的聚乙二醇(PEG),相对于TPE的重量。有利地,热塑性淀粉的百分比占在该薄膜中的合金的10%至90%,和亲水TPE的百分比占90%至10%。
根据一种实施方案,本发明的防水-透气薄膜在根据以下步骤制备该合金之后直接进行制备:制备一种或多种TPE与热塑性淀粉(或者淀粉,水和增塑剂)的共混物,然后通过加热至高于该聚合物(一种或多种)的熔点和高于该淀粉的熔点的温度熔化该共混物,以便形成为合金的形式的均匀共混物。然后,获得的热塑性合金进行拉制以形成薄膜。一种或多种TPE的加热可以分别地与加热该淀粉的步骤分开地进行实施、随后使熔化TPE(一种或多种)和淀粉共混。
根据本发明的方法的优选的实施方案,实施以下步骤:
a)准备淀粉、增塑剂和水的共混物;
b)准备如上面所定义的亲水TPE;
c)挤出步骤a)的共混物然后在挤出结束时通常在高于步骤a)的一种或多种聚合物的熔点和高于淀粉的熔点的温度下向该共混物加入来自步骤b)的TPE;
d)拉制该共混物以形成薄膜。
优选地,步骤c)在100℃至300℃,优选地150℃至250℃的温度下进行实施。
根据一种实施方案,拉制该共混物的步骤通过挤出/吹塑进行实施。根据一种替代的实施方案,拉制该共混物的步骤通过扁平模头挤出(extrusion
à plat)进行实施。
本发明方法允许使该TPE维持在足够高的温度,高于该亲水TPE的熔点,以获得超薄的,即具有小于或等于25微米的厚度的薄膜,同时限制淀粉和TPE(一种或多种)退化的风险。优选地,在拉制该薄膜之前的加热或者挤出温度在100℃至300℃,优选地150℃至250℃的范围内。
有利地,根据本发明的防水-透气薄膜具有小于或等于25微米,优选地在5至25微米范围中的厚度。
本发明另一个主题是层压制品(在下文为层压物),其包含至少一种纺织材料和至少一个根据本发明的防水-透气薄膜,所述薄膜粘附在该纺织材料的至少一个表面上,具有0.5至50N,优选地0.5至10N的剥离强度。
有利地,根据本发明的薄膜通过任何已知的方法特别地适用于纺织材料,优选地在薄膜和织物之间不使用粘合剂。举例来说,可以提到该合金薄膜在该织物上方的挤出涂敷,或者在足以使该薄膜变得浸透和俘获该织物纤维的温度下,在织物上方或者在两个织物之间热压该薄膜(热层压或者使用粘合剂的层压)。根据一种替代实施方案或者与前述一种或多种实施方案组合的实施方案,还可以提及使用粘合剂接合层的胶合,该粘合剂接合层优选水基粘合剂接合层,即包含低于5%重量的溶剂,相对于该粘合剂接合层组合物。证明该使用根据本发明的合金的薄膜与现有的防水-透气薄膜相比较具有更好的与织物的粘合作用,即使不使用粘合剂。
根据一种优选的实施方案,用于加工该用于制备根据本发明的防水-透气材料和层压物的合金的方法的特征在于:所述组合物在流延挤塑或者吹胀挤塑作业线上以熔融状态在至少120℃的温度下进行施用,以形成具有5微米最小厚度的薄膜。这种类型方法还允许优化所述转化条件以制备为尽可能薄的,有利地具有5至50微米厚度,优选地具有5至25微米厚度的薄膜,该薄膜产生自以不同比例稀释的根据本发明的材料的线状共混物而不具有微穿孔。通过改变该作业线的温度和拉制速率参数,可以控制该薄膜的厚度。根据另一个优选的实施方案,该用于获得根据本发明的防水-透气薄膜和层压物的组合物的加工方法的特征在于将该组合物以熔融状态在挤出-涂敷工作线上施用在织物上或者在挤出-层压工作线上施用在两个织物(如由纤维材料制成的非编织物和/或任何其它纺织材料,包括纸)之间,以形成具有至少5g/m2克数的复合体。根据已知的方法,挤出根据本发明的薄膜然后以熔融状态涂覆在该织物上。优选地,该薄膜具有5至50微米,优选地大约5至10微米的厚度。有利地,在通过挤出-涂覆的应用的背景中,将10至50g/m2的热塑性薄膜沉积在该织物上。
在本发明的说明书中:
-“纺织材料”或者“织物”理解为表示由纤维或者长丝制备的任何材料和任何形成多孔膜的特征为长度/厚度比为至少300的材料,包括纸和纸板;
-“纤维”理解为表示任何合成或者天然材料,其特征为至少300的长度/直径比;
-“长丝”理解为表示无限长度的任何纤维。
在织物中,特别地包括纤维垫(绷带、过滤网或者毡)、粗纱(绷带)、纱(缝纫纱,针织纱或者编织纱),针织品(直型(rectiligne)、圆型或者全成形)、编织品(传统的、提花的、多重的、两面的、多轴向的、2D半,3D的)和许多其它物品。根据本发明的优选实施方案,所述至少一种纺织材料以多孔膜,编织织物或者非编织织物形式存在。
有利地,所述至少一种纺织材料包含合成纤维,特别地从生物来源化的原材料获得的合成纤维,天然纤维,由天然原材料制成的人造纤维,矿物纤维和/或金属纤维。
有利地,所述织物包含从生物来源化的原材料获得的合成纤维,如聚酰胺纤维,特别地聚酰胺11纤维。有利地,所述织物另外包含天然纤维,如棉花、羊毛和/或蚕丝,由天然原材料制成的人造纤维,矿物纤维如碳纤维、玻璃纤维、石英纤维和/或镁纤维。
优选地,所述纺织材料,无论它的形式是怎样,由至少一种以下材料制成:聚丙烯,聚醚,聚酯和/或棉花。
该织物特别地选自布或者纺织表面,如编织表面,针织表面,非编织表面或者毯子。这些制品例如可以是绒头织物、毛毯、家具覆盖物,表面覆盖物、沙发、帘、被褥、床垫和枕头、服装和药用纺织材料。
根据本发明纺织品有利地构成毡制品、过滤网、薄膜、纱布、帆布、绷带、敷层、织物、针织品、服装制品、服装、被褥品、家具制品、帘、座舱覆盖层、功能工业织物、土工织物和/或农用织物。
所述纺织品有利地用在药物领域,卫生学,行李,制衣业,服装业,家庭或者家用设备,家具,绒头织物,汽车,工业,特别地工业过滤,农业和/或建筑物中。
