JP2005089644A - Hydrophilic functional group-containing polyurethane resin and method for producing the same - Google Patents
Hydrophilic functional group-containing polyurethane resin and method for producing the same Download PDFInfo
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- JP2005089644A JP2005089644A JP2003326351A JP2003326351A JP2005089644A JP 2005089644 A JP2005089644 A JP 2005089644A JP 2003326351 A JP2003326351 A JP 2003326351A JP 2003326351 A JP2003326351 A JP 2003326351A JP 2005089644 A JP2005089644 A JP 2005089644A
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- Prior art keywords
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- compound
- active hydrogen
- polyurethane resin
- molecular weight
- 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.)
- Granted
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 44
- 125000000524 functional group Chemical group 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 90
- -1 polysiloxane Polymers 0.000 claims abstract description 84
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 37
- 150000002009 diols Chemical class 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 9
- 150000004985 diamines Chemical class 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims description 15
- 150000003077 polyols Chemical class 0.000 claims description 15
- 229920000768 polyamine Polymers 0.000 claims description 10
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 17
- 239000011248 coating agent Substances 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 abstract description 12
- 230000000903 blocking effect Effects 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 238000005299 abrasion Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 150000002222 fluorine compounds Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 12
- 239000011737 fluorine Substances 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- 239000003431 cross linking reagent Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 125000002947 alkylene group Chemical group 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 125000000962 organic group Chemical group 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 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 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 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
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 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 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 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
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical group 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- ZKSBDEFDWSDNPW-UHFFFAOYSA-N 1-butoxy-2,4-diisocyanatobenzene Chemical compound CCCCOC1=CC=C(N=C=O)C=C1N=C=O ZKSBDEFDWSDNPW-UHFFFAOYSA-N 0.000 description 1
- SZBXTBGNJLZMHB-UHFFFAOYSA-N 1-chloro-2,4-diisocyanatobenzene Chemical compound ClC1=CC=C(N=C=O)C=C1N=C=O SZBXTBGNJLZMHB-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- DZDVHNPXFWWDRM-UHFFFAOYSA-N 2,4-diisocyanato-1-methoxybenzene Chemical compound COC1=CC=C(N=C=O)C=C1N=C=O DZDVHNPXFWWDRM-UHFFFAOYSA-N 0.000 description 1
- VXQILLTWRZPRQF-UHFFFAOYSA-N 2,4-diisocyanato-1-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(N=C=O)C=C1N=C=O VXQILLTWRZPRQF-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- JJUBFBTUBACDHW-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decanol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JJUBFBTUBACDHW-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
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920002799 BoPET Polymers 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- VWYHWAHYVKZKHI-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC(N)=CC=C1C1=CC=C(N)C=C1 Chemical compound N=C=O.N=C=O.C1=CC(N)=CC=C1C1=CC=C(N)C=C1 VWYHWAHYVKZKHI-UHFFFAOYSA-N 0.000 description 1
- FSIWPDPQLFIDPY-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC(N)=CC=C1C1=CC=C(N)C=C1[N+]([O-])=O Chemical compound N=C=O.N=C=O.C1=CC(N)=CC=C1C1=CC=C(N)C=C1[N+]([O-])=O FSIWPDPQLFIDPY-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 239000010949 copper Substances 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
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- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
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- 239000000539 dimer Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
本発明は、各種フィルム、皮膜及びその他の樹脂成型品に優れた表面性質を付与し、各種有機溶剤に可溶で、低粘度で優れた塗工性を有する塗料用樹脂として有用な親水性官能基含有ポリウレタン樹脂に関する。 The present invention imparts excellent surface properties to various films, coatings and other resin molded products, is soluble in various organic solvents, has a low viscosity and is useful as a coating resin having excellent coating properties. The present invention relates to a group-containing polyurethane resin.
各種フィルム或いは各種皮膜等の樹脂成型品の表面は、耐汚染性、耐水性、耐磨耗性等に優れていることが要求され、又、用途によっては耐粘着性、低表面摩擦係数、耐熱ブロッキング性が要求される。 The surface of resin molded products such as various films or various coatings is required to have excellent contamination resistance, water resistance, abrasion resistance, etc., and depending on the application, adhesion resistance, low surface friction coefficient, heat resistance Blocking is required.
このような要求に対しては、ポリウレタン樹脂に、その成型品に滑性や撥水性等を付与するシリコーンオイル、フッ素樹脂、ワックス或いは脂肪酸等の潤滑剤を添加又は塗布する等の方法が行なわれている。この方法によれば、ある程度の目的は達成されるが、成型物中に添加した潤滑剤が経時的に成型物の表面にブリードアウトし汚染の原因となったり、払拭されて性能低下が引き起こされる等の問題が発生する。 In response to such demands, methods such as adding or applying a lubricant such as silicone oil, fluororesin, wax, or fatty acid to the polyurethane resin to impart lubricity, water repellency, etc. to the polyurethane resin are performed. ing. According to this method, a certain amount of purpose is achieved, but the lubricant added to the molded product bleeds out to the surface of the molded product over time, causing contamination or being wiped away, resulting in performance degradation. Problems occur.
