JPH0453842A - Production of porous sheet-like substance with low water absorption capacity - Google Patents
Production of porous sheet-like substance with low water absorption capacityInfo
- Publication number
- JPH0453842A JPH0453842A JP16227190A JP16227190A JPH0453842A JP H0453842 A JPH0453842 A JP H0453842A JP 16227190 A JP16227190 A JP 16227190A JP 16227190 A JP16227190 A JP 16227190A JP H0453842 A JPH0453842 A JP H0453842A
- Authority
- JP
- Japan
- Prior art keywords
- water
- dispersion
- oil repellent
- organic solvent
- polyurethane
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 238000010521 absorption reaction Methods 0.000 title abstract description 13
- 239000000126 substance Substances 0.000 title abstract 3
- 229920002635 polyurethane Polymers 0.000 claims abstract description 50
- 239000004814 polyurethane Substances 0.000 claims abstract description 50
- 239000006185 dispersion Substances 0.000 claims abstract description 47
- 239000005871 repellent Substances 0.000 claims abstract description 47
- 239000003960 organic solvent Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 44
- 230000002940 repellent Effects 0.000 claims description 40
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 19
- 239000000839 emulsion Substances 0.000 claims description 17
- 239000000835 fiber Substances 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 23
- -1 polytetramethylene Polymers 0.000 abstract description 15
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 abstract description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 4
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 abstract description 3
- 229920001451 polypropylene glycol Polymers 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 41
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 36
- 150000002009 diols Chemical class 0.000 description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- 239000002585 base Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 125000005442 diisocyanate group Chemical group 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007764 o/w emulsion Substances 0.000 description 6
- 229920003009 polyurethane dispersion Polymers 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-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
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000921 polyethylene adipate Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-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
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- GNQKHBSIBXSFFD-UHFFFAOYSA-N 1,3-diisocyanatocyclohexane Chemical compound O=C=NC1CCCC(N=C=O)C1 GNQKHBSIBXSFFD-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-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
- PGRNEGLBSNLPNP-UHFFFAOYSA-N 1,6-dichloro-3-methylhex-1-ene Chemical compound ClC=CC(C)CCCCl PGRNEGLBSNLPNP-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- PIPWSBOFSUJCCO-UHFFFAOYSA-N 2,2-dimethylpiperazine Chemical compound CC1(C)CNCCN1 PIPWSBOFSUJCCO-UHFFFAOYSA-N 0.000 description 1
- XAQCYASNAMYTQA-UHFFFAOYSA-N 2,4-diamino-5-methylbenzenesulfonic acid Chemical compound CC1=CC(S(O)(=O)=O)=C(N)C=C1N XAQCYASNAMYTQA-UHFFFAOYSA-N 0.000 description 1
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 1
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- ZMPYMKAWMBVPQE-UHFFFAOYSA-N 2-[(6-chloropyridin-3-yl)methyl-ethylamino]-2-methyliminoacetic acid Chemical compound CCN(CC1=CN=C(C=C1)Cl)C(=NC)C(=O)O ZMPYMKAWMBVPQE-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- IAXFZZHBFXRZMT-UHFFFAOYSA-N 2-[3-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=CC(OCCO)=C1 IAXFZZHBFXRZMT-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-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
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 description 1
- HEMGYNNCNNODNX-UHFFFAOYSA-N 3,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1N HEMGYNNCNNODNX-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
- VLRGXXKFHVJQOL-UHFFFAOYSA-N 3-chloropentane-2,4-dione Chemical compound CC(=O)C(Cl)C(C)=O VLRGXXKFHVJQOL-UHFFFAOYSA-N 0.000 description 1
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 1
- QLIQIXIBZLTPGQ-UHFFFAOYSA-N 4-(2-hydroxyethoxy)benzoic acid Chemical compound OCCOC1=CC=C(C(O)=O)C=C1 QLIQIXIBZLTPGQ-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- VAWFFNJAPKXVPH-UHFFFAOYSA-N naphthalene-1,6-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC2=CC(C(=O)O)=CC=C21 VAWFFNJAPKXVPH-UHFFFAOYSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、低吸水率多孔質シート状物質の製造法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a porous sheet material with low water absorption.
生産性が高い多孔質シート状物質の製造方法としては、
ポリウレタンの油中水型の有機溶剤−水分散液を繊維基
材に含浸及び/又は塗布せしめた後、該分散液から有機
溶剤を蒸発せしめてゲル化させる方法が一般的に知られ
ている(特開昭48−4380号公報、特開昭54−6
6961号公報、特開昭54−68498号公報、特開
昭58−194926号公報、特開昭61−72032
号公報、特開昭61−72033号公報)。As a highly productive method for manufacturing porous sheet materials,
A generally known method is to impregnate and/or apply a water-in-oil organic solvent-water dispersion of polyurethane onto a fiber base material, and then evaporate the organic solvent from the dispersion to form a gel. JP-A-48-4380, JP-A-54-6
6961, JP 54-68498, JP 58-194926, JP 61-72032
(Japanese Patent Application Laid-open No. 61-72033).
しかしながら、上記製造方法においては、吸水率の著し
く小さい多孔質シート状物質は全く得られていない。However, in the above production method, no porous sheet-like material having a significantly low water absorption rate has been obtained.
そこで本発明者は、上記実情に鑑みて吸水率の著しく小
さい多孔質シート状物質を得る方法について鋭意検討し
たところ、ポリウレタンの油中水型の有機溶剤−水分散
液として、撥水撥油剤を含有するポリウレタンの油中水
型の有機溶剤−水分散液を用いて上記方法で得られる多
孔質シート状物質が、著しく小さい吸水率を有すること
を見いだし、本発明を完成するに至った。Therefore, in view of the above circumstances, the inventors of the present invention have conducted intensive studies on a method for obtaining a porous sheet-like material with a significantly low water absorption rate. It was discovered that a porous sheet-like material obtained by the above method using a water-in-oil type organic solvent-water dispersion of polyurethane contained therein had a significantly low water absorption rate, and the present invention was completed.
即ち本発明は、ポリウレタン(A)の油中水型の有機溶
剤−水分散液を、繊維基材(B)に含浸および/または
塗布せしめた後、該分散液から有機溶剤(C)を蒸発せ
しめてゲル化させて多孔質シート状物質を製造する方法
において、該分散液として、撥水撥油剤(D)を含有す
る分散液を用いることを特徴とする多孔質シート状物質
の製造方法、及び親水性ポリウレタン系重合体(A1)
又は重合体(AI)と疎水性ポリウレタン系重合体(A
2)との混合物の油中水型の有機溶剤−水分散液を、繊
維基材(B)に含浸および/または塗布せしめた後、該
分散液から有機溶剤(C)を蒸発せしめてゲル化させて
多孔質シート状物質を製造する方法において、該分散液
として、撥水撥油剤(D)を含有する分散液を用いるこ
とを特徴とする多孔質シート状物質の製造方法を提供す
るものである。That is, the present invention impregnates and/or coats a fiber base material (B) with a water-in-oil organic solvent-water dispersion of polyurethane (A), and then evaporates the organic solvent (C) from the dispersion. A method for producing a porous sheet-like material by at least gelling the material, characterized in that a dispersion containing a water- and oil-repellent (D) is used as the dispersion; and hydrophilic polyurethane polymer (A1)
Or polymer (AI) and hydrophobic polyurethane polymer (A
After impregnating and/or coating the fiber base material (B) with a water-in-oil type organic solvent-water dispersion of the mixture with 2), the organic solvent (C) is evaporated from the dispersion to form a gel. The present invention provides a method for producing a porous sheet-like material, characterized in that a dispersion containing a water- and oil-repellent (D) is used as the dispersion. be.
本発明で用いることのできる撥水撥油剤(D)は特に制
限されるものではな(、公知慣用のものがいずれも使用
できる。撥水撥油剤CD)は通常フッ素系である。撥水
撥油剤(D)としては、例、tlfパーフルオロアルキ
ル基含有アルコール又はパーフルオロアルキレン基含有
多価アルコールドカルボン酸とから得られるエステルや
ポリエステル、パーフルオロアルキル基含有アルコール
又はパーフルオロアルキレン基含有多価アルコールとイ
ンシアネートとから得られるウレタンやポリウレタン、
パーフルオロアルキル基含有エチレン性不飽和単量体又
はパーフルオロアルキレン基含有エチレン性不飽和単量
体の重合体や共重合体等が挙げられる。The water and oil repellent (D) that can be used in the present invention is not particularly limited (any known and commonly used agent can be used. The water and oil repellent CD) is usually fluorine-based. Examples of the water and oil repellent (D) include esters and polyesters obtained from TLF perfluoroalkyl group-containing alcohols or perfluoroalkylene group-containing polyhydric alcohols and carboxylic acids, and perfluoroalkyl group-containing alcohols or perfluoroalkylene groups. Urethane and polyurethane obtained from polyhydric alcohol and incyanate,
Examples include polymers and copolymers of ethylenically unsaturated monomers containing perfluoroalkyl groups or ethylenically unsaturated monomers containing perfluoroalkylene groups.