这种薄膜同时具有优良的耐久性和更好的透水汽性。该薄膜随着时间保持它的对可以渗入纺织品中的外界元素的阻挡层性质。该薄膜对水汽的渗透性的改善促进穿过该纺织品的透气。
实施例
防水-透气薄膜由包含不同比例的TPU、共聚多醚-嵌段-酰胺PEBA、官能化聚烯烃和热塑性淀粉的共混物进行制备。在下面的实施例中使用的TPU是由Bayer销售的Desmopan DP9370A等级。在下面的实施例中使用的TPE属于由Arkema销售的亲水PEBA系列,特别地其中聚醚嵌段来源于聚乙二醇的那些。在这里,它是Pebax®
MV3000。该官能化聚烯烃是Lotryl® 20MA08,其是具有8g/10min的MFI(190℃/2.16kg)的并具有20%丙烯酸酯重量含量的乙烯与丙烯酸正甲基酯的共聚物。使用的淀粉是由Roquette公司销售的改性淀粉(TPS 3947)。
该具有组成A至I的不同薄膜的防水-透气性(或者MVTR)根据标准ASTM E96,BW方法,38℃/50%相对湿度,对于25微米薄膜进行测量。
基材的粘合力与剥离强度值直接地相关的。剥离试验(根据标准ISO
11339)对测试A至I中每个的层压物,在层压物的15mm宽的带上进行实施,该带预备好(amorcée)然后以200mm/分钟的速度进行拉伸。剥离试验优选地在通过在非编织聚丙烯织物上的挤出涂覆来制备包含25微米的粘性薄膜的层压物之后的2小时至48小时的时间段内进行实施。
制备的不同共混物的组成概括在下面的表1中。实施例A-E是对比实施例。实施例F至I为根据本发明。
。
Claims (17)
1.热塑性淀粉用于制备粘合性超薄防水-透气薄膜的用途,所述热塑性淀粉以与亲水TPE的合金的形式存在,该亲水TPE包含至少10%重量,优选地至少20%重量,优选地至少30%重量,优选地至少40%重量,优选地至少50%重量的聚乙二醇(PEG),相对于TPE的重量。
2.根据权利要求1的用途,其中热塑性淀粉的百分比占该合金重量的10%-90%,优选地30%-80%,更优选地40%-70%,更优选地该合金重量的50%-70%。
3.根据前述权利要求任一项的用途,其中该亲水TPE包含:
- 1%至100%,优选地50%至100%的包含聚氨酯嵌段和PEG嵌段的共聚物(TPU),和
- 99%至0%,优选地50%至0%的至少一种其它亲水TPE,其选自包含聚酰胺嵌段和PEG嵌段的共聚物(PEBA),包含聚酯嵌段和PEG嵌段的共聚物(COPE)和它们的共混物,
相对于该亲水TPE的重量。
4.粘合性超薄防水-透气薄膜,特征在于它包含热塑性淀粉和亲水TPE的合金,所述TPE包含至少10%重量,优选地至少20%重量,优选地至少30%重量,优选地至少40%重量,优选地至少50%重量的聚乙二醇(PEG),相对于TPE的重量。
5.根据权利要求4的薄膜,其中:
- 热塑性淀粉的百分比占该合金重量的10%至90%,
- 亲水TPE的百分比占该合金重量的90%至10%。
6.根据权利要求4或5的薄膜,其还包括含用选自以下的单体的接枝的官能化聚烯烃:不饱和羧酸、不饱和羧酸酐、乙烯类单体、丙烯酸类单体和它们的混合物。
7.根据权利要求6的防水-透气薄膜,其中官能化聚烯烃选自乙烯-丙烯酸酯共聚物,乙烯-丙烯酸酯-马来酸酐共聚物,乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯共聚物。
8.根据权利要求4-7任一项的防水-透气薄膜,其中该薄膜具有小于或等于25微米,优选地在5至25微米范围中的厚度。
9.制备根据权利要求4-8任一项的薄膜的方法,包括以下步骤:
a) 准备淀粉、增塑剂和水的共混物;
b) 准备如权利要求1或3任一项中所定义的亲水TPE;
c) 挤出步骤a)的共混物然后在挤出结束时向该共混物加入来自步骤b)的TPE;
d) 拉制该共混物以形成薄膜。
10.根据权利要求9的方法,其中拉制该共混物的步骤通过挤出-吹塑进行实施。
11.根据权利要求9的方法,其中拉制该共混物的步骤通过扁平模头挤出进行实施。
12.根据权利要求9-11任一项的方法,其中步骤c)在100℃至300℃,优选地150℃至250℃的范围内的温度下进行。
13.层压制品,其包含至少一种纺织材料和至少一种根据权利要求4-8任一项的防水-透气薄膜,所述薄膜粘附在该纺织材料的至少一个表面上,具有0.5至50N,优选地0.5至10N的剥离强度。
14.根据权利要求13的层压制品,其中所述至少一种纺织材料以多孔膜,编织织物或者非编织织物形式存在。
15.根据权利要求13或14的层压制品,其中所述至少一种纺织材料包含合成纤维,特别地从生物来源化的原材料获得的合成纤维,天然纤维,由天然原材料制成的人造纤维,矿物纤维和/或金属纤维。
16.根据权利要求13-15任一项的层压制品,其中所述至少一种纺织材料构成毡制品、过滤网、薄膜、纱布、帆布、绷带、敷层、织物、针织品、服装制品、服装、被褥品、家具制品、帘、座舱覆盖层、功能工业织物、土工织物和/或农用织物。