又、ポリウレタン樹脂中にポリシロキサンセグメント或いはフッ素含有セグメントを共重合させ、ブリードアウトを克服する方法があるが、これらのセグメント含有量が少ないと充分な表面特性が得られず、セグメント含有量が多い場合には、皮膜の機械的強度の低下や基材との密着性が損なわれる等の欠点が指摘される。又、ポリシロキサン或いはフッ素含有セグメントの含有量を低く抑え、かつ機械的強度、耐熱性、非粘着性を発揮させるために樹脂中にアミド基或いはイミド基等を導入して高いＴｇを有する樹脂とする技術が公知となっているが、溶剤が限定されたり、溶液粘度が高くなる等の実使用に不便を生ずる等の欠点があった（特許文献１〜５参照）。 In addition, there is a method of overcoming bleed out by copolymerizing polysiloxane segments or fluorine-containing segments in polyurethane resin, but if these segment contents are low, sufficient surface properties cannot be obtained, and the segment content is high. In such a case, defects such as a decrease in the mechanical strength of the film and a loss of adhesion to the substrate are pointed out. Also, a resin having a high Tg by introducing an amide group or an imide group into the resin in order to keep the content of the polysiloxane or fluorine-containing segment low and exhibit mechanical strength, heat resistance and non-adhesiveness However, there have been disadvantages such as inconvenience in actual use such as limited solvent and increased solution viscosity (see Patent Documents 1 to 5).
本発明者らは、上記目的を達成すべく鋭意検討の結果、“官能基を導入したセグメント化ウレタン樹脂の相構造と界面構造との関連性”において報告されている、スルホン基導入ポリウレタンが乾燥塗膜形成時に相分離構造を発現して、基材界面に極性基が配向するため密着性に優れた塗膜が得られる現象（非特許文献１参照）をさらに発展させることで問題の解決を見た。 As a result of intensive studies to achieve the above object, the present inventors have reported that the sulfone group-introduced polyurethane reported in “Relationship between phase structure and interface structure of segmented urethane resin into which functional group is introduced” is dried. Solve the problem by further developing the phenomenon (see Non-Patent Document 1) that expresses a phase separation structure at the time of coating film formation, and a polar group is oriented at the substrate interface, so that a coating film with excellent adhesion can be obtained. saw.
すなわち、低分子量ポリマー鎖とポリシロキサンセグメントとを含有するポリウレタン樹脂に、更に親水性官能基を導入して得られた親水性官能基含有シリコーン変性櫛型ポリウレタン樹脂は、その乾燥塗膜をプラスチック表面上に形成させた場合、塗膜表面層には疎水性の低分子量ポリマー鎖とポリシロキサンセグメントが、又、基材との界面には親水性基が効果的に相分離・配向された構造の膜となる。このことにより、上記の親水性官能基含有シリコーン変性櫛型ポリウレタン樹脂は、ポリシロキサンセグメントを同率で含有する一般的なポリウレタン樹脂に較べて、高い耐汚染性、耐水性、機械的強度、耐磨耗性、耐粘着性、低表面摩擦係数、耐熱ブロッキング性と、更に優れた基材密着性、低いＴｇ特性による、ＭＥＫ等のソフトソルベントに可溶で且つ低粘度であるといった良好なハンドリング性をも兼備えるポリウレタン樹脂であることが判明した。 That is, a hydrophilic functional group-containing silicone-modified comb polyurethane resin obtained by further introducing a hydrophilic functional group into a polyurethane resin containing a low molecular weight polymer chain and a polysiloxane segment has a dry coating film on the plastic surface. When formed above, the coating surface layer has a structure in which hydrophobic low molecular weight polymer chains and polysiloxane segments are effectively phase separated and oriented at the interface with the substrate. Become a film. Accordingly, the above-mentioned hydrophilic functional group-containing silicone-modified comb polyurethane resin has higher stain resistance, water resistance, mechanical strength, and abrasion resistance than general polyurethane resins containing polysiloxane segments at the same rate. Good handling properties, such as wear resistance, adhesion resistance, low surface friction coefficient, heat blocking resistance, excellent base material adhesion, low Tg characteristics, soluble in MEK and other soft solvents and low viscosity Was also found to be a polyurethane resin.
本発明の課題は、耐汚染性、耐水性、耐磨耗性、耐粘着性、耐ブリード性、耐熱ブロッキング性、撥水性に優れ、ＭＥＫ等のソフトソルベントに可溶で、低粘度の塗料を与える親水性ポリウレタン樹脂を提供することを目的とする。 The object of the present invention is to provide a stain-resistant, water-resistant, abrasion-resistant, adhesive-resistant, bleed-resistant, heat-resistant blocking property, water repellency, soluble in a soft solvent such as MEK, and a low-viscosity paint. It aims at providing the hydrophilic polyurethane resin to give.