例えば、一般式(I)
R,A−OCC=CH,(I)
R3
但し、R,は炭素原子数4〜20のパーフルオロアルキ
ル基、
R3は−Hあるいは−CH,、
Aは−Q−−CON(Rx)−Q−
−30.N(R,)−Q
(但し、−〇−は炭素原子数1〜1゜
のアルキレン基、R2は炭素原子数
1〜4のアルキル基である。)
で示されるパーフルオロアルキル基含有エチレン性不飽
和単量体の単独重合体あるいはパーフルオロアルキル基
含有エチレン性不飽和単量体とパーフルオロアルキル基
不含のエチレン性不飽和単量体との共重合体が挙げられ
る。For example, general formula (I) R,A-OCC=CH, (I) R3 However, R is a perfluoroalkyl group having 4 to 20 carbon atoms, R3 is -H or -CH, A is -Q- -CON(Rx)-Q- -30. N(R,)-Q (However, -〇- is an alkylene group having 1 to 1 degrees of carbon atoms, and R2 is an alkyl group having 1 to 4 carbon atoms.) Examples include homopolymers of unsaturated monomers and copolymers of ethylenically unsaturated monomers containing perfluoroalkyl groups and ethylenically unsaturated monomers containing no perfluoroalkyl groups.
パーフルオロアルキル基含有エチレン性不飽和単量体と
しては、例えば、
A−1: CFs(CFi)−CHaCHzOCOCH
=CH2(n=5−11.nの平均=9)
A−2: CF、(CF、)、CH,CH,0COC(
CHI)=CH。As the perfluoroalkyl group-containing ethylenically unsaturated monomer, for example, A-1: CFs(CFi)-CHaCHzOCOCH
=CH2 (n=5-11.Average of n=9) A-2: CF, (CF, ), CH, CH, 0COC (
CHI)=CH.
A−3: CFs(CFi)icHscHzOcOc(
CHs)=CH2A−4: (CFx)zcF(CFz
)s(CHz)sOcOcトcHzA−5: (CFi
)zcF(CFz)to(CHz)xOcOcH=cH
zA−6: CF、(CF2)?502N(C,H?)
CH,CH20COCH=CH。A-3: CFs(CFi)icHscHzOcOc(
CHs)=CH2A-4: (CFx)zcF(CFz
)s(CHz)sOcOctocHzA-5: (CFi
)zcF(CFz)to(CHz)xOcOcH=cH
zA-6: CF, (CF2)? 502N (C, H?)
CH, CH20COCH=CH.
A−7: CF3(CFり、S0.N(CH,)CH
ICH20COC(CHI)=CHIA−8: CF
s(CFi)ysOJ(CHx)CHzCH*0COC
H=CHxA 9 : CF=(CFi)−(C
Hi)40COCH=CH−A−10: CF、(C
F、)、COOCH=CH。A-7: CF3(CFri, S0.N(CH,)CH
ICH20COC(CHI)=CHIA-8: CF
s(CFi)ysOJ(CHx)CHzCH*0COC
H=CHxA 9: CF=(CFi)-(C
Hi) 40COCH=CH-A-10: CF, (C
F, ), COOCH=CH.
A−11: CFs(CFり7SOJ(C4HI)(
CHI)、0COCH=CH2A−12: CF、(
CF、)ycH,cH(OH)CH,0COCH=CH
。A-11: CFs (CFri7SOJ(C4HI)(
CHI), 0COCH=CH2A-12: CF, (
CF,)ycH,cH(OH)CH,0COCH=CH
.
A−13: CF、(CFり、C0N(C,H,)C
H,CH,0COC(CHI)=CH2A−14:
CFm(CFz)7CON(CJs)CHzCHzOC
OCH=C)lx等の単量体があげられる。A-13: CF, (CFri, C0N(C,H,)C
H,CH,0COC(CHI)=CH2A-14:
CFm(CFz)7CON(CJs)CHzCHzOC
Examples include monomers such as OCH=C)lx.
パーフルオロアルキル基不含のエチレン性不飽和単量体
は特に限定されないが、例えば、エチレン、プロピレン
、塩化ビニル、塩化ビニリデン、スチレン、α−メチル
スチレン、酢酸ビニル、メチル(メタ)アクリレート、
エチル(メタ)アクリレート、n−ブチル(メタ)アク
リレート、1so−ブチル(メタ)アクリレート、te
rt−ブチル(メタ)アクリレート、ヘキシル(メタ)
アクリレート、n−オクチル(メタ)アクリレート、2
−エチルへ牛シル(メタ)アクリレート、ステアリル(
メタ)アクリレート、ベンジル(メタ)アクリレート、
シクロへ牛シル(メタ)アクリレート、インボロニル(
メタ)アクリレート、ジシクロペンタニル(メタ)アク
リレート、ジシクロペンテニル(メタ)アクリレート、
メチルビニルエーテル、プロピルビニルエーテル、オク
チルビニルエーテル、ブタジェン、イソプレン、クロロ
プレン、2−ヒドロキシエチル(メタ)アクリレート、
(メタ)アクリル酸、 (メタ)アクリルアミド、N
−メチロール(メタ)アクリルアミド、3−クロロ−2
−ヒドロキシ(メタ)アクリレート、ジアセトンアクリ
ルアミド等の単量体が例示される。Ethylenically unsaturated monomers containing no perfluoroalkyl group are not particularly limited, but include, for example, ethylene, propylene, vinyl chloride, vinylidene chloride, styrene, α-methylstyrene, vinyl acetate, methyl (meth)acrylate,
Ethyl (meth)acrylate, n-butyl (meth)acrylate, 1so-butyl (meth)acrylate, te
rt-butyl (meth)acrylate, hexyl (meth)
Acrylate, n-octyl (meth)acrylate, 2
- Ethyl to bovine syl (meth)acrylate, stearyl (
meth)acrylate, benzyl(meth)acrylate,
Cyclohesyl (meth)acrylate, inbornyl (
meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate,
Methyl vinyl ether, propyl vinyl ether, octyl vinyl ether, butadiene, isoprene, chloroprene, 2-hydroxyethyl (meth)acrylate,
(meth)acrylic acid, (meth)acrylamide, N
-methylol(meth)acrylamide, 3-chloro-2
- Monomers such as hydroxy (meth)acrylate and diacetone acrylamide are exemplified.
パーフルオロアルキル基不含のエチレン性不飽和単量体
として、例えばステアリル(メタ)アクリレート、イソ
ステアリル(メタ)アクリレート等の高級アルキル基を
含有するエチレン性不飽和単量体を併用するとさらに撥
水性が向上するし、ブロック化インシアネート基を含有
するエチレン性不飽和単量体を併用すると撥水撥油効果
の耐摩耗性が向上するという傾向がある。If an ethylenically unsaturated monomer containing a higher alkyl group such as stearyl (meth)acrylate or isostearyl (meth)acrylate is used in combination with an ethylenically unsaturated monomer that does not contain a perfluoroalkyl group, water repellency can be further improved. There is a tendency that when an ethylenically unsaturated monomer containing a blocked incyanate group is used in combination, the abrasion resistance of the water and oil repellent effect is improved.
本発明で用いられるパーフルオロアルキル基含有エチレ
ン性不飽和単量体と、パーフルオロアルキル基不含のエ
チレン性不飽和単量体とを共重合体する場合における両
岸量体の共重合割合は特に限定されないが、通常側単量
体の合計を100重量部としたとき、パーフルオロアル
キル基含有エチレン性不飽和単量体の使用量は30〜9
0重量部、中でも50〜90重量部とすることが好まし
い。When the perfluoroalkyl group-containing ethylenically unsaturated monomer used in the present invention is copolymerized with the perfluoroalkyl group-free ethylenically unsaturated monomer, the copolymerization ratio of the monomers on both sides is Although not particularly limited, when the total of the normal side monomers is 100 parts by weight, the amount of the perfluoroalkyl group-containing ethylenically unsaturated monomer used is 30 to 9 parts by weight.
0 parts by weight, preferably 50 to 90 parts by weight.