17.根据权利要求4-8任一项的薄膜在药物领域、卫生学、行李、制衣业、服装业、家庭或者家用设备、家具、绒头织物、汽车、工业,特别地工业过滤,农业和/或建筑物中的用途。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911045563.1A CN110698842A (zh) | 2012-06-27 | 2013-06-07 | 热塑性淀粉和tpe的合金用于制备薄膜的用途 |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1256143A FR2992652B1 (fr) | 2012-06-27 | 2012-06-27 | Utilisation d'un alliage d'amidon thermoplastique et de tpe pour la fabrication d'un film ultra-fin imper-respirant adhesif. |
FR1256143 | 2012-06-27 | ||
PCT/FR2013/051321 WO2014001674A1 (fr) | 2012-06-27 | 2013-06-07 | Utilisation d'un alliage d'amidon thermoplastique et de tpe pour la fabrication d'un film ultra-fin imper-respirant adhesif |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911045563.1A Division CN110698842A (zh) | 2012-06-27 | 2013-06-07 | 热塑性淀粉和tpe的合金用于制备薄膜的用途 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN104379642A true CN104379642A (zh) | 2015-02-25 |
Family
ID=47137821
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201380033737.7A Pending CN104379642A (zh) | 2012-06-27 | 2013-06-07 | 热塑性淀粉和tpe的合金用于制备粘合性超薄防水透气薄膜的用途 |
CN201911045563.1A Pending CN110698842A (zh) | 2012-06-27 | 2013-06-07 | 热塑性淀粉和tpe的合金用于制备薄膜的用途 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911045563.1A Pending CN110698842A (zh) | 2012-06-27 | 2013-06-07 | 热塑性淀粉和tpe的合金用于制备薄膜的用途 |
Country Status (7)
Country | Link |
---|---|
US (1) | US11352467B2 (zh) |
EP (1) | EP2867279B1 (zh) |
JP (2) | JP2015529696A (zh) |
CN (2) | CN104379642A (zh) |
CA (1) | CA2873383C (zh) |
FR (1) | FR2992652B1 (zh) |
WO (1) | WO2014001674A1 (zh) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2992652B1 (fr) * | 2012-06-27 | 2014-06-20 | Arkema France | Utilisation d'un alliage d'amidon thermoplastique et de tpe pour la fabrication d'un film ultra-fin imper-respirant adhesif. |
CN105518098B (zh) | 2013-09-10 | 2018-10-16 | 阿科玛股份有限公司 | 抗静电热塑性淀粉掺混物 |
US11879058B2 (en) | 2015-06-30 | 2024-01-23 | Biologiq, Inc | Yarn materials and fibers including starch-based polymeric materials |
US11111363B2 (en) | 2015-06-30 | 2021-09-07 | BiologiQ, Inc. | Articles formed with renewable and/or sustainable green plastic material and carbohydrate-based polymeric materials lending increased strength and/or biodegradability |
US11674014B2 (en) | 2015-06-30 | 2023-06-13 | BiologiQ, Inc. | Blending of small particle starch powder with synthetic polymers for increased strength and other properties |
US11926929B2 (en) | 2015-06-30 | 2024-03-12 | Biologiq, Inc | Melt blown nonwoven materials and fibers including starch-based polymeric materials |