上記課題は以下の本発明によって達成される。即ち本発明は、１方の末端にＨＯ−ＣＨ2−ＣＨ（ＯＨ）−基を有する低分子量ポリマー（Ａ）、分子内に２個の活性水素含有基と少なくとも１個の上記活性水素含有基以外の親水性基とを両有する化合物（Ｂ）、ジオール及び／又はジアミン（Ｃ）とジイソシアネートを反応させて得られる、重量平均分子量が１０，０００〜５００，０００で、上記の各化合物から誘導される単位がランダムにウレタン結合及び／又はウレア結合で結合され、上記の化合物（Ａ）からの単位が１０〜９９．９重量％、化合物（Ｂ）からの単位が０．１〜３０重量％、化合物（Ｃ）からの単位が０〜５０重量％（但し、化合物（Ａ）〜（Ｃ）からの単位の合計は１００重量％である。）であることを特徴とする親水性官能基含有ポリウレタン樹脂である。 The above-mentioned subject is achieved by the following present invention. That is, the present invention relates to a low molecular weight polymer (A) having a HO—CH 2 —CH (OH) — group at one end, two active hydrogen-containing groups and at least one active hydrogen-containing group in the molecule. Derived from the above compounds having a weight average molecular weight of 10,000 to 500,000 obtained by reacting a diisocyanate with a compound (B) having both a hydrophilic group other than diol and / or diamine (C) Unit is randomly bonded by urethane bond and / or urea bond, the unit from the compound (A) is 10 to 99.9% by weight, the unit from the compound (B) is 0.1 to 30% by weight. Hydrophilic functional group-containing, wherein the unit from the compound (C) is 0 to 50% by weight (however, the total of the units from the compounds (A) to (C) is 100% by weight) Polyurethane resin.
又、本発明は、１方の末端にＨＯ−ＣＨ2−ＣＨ（ＯＨ）−基を有する低分子量ポリマー（Ａ）、分子内に２個の活性水素含有基と少なくとも１個の上記活性水素含有基以外の親水性基とを両有する化合物（Ｂ）、ジオール及び／又はジアミン（Ｃ）、分子中に１個又は２個の活性水素含有基を有するポリシロキサン化合物（Ｄ）及び／又はパーフルオロアルキル基含有化合物（Ｅ）をジイソシアネートと反応させて得られる、重量平均分子量が１０，０００〜５００，０００で、上記の各化合物から誘導される単位がランダムにウレタン結合及び／又はウレア結合で結合されてなり、化合物（Ａ）からの単位が１０〜９９．８重量％、化合物（Ｂ）からの単位が０．１〜３０重量％、化合物（Ｃ）からの単位が０〜５０重量％、化合物（Ｄ）及び／又は（Ｅ）からの単位が０．１〜８０重量％（但し、化合物Ａ〜Ｅからの単位の合計は１００重量％である。）であることを特徴とする親水性官能基含有ポリウレタン樹脂である。 The present invention also provides a low molecular weight polymer (A) having a HO—CH 2 —CH (OH) — group at one end, two active hydrogen-containing groups and at least one of the above active hydrogens in the molecule. Compound (B) having both a hydrophilic group other than the group, diol and / or diamine (C), polysiloxane compound (D) having one or two active hydrogen-containing groups in the molecule and / or perfluoro The weight average molecular weight obtained by reacting the alkyl group-containing compound (E) with diisocyanate is 10,000 to 500,000, and the units derived from the above compounds are randomly bonded by urethane bonds and / or urea bonds. The unit from compound (A) is 10 to 99.8% by weight, the unit from compound (B) is 0.1 to 30% by weight, the unit from compound (C) is 0 to 50% by weight, Compound (D And / or hydrophilic functional group-containing polyurethane characterized in that the unit from (E) is 0.1 to 80% by weight (provided that the total of units from compounds A to E is 100% by weight) Resin.
さらに、本発明は、溶剤の存在下又は不存在下に、１方の末端に少なくとも１個の活性水素含有基を有する低分子量ポリマー、分子内に少なくとも１個の活性水素含有基と上記活性水素含有基以外の親水性基とを両有する化合物、ポリオール及び／又はポリアミンと、ポリイソシアネートとを、又はこれらと少なくとも１個の活性水素含有基を有するポリシロキサン化合物及び／又はパーフルオロアルキル基含有化合物を加えて反応させることを特徴とする親水性官能基含有ポリウレタン樹脂の製造方法である。 Furthermore, the present invention provides a low molecular weight polymer having at least one active hydrogen-containing group at one end in the presence or absence of a solvent, at least one active hydrogen-containing group in the molecule and the active hydrogen. Compound having both hydrophilic group other than containing group, polyol and / or polyamine, and polyisocyanate, or polysiloxane compound having at least one active hydrogen-containing group and / or perfluoroalkyl group-containing compound Is a method for producing a hydrophilic functional group-containing polyurethane resin.
（作用）
本発明の親水性官能基含有ポリウレタン樹脂は、親水性官能基、低分子量ポリマー鎖、又はこれらとともにポリシロキサンセグメント及び／又はパーフルオロアルキル基含有セグメントが、ウレタン結合及び／又はウレア結合で連結されたポリウレタン樹脂である。前者のポリウレタン樹脂は、ウレタン結合等を有する部分が幹部分を、低分子量ポリマー鎖が枝部分を形成する。後者のポリウレタン樹脂は、上記部分に加えて、ポリシロキサンセグメント及び／又はパーフルオロアルキル基含有セグメントが、その原料成分が両末端反応型であれば幹部分に、片末端反応型であれば枝部分に導入される。
(Function)
In the hydrophilic functional group-containing polyurethane resin of the present invention, a hydrophilic functional group, a low molecular weight polymer chain, or a polysiloxane segment and / or a perfluoroalkyl group-containing segment is connected with urethane bonds and / or urea bonds. Polyurethane resin. In the former polyurethane resin, a portion having a urethane bond or the like forms a trunk portion, and a low molecular weight polymer chain forms a branch portion. The latter polyurethane resin has a polysiloxane segment and / or a perfluoroalkyl group-containing segment in addition to the above-mentioned part, a trunk part if the raw material component is a double-end reactive type, and a branch part if it is a single-terminal reactive type. To be introduced.