また、本発明で用いることのできる撥水撥油剤(D)の
別の例としては、
例えば、一般式(II)
(R,−A−OCN)、−U−
但し、R1は炭素原子数4〜20のパーフルオロアルキ
ル基、
Aは−Q−C0N(Ra) Q−
−3o、N(R1)−Q−1
(但し、−Q−は炭素原子数1〜10
のアルキレン基、R2は炭素原子数
1〜4のアルキル基)、
U l−i b価の有機基、
R1は炭素原子数1から20のアルキル基、
aは1〜4の整数、
bは2〜4の整数
である。Further, as another example of the water and oil repellent (D) that can be used in the present invention, for example, general formula (II) (R, -A-OCN), -U- where R1 has 4 carbon atoms ~20 perfluoroalkyl groups, A is -Q-C0N(Ra) Q- -3o, N(R1)-Q-1 (however, -Q- is an alkylene group having 1 to 10 carbon atoms, R2 is a carbon R1 is an alkyl group having 1 to 20 carbon atoms, a is an integer of 1 to 4, and b is an integer of 2 to 4.
で示されるパーフルオロアルキル基含有ウレタンアダク
トが挙げられる。Examples include perfluoroalkyl group-containing urethane adducts represented by:
このようなパーフルオロアルキル基含有ウレタンアダク
トとしては例えば、
U−4:
CsF 1tS(hN(CJs)CHzC)Iz−°0
°NH(□1″“ゞ”C00CH,諏MH,CH・0”
・などがあげられる。Examples of such perfluoroalkyl group-containing urethane adducts include: U-4: CsF 1tS(hN(CJs)CHzC)Iz-°0
°NH(□1″“ゞ”C00CH, Su MH, CH・0”
・And so on.
撥水撥油剤(D)の形態は特に制限されるものではなく
、有機溶剤溶液、有機溶剤分散液、水溶液、水分散液、
有機溶剤−水分散液等あらゆる形態のものが使用できる
。しかしながら、撥水撥油剤(D)を水中油型エマルジ
ョンとして含有させるのと、有機溶剤溶液として含有さ
せるのとてはポリウレタン固形分当たり同じ重量用いた
としても、水中油型エマルジョンとして用いたほうが、
得られる多孔質シート状物質の吸水率はより低くなるの
で好ましい。水中油型エマルジョンとして撥水撥油剤(
D)を用いて得られる多孔質シート状物質と同じ程度の
吸水率を、有機溶剤溶液として撥水撥油剤(D)を用い
て得ようとすれば、水中油型エマルジョンとして用いた
撥水撥油剤(D)固形分重量の2〜3倍の固形分重量の
撥水撥油剤(D)を使用する必要がある。The form of the water and oil repellent (D) is not particularly limited, and may include an organic solvent solution, an organic solvent dispersion, an aqueous solution, an aqueous dispersion,
Any form of organic solvent-water dispersion can be used. However, even if the same weight of water and oil repellent (D) is used as an oil-in-water emulsion and as an organic solvent solution, the oil-in-water emulsion is better than the oil-in-water emulsion, even if the same weight is used per solid content of polyurethane.
This is preferable because the resulting porous sheet-like material has a lower water absorption rate. Water and oil repellent (as an oil-in-water emulsion)
If you want to obtain the same level of water absorption as the porous sheet-like material obtained using D) using the water and oil repellent (D) as an organic solvent solution, the water and oil repellent used as an oil-in-water emulsion should be used. It is necessary to use a water and oil repellent (D) with a solid content weight that is 2 to 3 times the solid content weight of the oil agent (D).
撥水撥油剤(D)を水中油型エマルジョンとする方法は
、従来公知の方法がいずれも採用できる。Any conventionally known method can be used to form the water and oil repellent (D) into an oil-in-water emulsion.
例えばパーフルオロアルキル基含有エチレン性不飽和単
量体を乳化剤の存在下で乳化重合する方法、パーフルオ
ロアルキル基含有エチレン性不飽和単量体の1合体やパ
ーフルオロアルキル基含有ウレタンアダクトを予め製造
し、それを乳化剤で水に強制乳化する方法等があげられ
る。For example, a method of emulsion polymerization of a perfluoroalkyl group-containing ethylenically unsaturated monomer in the presence of an emulsifier, or a method of pre-producing a monomer of perfluoroalkyl group-containing ethylenically unsaturated monomers or a perfluoroalkyl group-containing urethane adduct. Then, a method of forcibly emulsifying it in water using an emulsifier can be mentioned.
本発明で用いられる撥水撥油剤(D)の使用量は、特に
制限されないが、後述するポリウレタン(A)の固型分
100重量部当たり撥水撥油剤(D)の固型分が通常0
.01〜10重量部であることが好ましく、中でもエマ
ルジョンとして添加する場合は 0.1〜3重量部が、
有機溶剤溶液として添加する場合は0.3〜Qfi量部
が更に好ましい。The amount of the water and oil repellent (D) used in the present invention is not particularly limited, but the solid content of the water and oil repellent (D) is usually 0 per 100 parts by weight of the solid content of the polyurethane (A) described below.
.. It is preferably 0.1 to 10 parts by weight, especially 0.1 to 3 parts by weight when added as an emulsion.
When added as an organic solvent solution, 0.3 to Qfi parts is more preferable.
本発明は、ポリウレタン(A)の油中水型の有機溶剤−
水分散液を、繊維基材(B)に含浸および/または塗布
せしめた後、該分散液から有機溶剤(C)を蒸発せしめ
てゲル化させて多孔質シート状物質を製造する方法にお
いて、該分散液として、撥水撥油剤(D)を含有する分
散液を用いることを特徴とする多孔質シート状物質の製
造方法である。The present invention provides water-in-oil organic solvents for polyurethane (A).
A method for manufacturing a porous sheet-like material by impregnating and/or applying an aqueous dispersion onto a fiber base material (B), and then evaporating the organic solvent (C) from the dispersion to gel it. This is a method for producing a porous sheet material, characterized in that a dispersion containing a water and oil repellent (D) is used as a dispersion.
本発明で用いることのできるポリウレタン(A)の油中
水型の有機溶剤−水分散液は特に制限されるものではな
いが、通常ポリウレタン(A)の有機溶剤溶液に水を添
加混合し分散させたものが使用される。The water-in-oil organic solvent-water dispersion of polyurethane (A) that can be used in the present invention is not particularly limited, but is usually prepared by adding water to an organic solvent solution of polyurethane (A) and dispersing it. is used.
本発明においてポリウレタン(A)は、親水性ポリウレ
タン系重合体(A1)と疎水性ポリウレタン系重合体(
A2)とに分類できるが、ポリウレタン(A)は、親水
性ポリウレタン系重合体(A1)を必須成分とすること
が好ましく、親水性ポリウレタン系重合体(A1)と疎
水性ポリウレタン系重合体(A2)とから構成されてい
ることがより好ましく、重合体(A1)と重合体(A2
)との合計を100重量部としたとき、重合体(Al)
10〜90重量部と重合体(A2)90〜10重量部と
の混合物であることが特に好ましい。In the present invention, the polyurethane (A) is a hydrophilic polyurethane polymer (A1) and a hydrophobic polyurethane polymer (A1).
It is preferable that polyurethane (A) has a hydrophilic polyurethane polymer (A1) as an essential component. ), and the polymer (A1) and the polymer (A2
) and the total amount is 100 parts by weight, the polymer (Al)
Particularly preferred is a mixture of 10 to 90 parts by weight and 90 to 10 parts by weight of polymer (A2).
ポリウレタン(A)としては公知慣用のものがいずれも
使用できる。ポリウレタン(A)は、例えばジオールと
ジイソシアネートを必須成分として、必要に応じて3官
能以上のアルコール、モノアルコール、3官能以上のイ
ソシアネート、モノイソシアネート等を用いれば容易に
得ることができる。As the polyurethane (A), any known and commonly used polyurethane can be used. Polyurethane (A) can be easily obtained by using, for example, a diol and a diisocyanate as essential components, and optionally using a trifunctional or higher functional alcohol, a monoalcohol, a trifunctional or higher functional isocyanate, a monoisocyanate, or the like.
ポリウレタン(A)の製造方法は特に限定されるもので
はないが、例えば■ジイソシアネートとジオールとを反
応させる方法、■ジイソシアネートとジオールとを反応
させ末端イソシアネート基のウレタンプレポリマーを製
造し、これとジオールないしはジアミンとを反応させる
方法が挙げられる。The method for producing polyurethane (A) is not particularly limited, but examples include: (1) reacting a diisocyanate and a diol; (2) reacting a diisocyanate and a diol to produce a urethane prepolymer with terminal isocyanate groups; Alternatively, a method of reacting with a diamine can be mentioned.