US11926940B2 (en) | 2015-06-30 | 2024-03-12 | BiologiQ, Inc. | Spunbond nonwoven materials and fibers including starch-based polymeric materials |
US11674018B2 (en) | 2015-06-30 | 2023-06-13 | BiologiQ, Inc. | Polymer and carbohydrate-based polymeric material blends with particular particle size characteristics |
EP3536468B1 (en) | 2018-03-09 | 2023-09-13 | BIC Violex Single Member S.A. | Razor cartridge with lubricating strip |
FR3108911B1 (fr) * | 2020-04-07 | 2023-06-30 | Arkema France | Composition de polymères pour films imper-respirants |
CN111763302B (zh) * | 2020-07-08 | 2022-01-07 | 清远新力化机有限公司 | 一种薄膜用tpu配方及其制备方法 |
FR3115491A1 (fr) | 2020-10-27 | 2022-04-29 | Arkema France | Structure multicouche imper-respirante |
FR3118051A1 (fr) | 2020-12-21 | 2022-06-24 | Arkema France | Compositions durcissables par rayonnement actinique contenant un polyamide |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4367327A (en) * | 1980-11-22 | 1983-01-04 | Shirley Institute | Breathable, non-porous polyurethane film prepared from a low molecular weight difunctional compound, a polyethylene glycol and a diisocyanate |
US6096809A (en) * | 1995-04-07 | 2000-08-01 | Bio-Tec Biologische Naturverpackungen Gmbh & Co. Kg | Biologically degradable polymer mixture |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4454268A (en) * | 1983-06-23 | 1984-06-12 | The United States Of America As Represented By The Secretary Of Agriculture | Starch-based semipermeable films |
US4988740A (en) | 1989-06-15 | 1991-01-29 | E. I. Du Pont De Nemours And Company | Low density foamed thermoplastic elastomers |
US4984376A (en) | 1989-06-15 | 1991-01-15 | E. I. Du Pont De Nemours And Company | Midsole for footwear |
NZ239723A (en) * | 1990-09-18 | 1993-06-25 | Chicopee | Blends comprising a hydrophilic block poly (ether-co-amide) and a hydrophobic polymer |
DE4339475A1 (de) * | 1993-11-19 | 1995-05-24 | Wolff Walsrode Ag | Knisterfreie, antistatische Polyurethanfolie mit hoher Atmungsaktivität sowie ihre Verwendung |
DE4410921C2 (de) * | 1994-03-29 | 1996-12-19 | Atochem Elf Deutschland | Polymermischung und deren Verwendung |
FR2721320B1 (fr) * | 1994-06-20 | 1996-08-14 | Atochem Elf Sa | Film imper-respirant. |
DE19624641A1 (de) * | 1996-06-20 | 1998-01-08 | Biotec Biolog Naturverpack | Biologisch abbaubarer Werkstoff, bestehend im wesentlichen aus oder auf Basis thermoplastischer Stärke |