これらの親水性官能基含有ポリウレタン樹脂溶液からプラスチック基材表面に乾燥皮膜を形成させると、セグメント間の表面エネルギーの相違から、表面エネルギーの低いポリシロキサンセグメント及び／又はパーフルオロアルキル基含有セグメントと枝部分の低分子量ポリマー鎖は皮膜表面層に、幹のウレタン結合等を有する部分と親水性基は基材側に配向する。 When a dry film is formed on the surface of a plastic substrate from these hydrophilic functional group-containing polyurethane resin solutions, polysiloxane segments and / or perfluoroalkyl group-containing segments and branches having a low surface energy are caused by the difference in surface energy between the segments. The low molecular weight polymer chain of the portion is oriented on the surface layer of the coating, and the portion having a urethane bond of the trunk and the hydrophilic group are oriented on the substrate side.
従来のポリシロキサンセグメント或いはフッ素含有セグメントを有する耐熱性或いは撥水性材料では、基材表面に配向したこれらのセグメントの効果により上記特性が得られていたが、本発明の親水性官能基含有ポリウレタン樹脂では、表面エネルギーの低い低分子量ポリマー鎖を皮膜表面に配向させることにより、ポリシロキサンセグメント或いはパーフルオロアルキル基含有セグメントを含有していない場合にも充分なる耐熱性或いは撥水性が発揮される。さらに、ポリシロキサンセグメント或いはパーフルオロアルキル基含有セグメントをポリウレタン樹脂に導入することで、耐熱性、滑り性、汚れ防止性等が一段と向上する。 In the conventional heat-resistant or water-repellent material having a polysiloxane segment or a fluorine-containing segment, the above characteristics were obtained by the effect of these segments oriented on the surface of the substrate, but the hydrophilic functional group-containing polyurethane resin of the present invention Then, by aligning a low molecular weight polymer chain having a low surface energy on the film surface, sufficient heat resistance or water repellency is exhibited even when the polysiloxane segment or the perfluoroalkyl group-containing segment is not contained. Furthermore, by introducing the polysiloxane segment or the perfluoroalkyl group-containing segment into the polyurethane resin, the heat resistance, slipping property, antifouling property and the like are further improved.
以上のように、本発明の親水性官能基含有ポリウレタン樹脂は、耐汚染性、耐水性、機械的強度、耐磨耗性、耐粘着性、低表面摩擦係数、耐熱ブロッキング性及び撥水性に優れ、更に基材密着性、ＭＥＫ等のソフトソルベントに可溶で且つ低粘度であるといった良好なハンドリング性をも兼備えた素材であり、塗料、感熱記録用のバックコート剤等に応用できる。 As described above, the hydrophilic functional group-containing polyurethane resin of the present invention is excellent in stain resistance, water resistance, mechanical strength, abrasion resistance, adhesion resistance, low surface friction coefficient, heat blocking resistance and water repellency. Furthermore, it is a material that also has good handling properties such as adhesion to a base material, solubility in a soft solvent such as MEK and low viscosity, and can be applied to paints, backcoat agents for thermal recording, and the like.
次に本発明を更に詳細に説明する。
まず本発明の親水性官能基含有ポリウレタン樹脂（以下では親水性ポリウレタン樹脂ということがある。）に使用する原料成分について説明する。
本発明に使用する１方の分子末端にＨＯ−ＣＨ2−ＣＨ（ＯＨ）−基を有する低分子量ポリマー（Ａ）は、上記の基を一方の末端に有しているものであれば、ポリマー鎖を構成するモノマーの種類は特に限定されない。モノマーとしては、それを（共）重合してなるポリマーのガラス転移温度（Ｔｇ）が８０℃以下となるものが好ましく、さらに好ましくは−１００℃〜２０℃となるものである。又、低分子量ポリマーの分子量は、重量平均分子量（ＧＰＣ法、標準ポリスチレン換算）が、通常、１，０００〜２０，０００程度である。
Next, the present invention will be described in more detail.
First, raw material components used in the hydrophilic functional group-containing polyurethane resin of the present invention (hereinafter sometimes referred to as hydrophilic polyurethane resin) will be described.
The low molecular weight polymer (A) having a HO—CH 2 —CH (OH) — group at one molecular end used in the present invention is a polymer as long as it has the above group at one end. The kind of monomer constituting the chain is not particularly limited. The monomer is preferably one having a glass transition temperature (Tg) of a polymer obtained by (co) polymerizing it of 80 ° C. or less, more preferably −100 ° C. to 20 ° C. The molecular weight of the low molecular weight polymer is usually about 1,000 to 20,000 in terms of weight average molecular weight (GPC method, standard polystyrene conversion).