本発明で用いることのできるポリウレタン(A)を製造
するに当たって使用することの出来るジイソシアネート
としては、例えば2.4−1−リレンジイソシアネート
、2,6−ドリレンジイソシア不−ト、m−フェニレン
ジイソシアネート、p−フェニレンジイソシアネート、
4. 4’ −ジフェニルメタンジイソシアネート、2
,4” −ジフェニルメタンジイソシアネート、2.
2’ −ジフェニルメタンジイソシアネート、3. 3
’ −ジメチル−4,4′ −ビフェニレンジイソシア
ネート、3.3゛−ジメトキシ−4,4′ −ビフェニ
レンジイソシアネート、3,3° −ジクロロ−4゜4
′−ビフェニレンジイソシアネート、1. 5−ナフタ
レンジイソシアネート、1,5−テトラヒドロナフタレ
ンジイソシアネート、テトラメチレンジイソシアネート
、1.6−へキサメチレンジイソシアネート、ドデカメ
チレンジイソシアネート、トリメチルへキサメチレンジ
イソシアネート、1、 3−シクロヘキシレンジイソシ
アネート、l。Examples of diisocyanates that can be used in producing the polyurethane (A) that can be used in the present invention include 2,4-1-lylene diisocyanate, 2,6-lylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate,
4. 4'-diphenylmethane diisocyanate, 2
, 4''-diphenylmethane diisocyanate, 2.
2'-diphenylmethane diisocyanate, 3. 3
'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4
'-biphenylene diisocyanate, 1. 5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1, 3-cyclohexylene diisocyanate, l.
4−シクロヘキシレンジイソシアネート、キシリレンジ
イソシアネート、テトラメチルキシリレンジイソシアネ
ート、水素添加キシリレンジイソシアネート、リジンジ
イソシアネート、イソホロンジイソシアネー)、4.
4’ −ジシクロヘキシルメタンジイソシア不一ト、3
. 3’ −ジメチル−4,4′−ジシクロヘキシルメ
タンジイソシア不一ト等が挙げられる。4-cyclohexylylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate), 4.
4'-dicyclohexylmethane diisocyanate, 3
.. Examples include 3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate.
本発明で用いられるポリウレタン(A)の製造において
用いられるジオールは、便宜上平均分子j1300〜1
0,000好ましくは500〜5.000の高分子量ジ
オールと、分子量300以下の低分子量ジオールに分け
られる。For convenience, the diol used in the production of the polyurethane (A) used in the present invention has an average molecular weight of j1300 to 1.
It is divided into high molecular weight diols having a molecular weight of 0,000, preferably 500 to 5,000, and low molecular weight diols having a molecular weight of 300 or less.
上記高分子ジオールとしては、例えば、ポリエステルジ
オール、ポリエーテルジオール、ポリカーボネートジオ
ール、ポリアセタールジオール、ポリアクリレートジオ
ール、ポリエステルアミドジオール、ポリチオエーテル
ジオール等が挙げられる。Examples of the polymer diol include polyester diol, polyether diol, polycarbonate diol, polyacetal diol, polyacrylate diol, polyester amide diol, polythioether diol, and the like.
ポリエステルジオールとしては、エチレングリコール、
プロピレングリコール、1.3−プロパンジオ−ル、1
,4−ブタンジオール、1,5−ペンタンジオール、3
−メチル−1,5−ベンタンジオール、1.6−ヘキサ
ンジオール、ネオペンチルグリコール、ジエチレングリ
コール、トリエチレングリコール、テトラエチレングリ
コール、ポリエチレングリコール(分子量300〜6.
000)、ジプロピレングリフール、トリプロピレング
リコール、ビスヒドロキシエトキシベンゼン、1,4−
シクロヘキサンジオール、1゜4−シクロヘキサンジメ
タツール、ビスフェノールA1 水素添加ビスフェノー
ルA1 ハイドロキノン及びそれらのアルキレンオキシ
ド付加体等のグリコール成分とコハク酸、アジピン酸、
アゼライン酸、セバシン酸、ドデカンジカルボン酸、無
水マレイン酸、フマル酸、1. 3−シクロペンクンジ
カルボン酸、1. 4−シクロヘキサンジ力ルボン酸、
テレフタル酸、イソフタル酸、フタル酸、1. 4−ナ
フタレンジカルボン酸、2.5−ナフタレンジカルボン
酸、2,6−ナフタレンジカルボン酸、ナフタル酸、ビ
フェニルジカルボン酸、1.2−ビス(フェノキシ)エ
タン−p、 p’ジカルボン酸及びこれらジカルボン
酸の無水物あるいはエステル形成性誘導体;p−ヒドロ
キシ安息香酸、p−(2−ヒドロキシエトキシ)安息香
酸及びこれらのヒジロキシカルボン酸のエステル形成性
誘導体等の酸成分とから脱水縮合反応によって得られる
ポリエステルの他にε−カプロラクトン等の環状エステ
ル化合物の開環重合反応によって得られるポリエステル
及びこれらの共重合ポリエステルが挙げられる。As polyester diol, ethylene glycol,
Propylene glycol, 1,3-propanediol, 1
, 4-butanediol, 1,5-pentanediol, 3
-Methyl-1,5-bentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300-6.
000), dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-
Cyclohexanediol, 1゜4-cyclohexane dimetatool, bisphenol A1, hydrogenated bisphenol A1, glycol components such as hydroquinone and their alkylene oxide adducts, succinic acid, adipic acid,
Azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1. 3-cyclopencune dicarboxylic acid, 1. 4-cyclohexane dicarbonic acid,
Terephthalic acid, isophthalic acid, phthalic acid, 1. 4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, naphthalic acid, biphenyl dicarboxylic acid, 1,2-bis(phenoxy)ethane-p, p' dicarboxylic acid and these dicarboxylic acids Anhydride or ester-forming derivative; polyester obtained by dehydration condensation reaction with an acid component such as p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and ester-forming derivatives of these hydroxycarboxylic acids. Other examples include polyesters obtained by ring-opening polymerization of cyclic ester compounds such as ε-caprolactone, and copolyesters thereof.
ポリエーテルジオールとしては、エチレングリコール、
ジエチレングリコール、トリエチレングリコール、プロ
ピレングリコール、トリメチレングリコール、1,3−
ブタンジオール、1,4−ブタンジオール、19.6−
へ牛サンジオール、ネオペンチルグリコール、エチレン
ジアミン、ジヒドロキシ安息香酸等の活性水素原子を2
個有する化合物の1種または2種以上を開始剤としてエ
チレンオキサイド、プロピレンオキサイド、ブチレンオ
キサイド、スチレンオキサイド、エピクロルヒドリン、
テトラヒドロフラン、シクロヘキシレン等のモノマーの
1種または2種以上を常法により付加重合したものが挙
げられる。Examples of polyether diol include ethylene glycol,
Diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-
Butanediol, 1,4-butanediol, 19.6-
2 active hydrogen atoms such as hegyosandiol, neopentyl glycol, ethylenediamine, dihydroxybenzoic acid, etc.
Ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin,
Examples include those obtained by addition polymerization of one or more monomers such as tetrahydrofuran and cyclohexylene by a conventional method.
ポリカーボネートジオールとしては、1.4−ブタンジ
オール、1.6−ヘキサンジオール、ジエチレングリコ
ール等のグリコールとジフェニルカーボネート、ホスゲ
ンとの反応によって得られる化合物が挙げられる。Examples of the polycarbonate diol include compounds obtained by reacting glycols such as 1.4-butanediol, 1.6-hexanediol, and diethylene glycol with diphenyl carbonate and phosgene.
上記■のポリウレタンの製造方法で用いるジオール、ジ
アミンとしては、分子fi300以下のジオールで例え
ば、ポリエステルジオールの原料として用いたグリコー
ル成分の他、エチレンジアミン、1,6−へキサメチレ
ンジアミン、ピペラジン、2.5−ジメチルピペラジン
、イソホロンジアミン、4. 4’ −ジシクロヘキシ
ルメタンジアミン、3.3′−ジメチル−4,4′ −
ジシクロヘキシルメタンジアミン、1,4−シクロヘキ
サンジアミン、1.2〜プロパンジアミン、ヒドラジン
、ジエチレントリアミン、トリエチレンテトラミン等の
アミン化合物が挙げられる。The diols and diamines used in the method for producing polyurethane in (2) above include diols with a molecular fi of 300 or less, such as the glycol component used as a raw material for polyester diol, ethylenediamine, 1,6-hexamethylenediamine, piperazine, 2. 5-dimethylpiperazine, isophoronediamine, 4. 4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-
Amine compounds such as dicyclohexylmethanediamine, 1,4-cyclohexanediamine, 1,2-propanediamine, hydrazine, diethylenetriamine, and triethylenetetramine are mentioned.