ES2241051T3 (es) * | 1996-07-08 | 2005-10-16 | Vivoxid Oy | Material biodegradable de alta resistencia al impacto. |
DE19652037A1 (de) * | 1996-12-13 | 1998-06-18 | Wolff Walsrode Ag | Elastische Folien mit verbesserter biologischer Abbaubarkeit sowie Verfahren für ihre Herstellung |
US6191221B1 (en) * | 1998-09-29 | 2001-02-20 | Polymer Group, Inc. | Breathable film compositions and articles and method |
US6590065B1 (en) | 2001-12-10 | 2003-07-08 | E. I. Du Pont De Nemours And Company | Polytrimethylene ether ester amide and use thereof |
JP3851566B2 (ja) * | 2002-01-17 | 2006-11-29 | 新和興化成株式会社 | 無孔透湿性フィルム |
EP1388345A1 (en) * | 2002-08-09 | 2004-02-11 | The Procter & Gamble Company | Polymeric compositions with enhanced vapour permeability and washability |
FR2846332B1 (fr) | 2002-10-23 | 2004-12-03 | Atofina | Copolymeres transparents a blocs polyamides et blocs polyethers |
JP4193588B2 (ja) | 2003-05-26 | 2008-12-10 | 宇部興産株式会社 | ポリアミド系エラストマー |
US7056975B2 (en) | 2003-05-27 | 2006-06-06 | Ube Industries, Ltd. | Thermoplastic resin composition having improved resistance to hydrolysis |
JP4161802B2 (ja) | 2003-05-27 | 2008-10-08 | 宇部興産株式会社 | ポリアミド組成物 |
FR2897356B1 (fr) * | 2006-02-16 | 2012-07-13 | Arkema | Utilisation de compositions thermoplastiques a base de polyolefines fonctionnalisees greffees par des motifs polyethers pour realiser des materiaux imper-respirants et leurs applications |
CN101311208B (zh) * | 2007-05-25 | 2011-09-07 | 江华 | 热塑性淀粉及其制备方法 |
WO2010074185A1 (ja) * | 2008-12-26 | 2010-07-01 | 三菱化学株式会社 | 樹脂組成物、フィルム、袋製品、および、樹脂組成物の製造方法 |
CN102115576B (zh) * | 2009-12-31 | 2014-09-17 | 金伯利-克拉克环球有限公司 | 天然生物聚合物热塑性膜 |
FR2959939B1 (fr) | 2010-05-17 | 2013-08-02 | Francois Emmanuel Vigneau | Espace multisports pour la pratique de plusieurs "sports de buts" et "sports de filets" se jouant avec une balle, un ballon, un volant ou un palet |
US8889945B2 (en) * | 2010-12-08 | 2014-11-18 | Kimberly-Clark Worldwide, Inc. | Elastic film containing a renewable starch polymer |
FR2992652B1 (fr) * | 2012-06-27 | 2014-06-20 | Arkema France | Utilisation d'un alliage d'amidon thermoplastique et de tpe pour la fabrication d'un film ultra-fin imper-respirant adhesif. |
-
2012
- 2012-06-27 FR FR1256143A patent/FR2992652B1/fr not_active Expired - Fee Related
-
2013
- 2013-06-07 CN CN201380033737.7A patent/CN104379642A/zh active Pending