このような低分子量ポリマーは、その製造方法は特に限定されないが、例えば、特開２０００−１２８９１１号公報に記載の下記のようなチオグリコール等を重合触媒として、ＭＭＡ等のモノマーを、塊状（共）重合することにより得ることができる。
少なくとも１個の活性水素含有基と上記活性水素含有基以外の親水性官能基とを同一分子内に両有する化合物（Ｂ）としては、例えば、活性水素含有基が水酸基の場合には、水酸基以外のスルホン酸系、カルボン酸系、燐酸系、アミン系等の化合物を用いることができる。
例えば、スルホン酸系化合物であれば、下記化合物及びその誘導体等が挙げられる。
以上は本発明において使用される好ましい化合物の例示であって、本発明はこれらの例示の化合物に限定されるものではない。従って、上述の例示化合物のみならず、その他現在市販されていて、市場から容易に入手できる化合物は、いずれも本発明に使用することができる。
As the compound (B) having both at least one active hydrogen-containing group and a hydrophilic functional group other than the active hydrogen-containing group in the same molecule, for example, when the active hydrogen-containing group is a hydroxyl group, other than the hydroxyl group The sulfonic acid type, carboxylic acid type, phosphoric acid type, amine type and the like can be used.
For example, if it is a sulfonic acid-type compound, the following compound, its derivative, etc. will be mentioned.
The above are examples of preferred compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only the exemplified compounds described above, but also any other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention.
ポリオール及びポリアミン（Ｃ）としては、ポリウレタンの製造に従来から使用されている短鎖ジオール、短鎖ジアミン、高分子ポリオール等の従来公知のものが使用でき特に限定されない。
短鎖ジオールとしては例えば、エチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、１，４−ブチレングリコール、１，６−ヘキサメチレングリコール、ネオペンチルグリコール等の脂肪族グリコール類及びそのアルキレンオキシド低モル付加物（数平均分子量５００未満）；１，４−ビスヒドロキシメチルシクロヘキサン、２−メチル−１，１−シクロヘキサンジメタノール等の脂環式系グリコール類及びそのアルキレンオキシド低モル付加物（数平均分子量５００未満）；キシリレングリコール等の芳香族グリコール類及びそのアルキレンオキシド低モル付加物（数平均分子量５００未満）；ビスフェノールＡ、チオビスフェノール、スルホンビスフェノール等のビスフェノール類及びそのアルキレンオキシド低モル付加物（数平均分子量５００未満）；Ｃ１〜Ｃ１８のアルキルジエタノールアミン等のアルキルジアルカノールアミン類等の化合物が挙げられる。又、多価アルコール系化合物としては、例えば、グリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール、トリス−（２−ヒドロキシエチル）イソシアヌレート、１，１，１−トリメチロールエタン、１，１，１−トリメチロールプロパン等が挙げられる。これらは単独或いは２種類以上を組み合わせて使用することができる。
As the polyol and polyamine (C), conventionally known ones such as a short-chain diol, a short-chain diamine, and a polymer polyol conventionally used in the production of polyurethane can be used and are not particularly limited.
Examples of the short-chain diol include aliphatic glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol, and the like. Alkylene oxide low molar adduct (number average molecular weight less than 500); 1,4-bishydroxymethylcyclohexane, alicyclic glycols such as 2-methyl-1,1-cyclohexanedimethanol, and alkylene oxide low molar adducts thereof (Number average molecular weight less than 500); Aromatic glycols such as xylylene glycol and their alkylene oxide low molar adducts (number average molecular weight less than 500); Bisphenols such as bisphenol A, thiobisphenol, sulfone bisphenol and their alkylenes Kishido low molar adduct (number average molecular weight of less than 500); compounds such as alkyl dialkanolamines such as alkyl diethanolamine of C1~C18 thereof. Examples of the polyhydric alcohol compound include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, tris- (2-hydroxyethyl) isocyanurate, 1,1,1-trimethylolethane, 1,1, Examples include 1-trimethylolpropane. These can be used alone or in combination of two or more.
短鎖ジアミンとしては、脂肪族系ポリアミン類、例えば、エチレンジアミン、Ｎ−ヒドロキシエチルエチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン等；脂環式ポリアミン、例えば、４，４−ジアミノジシクロヘキシルメタン、１，４−ジアミノシクロ類ヘキサン、イソホロンジアミン等；ヒドラジン類、例えば、ヒドラジン、カルボジヒドラジド、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド、フタル酸ジヒドラジド等；不飽和基を含むポリアミン類、例えば、ジアリルアミン化合物等が挙げられる。これらは単独で或いは２種類以上を組み合わせて使用することができる。 Examples of the short-chain diamine include aliphatic polyamines such as ethylene diamine, N-hydroxyethyl ethylene diamine, tetramethylene diamine, hexamethylene diamine, and diethylene triamine; alicyclic polyamines such as 4,4-diaminodicyclohexylmethane, 1, 4-diaminocyclos hexane, isophoronediamine, etc .; hydrazines such as hydrazine, carbodihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide, etc .; polyamines containing unsaturated groups such as diallylamine compounds . These can be used alone or in combination of two or more.