疎水性ポリウレタン系重合体(A2)は、例えば上記原
料から容易に製造できる。親水性ポリウレタン系重合体
(A1)は上記原料の他に、更に親水性原子団叉は中和
により親水性となりうる原子団を有しかつイソシアネー
ト基と反応し得る活性水素含有化合物を併用することに
より容易に製造できる。このような親水性原子団又は中
和により親水性となりうる原子団を有し、かつイソシア
ネート基と反応し得る活性水素含有化合物としては、例
えば、2−オキシエタンスルホン酸、フェノールスルホ
ン酸、スルホ安息香酸、スルホフハク酸、5−スルホイ
ソフタル酸、スルファニル酸、1゜3−フェニレンジア
ミン−4,6−ジスルホン酸、2.4−ジアミノトルエ
ン−5−スルホン酸等のスルホン酸含有化合物及びこれ
らの誘導体叉はこれらを共重合して得られるポリエステ
ルポリオール;2.2−ジメチロールプロピオン酸、2
,2−ジメチロール酪酸、2.2−ジメチロール吉草酸
、ジオキシマレイン酸、2.6−ジオキシ安息香酸、3
,4−ジアミノ安息香酸等のカルボン酸含有化合物及び
これらの誘導体又はこれらを共重合して得られるポリエ
ステルポリオール;エチレンオキシドの繰り返し単位を
少なくとも30重量%以上含有し、ポリマー中に少なく
とも1個以上の活性水素を含有する分子!300〜
10.000のポリオキシエチレン−ポリオキシアルキ
レン共重合体等のノニオン基含有化合物又はこれらを共
重合して得られるポリエステルポリエーテルボリオール
が挙げられ、これら単独で、もしくは組み合わせて使用
される。The hydrophobic polyurethane polymer (A2) can be easily produced, for example, from the above raw materials. In addition to the above-mentioned raw materials, the hydrophilic polyurethane polymer (A1) may further contain an active hydrogen-containing compound that has a hydrophilic atomic group or an atomic group that can become hydrophilic through neutralization and that can react with isocyanate groups. It can be easily manufactured by Examples of active hydrogen-containing compounds that have such hydrophilic atomic groups or atomic groups that can become hydrophilic through neutralization and that can react with isocyanate groups include 2-oxyethanesulfonic acid, phenolsulfonic acid, and sulfobenzoic acid. acids, sulfonic acid-containing compounds such as sulfophuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1゜3-phenylenediamine-4,6-disulfonic acid, 2,4-diaminotoluene-5-sulfonic acid, and derivatives thereof. is a polyester polyol obtained by copolymerizing these; 2,2-dimethylolpropionic acid, 2
, 2-dimethylolbutyric acid, 2.2-dimethylolvaleric acid, dioxymaleic acid, 2.6-dioxybenzoic acid, 3
, 4-diaminobenzoic acid and other carboxylic acid-containing compounds and their derivatives, or polyester polyols obtained by copolymerizing these; containing at least 30% by weight or more of ethylene oxide repeating units, and containing at least one active unit in the polymer. Molecules containing hydrogen! Examples include nonionic group-containing compounds such as polyoxyethylene-polyoxyalkylene copolymers having a molecular weight of 300 to 10,000, or polyester polyether polyols obtained by copolymerizing these, which may be used alone or in combination. .
ポリウレタン(A)の製造時あるいはポリウレタン(A
)の油中水型の有機溶剤−水分散液の調製時に用いる有
機溶剤は公知慣用のものがいずれも使用可能である。有
機溶剤としては、例えばメチルエチルケトン、メチルプ
ロピルケトン、メチルイソブチルケトン、ジメチルケト
ン、蟻酸メチル、蟻酸エチル、蟻酸プロピル、酢酸メチ
ル、酢酸エチル、酢酸プロピル、酢酸ブチル、アセトン
、テトラハイドロフラン、ジオキサン、ベンゼン、トル
エン、ヘキサン、ジクロルエタン等が挙げられ、これら
は単独でも2種以上を併用しても使用できる。有機溶剤
としては、沸点が120°C以下で25℃における水の
溶解度が有機溶剤100g当たり1〜50gである有機
溶剤が好ましく、メチルエチルケトンが特に好ましい。During the production of polyurethane (A) or
As the organic solvent used in preparing the water-in-oil type organic solvent-water dispersion, any known and commonly used organic solvent can be used. Examples of organic solvents include methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, dimethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetone, tetrahydrofuran, dioxane, benzene, Examples include toluene, hexane, dichloroethane, etc., and these can be used alone or in combination of two or more. The organic solvent is preferably an organic solvent having a boiling point of 120° C. or less and a water solubility of 1 to 50 g per 100 g of organic solvent at 25° C., and methyl ethyl ketone is particularly preferable.
ポリウレタン(A)の油中水型の有機溶剤−水分散液の
調製時に用いる水の使用量は特に制限されないが、通常
ポリウレタン(A)固形分100重量部当たり50重量
部以上である。勿論水の使用量はポリウレタン(A)の
油中水型の有機溶剤−水分散液の固形分濃度、後に説明
するシート製造時の雰囲気の温度、湿度等により適宜選
択することが好ましい。The amount of water used in preparing a water-in-oil organic solvent-water dispersion of polyurethane (A) is not particularly limited, but is usually 50 parts by weight or more per 100 parts by weight of solid content of polyurethane (A). Of course, the amount of water to be used is preferably selected appropriately depending on the solid content concentration of the water-in-oil organic solvent-water dispersion of polyurethane (A), the temperature and humidity of the atmosphere during sheet production, which will be explained later.
本発明で用いるポリウレタン(A)の油中水型の有機溶
剤−水分散液には上記した撥水撥油剤(D)の他に、シ
ートの耐摩耗性、触感、風合いをより向上させるために
必要に応じて他の重合体や縮合体を添加してもよい。こ
の様な重合体や縮合体としては、例えば酢ビ系、エチレ
ン酢ビ系、アクリル系、アクリルスチレン系等のエマル
ジョン;スチレン・ブタジェン系、アクリロニトリル・
ブタジェン系、アクリル・ブタジェン系等のラテックス
;ポリエチレン系、ポリオレフィン系等のアイオノマー
;ポリウレタン、ポリエステル、ポリアミド、エポキシ
系樹脂、セルロースアセテート、エチルセルロース、ブ
チルセルロース等カ挙げられる。In addition to the above-mentioned water and oil repellent (D), the water-in-oil organic solvent-water dispersion of polyurethane (A) used in the present invention is used to further improve the abrasion resistance, tactile feel, and texture of the sheet. Other polymers or condensates may be added as necessary. Examples of such polymers and condensates include emulsions such as vinyl acetate, ethylene vinyl acetate, acrylic, and acrylic styrene; styrene/butadiene, acrylonitrile, and
Latexes such as butadiene type and acrylic/butadiene type; ionomers such as polyethylene type and polyolefin type; polyurethane, polyester, polyamide, epoxy type resin, cellulose acetate, ethyl cellulose, and butyl cellulose.
本発明では、更にポリウレタン(A)の油中水型の有機
溶剤−水分散液に染料、顔料、界面活性剤、柔軟剤、架
橋剤、安定剤、難燃剤、充填剤等の添加剤を必要に応じ
て添加して用いてもよい。The present invention further requires additives such as dyes, pigments, surfactants, softeners, crosslinking agents, stabilizers, flame retardants, fillers, etc. to the water-in-oil organic solvent-water dispersion of polyurethane (A). It may be added and used depending on the situation.
本発明の多孔質シート状物質の製造方法では、撥水撥油
剤(D)を含有したポリウレタンの油中水型の有機溶剤
−水分散液を繊維基材(B)に含浸および/または塗布
せしめた後、該分散液から有機溶剤(C)を蒸発せしめ
てゲル化させることにより多孔質シート状物質が製造さ
れる。多孔質シート状物質は有機溶剤が蒸発し、ゲル化
した時点で形成されるので、その後の操作は特に必要な
いが、通常は有機溶剤(C)を蒸発させた後に更に水を
蒸発させてシートを乾燥させることが多い。In the method for producing a porous sheet material of the present invention, a water-in-oil organic solvent-water dispersion of polyurethane containing a water- and oil-repellent (D) is impregnated and/or applied to a fiber base material (B). Thereafter, the organic solvent (C) is evaporated from the dispersion to form a gel, thereby producing a porous sheet material. A porous sheet-like material is formed when the organic solvent evaporates and becomes a gel, so no further operations are required, but usually water is further evaporated after the organic solvent (C) is evaporated to form a sheet. is often dried.