- 2013-06-07 WO PCT/FR2013/051321 patent/WO2014001674A1/fr active Application Filing
- 2013-06-07 CN CN201911045563.1A patent/CN110698842A/zh active Pending
- 2013-06-07 CA CA2873383A patent/CA2873383C/fr not_active Expired - Fee Related
- 2013-06-07 EP EP13731394.6A patent/EP2867279B1/fr not_active Not-in-force
- 2013-06-07 JP JP2015519281A patent/JP2015529696A/ja active Pending
- 2013-06-07 US US14/411,820 patent/US11352467B2/en active Active
-
2017
- 2017-11-02 JP JP2017212469A patent/JP6456457B2/ja active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4367327A (en) * | 1980-11-22 | 1983-01-04 | Shirley Institute | Breathable, non-porous polyurethane film prepared from a low molecular weight difunctional compound, a polyethylene glycol and a diisocyanate |
US6096809A (en) * | 1995-04-07 | 2000-08-01 | Bio-Tec Biologische Naturverpackungen Gmbh & Co. Kg | Biologically degradable polymer mixture |
Also Published As
Publication number | Publication date |
---|---|
EP2867279B1 (fr) | 2017-08-23 |
US11352467B2 (en) | 2022-06-07 |
US20150166746A1 (en) | 2015-06-18 |
CN110698842A (zh) | 2020-01-17 |
WO2014001674A1 (fr) | 2014-01-03 |
FR2992652B1 (fr) | 2014-06-20 |
FR2992652A1 (fr) | 2014-01-03 |
JP2015529696A (ja) | 2015-10-08 |
CA2873383C (fr) | 2020-08-04 |
JP6456457B2 (ja) | 2019-01-23 |
CA2873383A1 (fr) | 2014-01-03 |
JP2018090778A (ja) | 2018-06-14 |
EP2867279A1 (fr) | 2015-05-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104379642A (zh) | 热塑性淀粉和tpe的合金用于制备粘合性超薄防水透气薄膜的用途 | |
CN103282413B (zh) | 用于防水透气性膜应用的包含共聚醚嵌段酰胺、共聚醚嵌段酯、官能化聚烯烃和淀粉的组合物 | |
CN101563499B (zh) | 特别是合成皮革的复合材料 | |
CN104302199B (zh) | 热熔粘合织物 | |
CN105669934A (zh) | 水性聚氨酯脲组合物包括分散体和膜 | |
JP2010516492A (ja) | 熱可塑性ポリウレタンを材料とするフィルムおよびウェブを含むラミネート | |
CN111356725A (zh) | 基于嵌段共聚物的可伸缩的、柔性的、防水的且透气的膜 | |
CN116490349A (zh) | 防水且透气的多层结构体 | |
CN104379641A (zh) | 热塑性淀粉和pof的合金用于制备粘合性超薄防水透气薄膜的用途 | |
CN105518098A (zh) | 抗静电热塑性淀粉掺混物 | |
CN212925249U (zh) | 生物可降解聚酯复合短纤维制备系统 | |
KR20220164730A (ko) | 방수-통기성 필름을 위한 폴리머 조성물 | |
CN100398306C (zh) | 可生化降解的共聚酯非织造布 | |
CN115380078A (zh) | 用于防水透气膜的聚合物组合物 | |
KR20240027577A (ko) | 생분해성, 산업적으로 퇴비화가능한, 및/또는 재활용가능한 압출 가죽-유사 재료 | |
CN117980552A (zh) | 基于聚酰胺-聚醚嵌段共聚物的可再循环的弹性丝状物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150225 |
|
RJ01 | Rejection of invention patent application after publication |