高分子ポリオールとしては、例えば、以下のものが挙げられる。
（１）ポリエーテルポリオール、例えば、アルキレンオキシド（エチレンオキシド、プロピレンオキシド、ブチレンオキシド等）及び／又は、複素環式エーテル（テトラヒドロフラン等）を重合又は共重合して得られるもの、具体的にはポリエチレングリコール、ポリプロピレングリコール、ポリエチレングリコール−ポリテトラメチレングリコール（ブロック又はランダム）、ポリテトラメチレンエーテルグリコール、ポリヘキサメチレングリコール等、
Examples of the polymer polyol include the following.
(1) Polyether polyols such as those obtained by polymerizing or copolymerizing alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) and / or heterocyclic ethers (tetrahydrofuran, etc.), specifically polyethylene glycol , Polypropylene glycol, polyethylene glycol-polytetramethylene glycol (block or random), polytetramethylene ether glycol, polyhexamethylene glycol, etc.
（２）ポリエステルポリオール、例えば、脂肪族系ジカルボン酸類（例えば、コハク酸、アジピン酸、セバシン酸、グルタル酸、アゼライン酸等）及び／又は芳香族系ジカルボン酸（例えば、イソフタル酸、テレフタル酸等）と低分子量グリコール類（例えば、エチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、１，４−ブチレングリコール、１，６−ヘキサメチレングリコール、ネオペンチルグリコール、１，４−ビスヒドロキシメチルシクロヘキサン等）とを縮重合したもの、具体的にはポリエチレンアジペートジオール、ポリブチレンアジペートジオール、ポリヘキサメチレンアジペートジオール、ポリネオペンチルアジペートジオール、ポリエチレン／ブチレンアジペートジオール、ポリネオペンチル／ヘキシルアジペートジオール、ポリ−３−メチルペンタンアジペートジオール、ポリブチレンイソフタレートジオール等、 (2) Polyester polyol, for example, aliphatic dicarboxylic acids (for example, succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.) and / or aromatic dicarboxylic acids (for example, isophthalic acid, terephthalic acid, etc.) And low molecular weight glycols (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol, 1,4-bishydroxy Methyl polycyclohexane etc.), specifically polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene / butylene adipate diol, polyneope Chill / hexyl adipate diol, poly-3-methylpentane adipate diol, polybutylene isophthalate diol,
（３）ポリラクトンポリオール、例えば、ポリカプロラクトンジオール又はトリオール、ポリ−３−メチルバレロラクトンジオール等、
（４）ポリカーボネートジオール、例えば、ポリヘキサメチレンカーボネート等、
（５）ポリオレフィンポリオール、例えば、ポリブタジエングリコール、ポリイソプレングリコール又は、その水素化物等、
（６）ポリメタクリレートジオール、例えば、α，ω−ポリメチルメタクリレートジオール、α，ω−ポリブチルメタクリレートジオール等が挙げられる。
これらのポリオールの分子量は特に限定されないが、通常数平均分子量は５００〜２，０００程度である。又、これらのポリオールは単独或いは２種類以上を組み合わせて使用することができる。
(3) Polylactone polyol, such as polycaprolactone diol or triol, poly-3-methylvalerolactone diol,
(4) Polycarbonate diol, such as polyhexamethylene carbonate,
(5) Polyolefin polyol, such as polybutadiene glycol, polyisoprene glycol or hydride thereof,
(6) Polymethacrylate diols, for example, α, ω-polymethyl methacrylate diol, α, ω-polybutyl methacrylate diol, and the like.
The molecular weight of these polyols is not particularly limited, but the number average molecular weight is usually about 500 to 2,000. Moreover, these polyols can be used individually or in combination of 2 or more types.
又、ポリアミンとしては、例えばメチレンジアミン、エチレンジアミン、トリメチレンジアミン、ヘキサメチレンジアミン、オクタメチレンジアミン等の脂肪族ジアミン化合物；フェニレンジアミン、３，３′−ジクロロ−４，４′−ジアミノジフェニルメタン、４，４′−メチレンビス（フェニルアミン）、４，４′−ジアミノジフェニルエーテル、４，４′−ジアミノジフェニルスルホン等の芳香族ジアミン化合物；シクロペンダジアミン、シクロヘキシルジアミン等の脂環式ジアミン化合物等が挙げられる。これら以外にもチオール基、カルボキシル基を持つ活性水素化合物が挙げられる。活性水素含有化合物としては、ジオール化合物、ジアミン化合物が好ましい。 Examples of the polyamine include aliphatic diamine compounds such as methylene diamine, ethylene diamine, trimethylene diamine, hexamethylene diamine, and octamethylene diamine; phenylene diamine, 3,3'-dichloro-4,4'-diaminodiphenyl methane, 4, Examples include aromatic diamine compounds such as 4'-methylenebis (phenylamine), 4,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenylsulfone; and alicyclic diamine compounds such as cyclopentadiamine and cyclohexyldiamine. In addition to these, active hydrogen compounds having a thiol group or a carboxyl group can be mentioned. As the active hydrogen-containing compound, a diol compound and a diamine compound are preferable.