含浸および/または塗布されるべき繊維基材(B)は、
特に制限がないが、例えば公知慣用の編織布、不織布、
短繊維等が挙げられる。これらの基材は予め撥水加工や
撥油加工が施されたものであってもよい。The fiber substrate (B) to be impregnated and/or coated is
There are no particular limitations, but for example, known and commonly used knitted and woven fabrics, non-woven fabrics,
Examples include short fibers. These base materials may be subjected to water-repellent or oil-repellent treatment in advance.
撥水撥油剤(D)を含有するポリウレタン(A)の油中
水型の有機溶剤−水分散液を繊維基材(B)に含浸およ
び/または塗布する方法は、特に制限されないが、例え
ば、コーティング、スプレーイング、ディッピング等の
従来の各種の方法が採用できる。The method of impregnating and/or coating the fiber base material (B) with a water-in-oil organic solvent-water dispersion of polyurethane (A) containing the water and oil repellent (D) is not particularly limited, but for example, Various conventional methods such as coating, spraying, dipping, etc. can be employed.
有機溶剤(C)を蒸発させる際の条件は特に制限されな
いが、できるだけ水を残しつつ、有機溶剤(C)をより
選択的に蒸発させることが好ましい。有機溶剤(C)を
より選択的に蒸発させる条件は、用いる有機溶剤(C)
の沸点、蒸気圧等により適宜選択することが好ましい。Although the conditions for evaporating the organic solvent (C) are not particularly limited, it is preferable to evaporate the organic solvent (C) more selectively while leaving as much water as possible. The conditions for more selectively evaporating the organic solvent (C) are as follows:
It is preferable to select it appropriately depending on the boiling point, vapor pressure, etc.
例えば、蒸気圧が高く、水より低沸点である有機溶剤(
C)を用いた場合には、水の沸点以下の温度で有機溶剤
(C)の蒸発を行えば良いし、蒸気圧が低く比較的高沸
点の有機溶剤(C)を用いた場合には、高い湿度の雰囲
気下で有機溶剤(C)の蒸発を行えば良い。For example, organic solvents with high vapor pressure and lower boiling points than water (
When C) is used, the organic solvent (C) may be evaporated at a temperature below the boiling point of water, and when an organic solvent (C) with a low vapor pressure and a relatively high boiling point is used, The organic solvent (C) may be evaporated in a high humidity atmosphere.
有機溶剤(C)を蒸発させる際の温度は、−船釣に80
℃以下でポリウレタン(A)の油中水型の有機溶剤−水
分散液中の最も低い沸点を有する有機溶剤(C)の沸点
よりも少なくとも10°C低い温度であることが好まし
い。この様な温度では水の蒸発が容易に抑制でき有機溶
剤(C)の選択的な蒸発が行えるばかりでなく、孔径が
小さく、表面状態にすぐれる多孔質シート状物質が得ら
れるので特に好ましい。The temperature when evaporating the organic solvent (C) is -80℃ for boat fishing.
The temperature is preferably at least 10°C lower than the boiling point of the organic solvent (C) having the lowest boiling point in the water-in-oil organic solvent-water dispersion of the polyurethane (A) at a temperature of at least 10°C. Such a temperature is particularly preferable because not only can evaporation of water be easily suppressed and the organic solvent (C) can be selectively evaporated, but also a porous sheet-like material with small pore diameter and excellent surface condition can be obtained.
有機溶剤(C)を蒸発させるための時間は、少なくとも
ポリウレタン(A)の油中水型の有機溶剤−水分散液中
のポリウレタン成分が凝固する時間は必要である。The time required to evaporate the organic solvent (C) is at least enough time for the polyurethane component in the water-in-oil organic solvent-water dispersion of the polyurethane (A) to coagulate.
本発明の製造方法でえられる多孔質シート状物質は、撥
水撥油剤(D)を含有しているのでそのままで優れた低
吸水率を有しているが、必要に応じてこのシートに更に
撥水撥油剤(D)を付与してもかまわない。The porous sheet-like material obtained by the production method of the present invention has an excellent low water absorption rate as it is because it contains a water and oil repellent (D), but if necessary, this sheet may be further added. A water and oil repellent (D) may be added.
本発明の製造方法でえられる多孔質シート状物質は、そ
のままあるいは他の基材と貼り合わせて合成皮革として
使用できる。より具体的には、レインコート等の衣料、
雨靴等の靴、鞄、自転車カバー テント等の防水布、エ
アコンフィルター、エンジンオイルフィルター等の濾過
材、壁紙、床材、帆布、医療材料等各種の用途が挙げら
れる。The porous sheet-like material obtained by the production method of the present invention can be used as synthetic leather as it is or by bonding it to another base material. More specifically, clothing such as raincoats,
Various uses include shoes such as rain boots, bags, bicycle covers, waterproof fabrics for tents, filtration materials such as air conditioner filters and engine oil filters, wallpaper, flooring materials, canvas, and medical materials.
つぎに、本発明を実施例及び比較例により具体的に説明
するが、部および%は特に断わりのない限りはすべて重
量基準であるものとする。Next, the present invention will be specifically explained with reference to Examples and Comparative Examples, where all parts and percentages are based on weight unless otherwise specified.
合成例 1
ポリエチレンアジペート(分子jll 710)171
0部及びジフェニルメタンジイソシアネート750部を
窒素気流下ioo℃で2時間反応完結せしめ、その後テ
トラメチレングリコール170部、メチルエチルケトン
3945部及びトリエチレンジアミン 3.0部からな
る混合物を加え70℃10時間反応せしめた後、更にメ
チルエチルケトン 2198.7部を加えることにより
固型分30%のポリウレタン分散体(P U−1)を得
た。Synthesis example 1 Polyethylene adipate (molecule jll 710) 171
0 parts and 750 parts of diphenylmethane diisocyanate were allowed to react for 2 hours at IOO°C under a nitrogen stream, and then a mixture consisting of 170 parts of tetramethylene glycol, 3945 parts of methyl ethyl ketone, and 3.0 parts of triethylene diamine was added and reacted at 70°C for 10 hours. Further, 2198.7 parts of methyl ethyl ketone was added to obtain a polyurethane dispersion (PU-1) with a solid content of 30%.
合成例 2
ポリテトラメチレングリコール(分子量1000)10
00部、エチレングリコール93部およびジフェニルメ
タンジインシアネート625部をメチルエチルケトン1
500部中に加え窒素気流下60℃で8時間反応完結せ
しめ、その後メチルエチルケトン2500部を加えるこ
とにより固型分30%のポリウレタン分散体(PU−2
)を得た。Synthesis Example 2 Polytetramethylene glycol (molecular weight 1000) 10
00 parts, 93 parts of ethylene glycol and 625 parts of diphenylmethane diincyanate were added to 1 part of methyl ethyl ketone.
The reaction was completed for 8 hours at 60°C under a nitrogen stream, and then 2500 parts of methyl ethyl ketone was added to form a polyurethane dispersion (PU-2) with a solid content of 30%.
) was obtained.
合成例 3
ポリエチレンアジペート(分子量1625)1300部
、ポリエチレングリコール(分子量1500)300部
及びジフェニルメタンジイソシアネート750部を窒素
気流下100°Cで2時間反応完結せしめ、その後テト
ラメチレングリコール170部、メチルエチルケトン3
780部及びトリエチレンジアミン 3.0部からなる
混合物を加え70℃で10時間反応せしめた後、更にメ
チルエチルケトン2107部を加えることにより固型分
30%のポリウレタン分散液(PU−3)を得た。Synthesis Example 3 1300 parts of polyethylene adipate (molecular weight 1625), 300 parts of polyethylene glycol (molecular weight 1500) and 750 parts of diphenylmethane diisocyanate were allowed to react at 100°C for 2 hours under a nitrogen stream, and then 170 parts of tetramethylene glycol and 3 parts of methyl ethyl ketone were added.
After adding a mixture of 780 parts and 3.0 parts of triethylenediamine and reacting at 70°C for 10 hours, 2107 parts of methyl ethyl ketone was further added to obtain a polyurethane dispersion (PU-3) with a solid content of 30%.
合成例 4
ポリプロピレングリコール(分子量2000)4000
部及びジフェニルメタンジイソシアネート750部を窒
素気流下80°Cで3時間反応完結せしめ、その後ポリ
エチレングリコール(分子量1000)2000部及び
メチルエチルケトン2000部からなる混合物を加え、
70℃で6時間反応せしめた後、更にメチルエチルケト
ン2500部を加えることにより固型分60%のポリウ
レタン溶液(PU−4)を得た。Synthesis example 4 Polypropylene glycol (molecular weight 2000) 4000
and 750 parts of diphenylmethane diisocyanate were allowed to complete the reaction at 80°C for 3 hours under a nitrogen stream, and then a mixture consisting of 2000 parts of polyethylene glycol (molecular weight 1000) and 2000 parts of methyl ethyl ketone was added,
After reacting at 70°C for 6 hours, 2500 parts of methyl ethyl ketone was further added to obtain a polyurethane solution (PU-4) with a solid content of 60%.
合成例 5
ガラス製反応容器中(内容積500m1)に、A−14
4g、 ステアリルアクリレート34.4g、 N
−メチロールアクリルアミド1.6g、 ドデシルメ
ルカプタン0.8g、脱e素した純水 276.8g、
アセトン40g1C+sHsmN(CHs)icl
1 、6 g及びCsH+yC,H40(CHsCH
,0)、H(n=8) 1 、6 gを入れ、アゾビ
スイソブチルアミジンニ塩酸塩 0,4gを加え、窒素
雰囲気下で攪拌しつつ60℃で10時間共重合反応せし
めた。得られた共重合体エマルジョンは固型分濃度20
.0%であった。Synthesis Example 5 In a glass reaction vessel (inner volume 500 m1), A-14
4g, stearyl acrylate 34.4g, N
- 1.6 g of methylol acrylamide, 0.8 g of dodecyl mercaptan, 276.8 g of deionized pure water,
Acetone 40g1C+sHsmN(CHs)icl
1,6 g and CsH+yC,H40(CHsCH
. The obtained copolymer emulsion had a solid content concentration of 20
.. It was 0%.
同様な方法で本発明に係わる共重合体エマルジョンを合
成しその共重合割合を合成例5における共重合割合とと
もに第1表に示した。尚、表中STAはステアリルアク
リレート、EHMAは2−エチルへキシルメタクリレー
ト、EHAは2−エチルへキシルアクリレート、MMA
はメチルメタクリレート、CPMAは3−クロロ−2−
ヒドロ牛ジプロピルメタクリレート、VCIは塩化ビニ
ル、N−MAMはN−メチロールアクリルアミド、OT
Aは2−ヒドロキシエチルアクリレート/2.4−1−
ルエンジイソシアネート/メチルエチルケトキシム=1
/1/1 (モル)の付加体を示す。A copolymer emulsion according to the present invention was synthesized in a similar manner, and its copolymerization ratio is shown in Table 1 together with the copolymerization ratio in Synthesis Example 5. In addition, in the table, STA is stearyl acrylate, EHMA is 2-ethylhexyl methacrylate, EHA is 2-ethylhexyl acrylate, MMA
is methyl methacrylate, CPMA is 3-chloro-2-
Hydrobovine dipropyl methacrylate, VCI is vinyl chloride, N-MAM is N-methylolacrylamide, OT
A is 2-hydroxyethyl acrylate/2.4-1-
Luene diisocyanate/methyl ethyl ketoxime = 1
/1/1 (mol) indicates the adduct.
第1表
合成例 6
パーフルオロアルキル基含有ウレタンアダクト(U=1
)のメチルイソブチルケトン50%溶液400 gSC
+iHxiN(CHm)scl 4.Og。Table 1 Synthesis Example 6 Perfluoroalkyl group-containing urethane adduct (U=1
) of 50% solution of methyl isobutyl ketone 400 gSC
+iHxiN(CHm)scl 4. Og.
CIH17C,H40(CH2CH20)、H(n=8
) 6 、0 g及び水590gを60℃に保温し1
0000回転でホモミキサー処理を行なうことにより固
型分 20.0%のパーフルオロアルキル基含有ウレタ
ンアダクトエマルジョン(F−7)を得た。CIH17C, H40 (CH2CH20), H (n=8
) 6,0 g and 590 g of water were kept warm at 60°C and 1
By performing homomixer treatment at 0,000 revolutions, a perfluoroalkyl group-containing urethane adduct emulsion (F-7) with a solid content of 20.0% was obtained.
合成例 7
ポリブチレンアジペート(分子量500)500部、ジ
フェニルメタンジイソシアネート500部及びメチルエ
チルケトン200部を窒素気流下70℃で3時間反応せ
しめた後、C=F+ySOJ(C−Hy)CJ40H1
170部を加え70℃で6時間反応せしめ、更にメチル
エチルケトン1970部をくわえることにより固型分5
0%のポリウレタン系重合体との相溶性ないし混和性に
優れるパーフルオロアルキル基含有ウレタンオリゴマー
溶液(F−8)を得た。Synthesis Example 7 After reacting 500 parts of polybutylene adipate (molecular weight 500), 500 parts of diphenylmethane diisocyanate and 200 parts of methyl ethyl ketone at 70°C under a nitrogen stream for 3 hours, C=F+ySOJ(C-Hy)CJ40H1
170 parts was added and reacted at 70°C for 6 hours, and then 1970 parts of methyl ethyl ketone was added to reduce the solid content to 5.
A perfluoroalkyl group-containing urethane oligomer solution (F-8) having excellent compatibility or miscibility with 0% polyurethane polymer was obtained.
合成例 8
ガラス製反応容器中(内容積500m1)に、A−75
6g、 ステアリルメタクリレート24g1 ドデシ
ルメルカプタン 0.2g。Synthesis Example 8 In a glass reaction vessel (inner volume 500 m1), A-75
6g, stearyl methacrylate 24g1 dodecyl mercaptan 0.2g.
1.1.1−トリクロロエタン119.8gを入れ、ア
ゾビスイソブチルニトリル0.4gを加え、窒素雰囲気
下で攪拌しつつ70℃で12時間共重合反応せしめた。1.1.1-Trichloroethane (119.8 g) was added, and azobisisobutylnitrile (0.4 g) was added, followed by a copolymerization reaction at 70° C. for 12 hours with stirring under a nitrogen atmosphere.
得られた粘稠溶液に1.1.1−トリクロロエタン20
0gを加え、固型分20.0%の共重合体溶液(F−9
)を得た。Add 20% of 1.1.1-trichloroethane to the resulting viscous solution.
0g of copolymer solution (F-9) with a solid content of 20.0%.
) was obtained.
合成例 9
A−756g、 ステアリルメタクリレート24g1
ドデシルメルカプタン 0.2gを用いる以外は合成
例5と全く同様にして共重合体エマルジョン(F−10
)を得た。Synthesis example 9 A-756g, stearyl methacrylate 24g1
A copolymer emulsion (F-10
) was obtained.
実施例 1〜15及び比較例 1〜2
合成例1〜4のポリウレタン、合成例5の共重合体エマ
ルジョン、合成例6のウレタンアダクトエマルジョン、
合成例7のウレタンオリゴマー溶液、合成例8の共重合
体溶液、合成例9の共重合体エマルジョン、有機溶剤及
び水を第2表に示す割合で混合しホモミキサーで攪拌す
ることにより乳白色の撥水撥油剤を含有するポリウレタ
ンの油中水型の有機溶剤−水分散液を調整した。この分
散液をポリエステル単繊維よりなる不織布に含浸し、直
ちに80℃で10分溶剤の選択蒸発を行い、次いで12
0℃で5分間乾燥した。かくして得られた多孔質シート
状物質の特性を第2表に示す。Examples 1 to 15 and Comparative Examples 1 to 2 Polyurethane of Synthesis Examples 1 to 4, copolymer emulsion of Synthesis Example 5, urethane adduct emulsion of Synthesis Example 6,
The urethane oligomer solution of Synthesis Example 7, the copolymer solution of Synthesis Example 8, the copolymer emulsion of Synthesis Example 9, an organic solvent, and water were mixed in the proportions shown in Table 2 and stirred with a homomixer to form a milky white repellent. A water-in-oil organic solvent-water dispersion of polyurethane containing a water and oil repellent was prepared. This dispersion was impregnated into a nonwoven fabric made of polyester single fibers, and the solvent was immediately selectively evaporated at 80°C for 10 minutes.
It was dried at 0°C for 5 minutes. The properties of the porous sheet material thus obtained are shown in Table 2.
尚、表中の吸水率はJIS K−6505、透湿度は
JIS L−0208の方法に準じて測定を行なった
。In addition, the water absorption rate in the table was measured according to the method of JIS K-6505, and the water vapor permeability was measured according to the method of JIS L-0208.
以上の通り本発明によれば、極めて吸水性の低い多孔質
シート状物質が得られることができる。As described above, according to the present invention, a porous sheet material with extremely low water absorption can be obtained.