本発明においては使用される、分子中に少なくとも１つの活性水素含有基を有するポリシロキサン化合物（Ｄ）としては、以下の化合物が挙げられる。
（１）アミノ変性ポリシロキサン化合物
(1) Amino-modified polysiloxane compound
（２）エポキシ変性ポリシロキサン化合物
（３）アルコール変性ポリシロキサン化合物
（４）メルカプト変性ポリシロキサン化合物
以上列記した活性水素基を有するポリシロキサン化合物は本発明において使用する好ましい化合物であって本発明はこれらの例示の化合物に限定されるものではない。従って上述の例示の化合物のみならず、その他現在市販されており、市場から容易に入手し得る化合物はいずれも本発明において使用することができる。本発明において特に好ましい化合物は２個の水酸基又はアミノ基を有するポリシロキサン化合物である。 The polysiloxane compounds having an active hydrogen group listed above are preferable compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only the above-exemplified compounds but also any other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention. Particularly preferred compounds in the present invention are polysiloxane compounds having two hydroxyl groups or amino groups.
本発明において使用する分子中に少なくとも１個の活性水素含有基とパーフルオロアルキル基を含有する化合物（Ｅ）としては、例えば、以下の化合物が挙げられる。パーフルオロアルキル基の炭素数は１〜２０程度である。
又、これら以外にも前記のモノアルコールタイプの化合物を特開２００１−３２９０３８号公報に記載の方法でジイソシアネート化合物と反応させ、生成した片末端にイソシアネート基を有する反応生成物とジアルカノールアミンとを反応させて得られる下記の一般式で表されるフッ素含有ジオール等も使用することができる。
（式中のＲfは炭素数が１〜２０のパーフルオロアルキル基であり、Ｍは置換基を有してもよい炭素数が１〜１０のアルキレン基（該基中にＯ、Ｎ又はＳ原子を有してもよい）、置換基を有してもよいアルケニレン基（−ＣＨ＝ＣＨ−（ＣＨ2）n−（ｎは１〜１０））、又は
以上列記した活性水素基を有するフッ素含有化合物は、本発明において使用する好ましい化合物の例示であって、本発明においてはこれらの例示に限定されるものではない。従って、上述の例示の化合物のみならず、その他公知の現在市販されており市場から入手し得る化合物は、いずれも本発明において使用できる。本発明において特に好ましいフッ素含有化合物は、前記例示のアルコールタイプのフッ素含有化合物である。 The fluorine-containing compounds having an active hydrogen group listed above are examples of preferable compounds used in the present invention, and the present invention is not limited to these examples. Accordingly, not only the above-exemplified compounds but also any other known and commercially available compounds can be used in the present invention. Particularly preferred fluorine-containing compounds in the present invention are the alcohol-type fluorine-containing compounds exemplified above.
本発明で使用するポリイソシアネートとしてはジイソシアネート化合物が好ましく、ジイソシアネート化合物としては、従来公知のいずれのものも使用でき特に限定されない。例えば、トルエン−２，４−ジイソシアネート、４−メトキシ−１，３−フェニレンジイソシアネート、４−イソプロピル−１，３−フェニレンジイソシアネート、４−クロル−１，３−フェニレンジイソシアネート、４−ブトキシ−１，３−フェニレンジイソシアネート、２，４−ジイソシアネートジフェニルエーテル、４，４′−メチレンビス（フェニレンイソシアネート）（ＭＤＩ）、ジュリレンジイソシアネート、トリジンジイソシアネート、キシリレンジイソシアネート（ＸＤＩ）、１，５−ナフタレンジイソシアネート、ベンジジンジイソシアネート、ｏ−ニトロベンジジンジイソシアネート、４，４′−ジイソシアネートジベンジル等の芳香族ジイソシアネート； The polyisocyanate used in the present invention is preferably a diisocyanate compound, and any conventionally known diisocyanate compound can be used and is not particularly limited. For example, toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3 -Phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4'-methylenebis (phenylene isocyanate) (MDI), jurylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o -Aromatic diisocyanates such as nitrobenzidine diisocyanate, 4,4'-diisocyanate dibenzyl;
メチレンジイソシアネート、１，４−テトラメチレンジイソシアネート、１，６−ヘキサメチレンジイソシアネート、１，１０−デカメチレンジイソシアネート等の脂肪族ジイソシアネート；１，４−シクロヘキシレンジイソシアネート、４，４−メチレンビス（シクロヘキシルイソシアネート）、１，５−テトラヒドロナフタレンジイソシアネート、イソホロンジイソシアネート、水添ＭＤＩ、水添ＸＤＩ等の脂環式ジイソシアネート等、或いはこれらのジイソシアネート化合物と低分子量のポリオールやポリアミンを末端がイソシアネートとなるように反応させて得られるポリウレタンプレポリマー等も当然使用することができる。 Aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate; 1,4-cyclohexylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), Obtained by reacting 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, alicyclic diisocyanates such as hydrogenated MDI, hydrogenated XDI, etc., or these diisocyanate compounds with low molecular weight polyols and polyamines so that the ends are isocyanates. Naturally, polyurethane prepolymers and the like can also be used.