本発明の方法で得られる多孔質シート状物質が如何なる
理由により吸水性が極めて低いかは不明であるが、ポリ
ウレタンの油中水型の有機溶剤水分散液を基材に含浸お
よび/または塗布せしめることにより多孔質シート状物
質を得る方法においては、撥水撥油剤、その有機溶剤溶
液は勿論、特に撥水撥油剤をエマルジョンとして用いた
場合には、そのエマルジョンが水層部分に存在する結果
として、水が蒸発する過程で生ずる多孔質皮膜に内在す
る気孔表面ばかりでなく基材である繊維表面にも撥水撥
油剤が付着することにより画部分の撥水性が得られ、特
に優れた低吸水性が得られることによるものと推察され
る。Although it is unclear why the porous sheet material obtained by the method of the present invention has extremely low water absorption, it is possible to impregnate and/or coat a base material with a water-in-oil type organic solvent aqueous dispersion of polyurethane. In the method of obtaining a porous sheet-like material by this method, not only the water and oil repellent agent and its organic solvent solution, but especially when the water and oil repellent agent is used as an emulsion, as a result of the emulsion existing in the water layer part. The water- and oil-repellent agent adheres not only to the surface of the pores in the porous film that is formed in the process of water evaporation, but also to the fiber surface of the base material, making the painting area water repellent, resulting in particularly excellent low water absorption. It is presumed that this is due to the fact that sex is obtained.
本発明のポリウレタンの油中水型の有機溶剤−水分散液
を繊維基材に含浸および/または塗布せしめた後、該分
散液から有機溶剤を蒸発せしめてゲル化させて、多孔質
シート状物質を製造する方法に分散液を用いることを特
徴とする多孔質シート状物質の製造方法で得られる多孔
質シート状物質は、極めて優れた低吸湿性を有するし、
透湿性も充分であるという格別顕著な効果をそうする。After impregnating and/or applying the water-in-oil type organic solvent-water dispersion of the polyurethane of the present invention to a fiber base material, the organic solvent is evaporated from the dispersion to form a gel. The porous sheet material obtained by the method for producing a porous sheet material characterized by using a dispersion liquid in the method for producing the porous sheet material has extremely low hygroscopicity, and
It has a particularly remarkable effect of having sufficient moisture permeability.
Claims (1)
液を、繊維基材(B)に含浸および/または塗布せしめ
た後、該分散液から有機溶剤(C)を蒸発せしめてゲル
化させて多孔質シート状物質を製造する方法において、
該分散液として、撥水撥油剤(D)を含有する分散液を
用いることを特徴とする多孔質シート状物質の製造方法
。 2、撥水撥油剤(D)が、フッ素系撥水撥油剤である請
求項1記載の製造方法。 3、撥水撥油剤(D)が、フッ素系撥水撥油剤エマルジ
ョンである請求項1記載の製造方法。 4、撥水撥油剤(D)が、一分子中にパーフルオロアル
キル基とブロック化イソシアネート基を有するアクリル
系重合体のエマルジョンである請求項1記載の製造方法
。 5、撥水撥油剤(D)が、パーフルオロアルキル基含有
エチレン性不飽和単量体50〜90重量%、パーフルオ
ロアルキル基不含のエチレン性不飽和単量体10〜50
重量%との共重合体エマエルジョンである請求項1記載
の製造方法。 6、ポリウレタン(A)固形分100重量部当たり、撥
水撥油剤(D)固形分を0.1〜3重量部用いる請求項
1、2、3、4または5記載の製造方法。 7、親水性ポリウレタン系重合体(A1)単独又は重合
体(A1)と疎水性ポリウレタン系重合体(A2)との
混合物の油中水型の有機溶剤−水分散液を、繊維基材(
B)に含浸および/または塗布せしめた後、該分散液か
ら有機溶剤(C)を蒸発せしめてゲル化させて多孔質シ
ート状物質を製造する方法において、該分散液として、
撥水撥油剤(D)を含有する分散液を用いることを特徴
とする多孔質シート状物質の製造方法。 8、撥水撥油剤(D)が、フッ素系撥水撥油剤である請
求項7記載の製造方法。 9、撥水撥油剤(D)が、フッ素系撥水撥油剤エマルジ
ヨンである請求項7記載の製造方法。 10、撥水撥油剤(D)が、一分子中にパーフルオロア
ルキル基とブロック化イソシアネート基を有するアクリ
ル系重合体のエマルジョンである請求項7記載の製造方
法。 11、撥水撥油剤(D)が、パーフルオロアルキル基含
有エチレン性不飽和単量体50〜90重量%、パーフル
オロアルキル基不含のエチレン性不飽和単量体10〜5
0重量%との共重合体エマエルジョンである請求項7記
載の製造方法。 12、ポリウレタン固形分100重量部当たり、撥水撥
油剤固形分を0.1〜3重量部用いる請求項7、8、9
、10または11記載の製造方法。[Claims] 1. After impregnating and/or coating a fiber base material (B) with a water-in-oil organic solvent-water dispersion of polyurethane (A), the organic solvent (C ) in a method for producing a porous sheet-like material by evaporating and gelling,
A method for producing a porous sheet material, characterized in that a dispersion containing a water and oil repellent (D) is used as the dispersion. 2. The manufacturing method according to claim 1, wherein the water and oil repellent (D) is a fluorine-based water and oil repellent. 3. The manufacturing method according to claim 1, wherein the water and oil repellent (D) is a fluorine-based water and oil repellent emulsion. 4. The production method according to claim 1, wherein the water and oil repellent (D) is an emulsion of an acrylic polymer having a perfluoroalkyl group and a blocked isocyanate group in one molecule. 5. The water and oil repellent (D) contains 50 to 90% by weight of an ethylenically unsaturated monomer containing a perfluoroalkyl group and 10 to 50% by weight of an ethylenically unsaturated monomer containing no perfluoroalkyl group.
The method according to claim 1, which is a copolymer emulsion with % by weight. 6. The manufacturing method according to claim 1, 2, 3, 4 or 5, wherein the solid content of the water and oil repellent (D) is used in an amount of 0.1 to 3 parts by weight per 100 parts by weight of the solid content of the polyurethane (A). 7. A water-in-oil organic solvent-water dispersion of the hydrophilic polyurethane polymer (A1) alone or a mixture of the polymer (A1) and the hydrophobic polyurethane polymer (A2) is added to the fiber base material (
In a method of manufacturing a porous sheet-like material by impregnating and/or applying B) and then evaporating the organic solvent (C) from the dispersion to gel it, as the dispersion,
A method for producing a porous sheet-like material, comprising using a dispersion containing a water and oil repellent (D). 8. The manufacturing method according to claim 7, wherein the water and oil repellent (D) is a fluorine-based water and oil repellent. 9. The manufacturing method according to claim 7, wherein the water and oil repellent (D) is a fluorine-based water and oil repellent emulsion. 10. The production method according to claim 7, wherein the water and oil repellent (D) is an emulsion of an acrylic polymer having perfluoroalkyl groups and blocked isocyanate groups in one molecule. 11. The water and oil repellent (D) contains 50 to 90% by weight of an ethylenically unsaturated monomer containing a perfluoroalkyl group and 10 to 5% of an ethylenically unsaturated monomer containing no perfluoroalkyl group.
The method according to claim 7, which is a copolymer emulsion with 0% by weight. 12. Claims 7, 8 and 9 in which 0.1 to 3 parts by weight of water and oil repellent solids are used per 100 parts by weight of polyurethane solids.
, 10 or 11.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16227190A JPH0453842A (en) | 1990-06-20 | 1990-06-20 | Production of porous sheet-like substance with low water absorption capacity |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16227190A JPH0453842A (en) | 1990-06-20 | 1990-06-20 | Production of porous sheet-like substance with low water absorption capacity |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0453842A true JPH0453842A (en) | 1992-02-21 |
Family
ID=15751291
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16227190A Pending JPH0453842A (en) | 1990-06-20 | 1990-06-20 | Production of porous sheet-like substance with low water absorption capacity |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0453842A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001044339A1 (en) * | 1999-12-14 | 2001-06-21 | E.I. Du Pont De Nemours And Company | Highly durable oil/water repellents for textiles |
US6479605B1 (en) | 2001-05-15 | 2002-11-12 | E. I. Du Pont De Nemours And Company | High-durability, low-yellowing repellent for textiles |
JP2018528318A (en) * | 2015-09-24 | 2018-09-27 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Thermoplastic polyurethane |
-
1990
- 1990-06-20 JP JP16227190A patent/JPH0453842A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001044339A1 (en) * | 1999-12-14 | 2001-06-21 | E.I. Du Pont De Nemours And Company | Highly durable oil/water repellents for textiles |
US6451717B1 (en) | 1999-12-14 | 2002-09-17 | E. I. Du Pont De Nemours And Company | Highly durable oil/water repellents for textiles |
US6479605B1 (en) | 2001-05-15 | 2002-11-12 | E. I. Du Pont De Nemours And Company | High-durability, low-yellowing repellent for textiles |
JP2018528318A (en) * | 2015-09-24 | 2018-09-27 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Thermoplastic polyurethane |
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