本発明の親水性官能基含有ポリウレタン樹脂は、無溶剤で合成しても、有機溶剤を用いて合成しても良い。有機溶剤として好ましいのは、例えば、メチルエチルケトン、メチル−ｎ−プロピルケトン、メチルイソブチルケトン、ジエチルケトン、ギ酸メチル、ギ酸エチル、ギ酸プロピル、酢酸メチル、酢酸エチル、酢酸ブチル等が挙げられる。又、アセトン、シクロヘキサン、テトラヒドロフラン、ジオキサン、メタノール、エタノール、イソプロピルアルコール、ブタノール、トルエン、キシレン、ジメチルホルムアミド、ジメチルスルホキシド、パークロルエチレン、トリクロルエチレン、メチルセロソルブ、ブチルセロソルブ、セロソルブアセテート等も使用することができる。 The hydrophilic functional group-containing polyurethane resin of the present invention may be synthesized without a solvent or may be synthesized using an organic solvent. Preferable examples of the organic solvent include methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, butyl acetate and the like. Acetone, cyclohexane, tetrahydrofuran, dioxane, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, dimethylformamide, dimethyl sulfoxide, perchlorethylene, trichloroethylene, methyl cellosolve, butyl cellosolve, cellosolve acetate, etc. can also be used. .
本発明の親水性官能基含有ポリウレタン樹脂を合成する場合には、前記の低分量ポリマー（Ａ）の使用割合は１０〜９９．９重量％、好ましくは３０〜９５重量％、前記の活性水素含有基と水酸基以外の親水性基、好ましくはカルボキシル基を両有する化合物（Ｂ）の使用割合は０．０５〜３０重量％、好ましくは２〜１５重量％、ポリオール及び／又はポリアミン（Ｃ）の使用割合は０〜５０重量％（但しこれらの化合物（Ａ）〜（Ｃ）の合計は１００重量％である。）を用い、これらの化合物と、これらの化合物中の全活性水素とほぼ等モルのジイソシアネート化合物と必要により鎖伸長剤（目的の分子量となる量の）とを反応させる。又、ポリウレタン樹脂中に更にポリシロキサンセグメント及び／又はパーフルオロアルキル基含有セグメントを導入する場合には、上記量の原料成分に加えて１個又は２個の活性水素含有基を有するポリシロキサン化合物（Ｄ）及び／又は１個又は２個の活性水素含有基を有するフッ素含有化合物（Ｅ）を０．１〜８０重量％（但し、該パーフルオロアルキル基含有化合物（Ｅ）を使用しない場合は、該ポリシロキサン化合物（Ｄ）を０．１〜８０重量％、好ましくは０．５〜５０重量％使用し、該ポリシロキサン化合物（Ｄ）を使用しない場合には該パーフルオロアルキル基含有化合物（Ｅ）を０．１〜５０重量％、好ましくは０．５〜３０重量％使用する。）（ジイソシアネート化合物を除く全原料成分（Ａ）〜（Ｅ）の合計は１００重量％である。）を反応させる。 When synthesizing the hydrophilic functional group-containing polyurethane resin of the present invention, the use amount of the low molecular weight polymer (A) is 10 to 99.9% by weight, preferably 30 to 95% by weight, containing the active hydrogen. The proportion of the compound (B) having both a hydrophilic group other than a group and a hydroxyl group, preferably a carboxyl group, is 0.05 to 30% by weight, preferably 2 to 15% by weight, and a polyol and / or polyamine (C) is used. The proportion is 0 to 50% by weight (provided that the total of these compounds (A) to (C) is 100% by weight), and these compounds and the total active hydrogen in these compounds are approximately equimolar. A diisocyanate compound and, if necessary, a chain extender (in an amount to achieve the target molecular weight) are reacted. When a polysiloxane segment and / or a perfluoroalkyl group-containing segment is further introduced into the polyurethane resin, a polysiloxane compound having one or two active hydrogen-containing groups in addition to the above raw material components ( D) and / or 0.1 to 80% by weight of the fluorine-containing compound (E) having one or two active hydrogen-containing groups (provided that the perfluoroalkyl group-containing compound (E) is not used) The polysiloxane compound (D) is used in an amount of 0.1 to 80% by weight, preferably 0.5 to 50% by weight. When the polysiloxane compound (D) is not used, the perfluoroalkyl group-containing compound (E 0.1 to 50% by weight, preferably 0.5 to 30% by weight.) (The total of all the raw material components (A) to (E) excluding the diisocyanate compound is 100 weights) % And a.) Reacting the.
得られる親水性ポリウレタン樹脂の分子量は、重量平均分子量（ＧＰＣで測定、標準ポリスチレン換算）が１０，０００〜５００，０００の範囲が好ましい。又、親水性ポリウレタン樹脂中の親水性官能基の含有量は、０．０５〜３０ｍｅｑ／ｇが好ましく、更に好ましくは０．１〜２５ｍｅｑ／ｇである。０．０５ｍｅｑ／ｇ未満ではポリシロキサンセグメント、パーフルオロアルキル基含有セグメント或いは疎水性低分子量ポリマー鎖の基材表面への配向性が低下し、滑り性や撥水性等が低下する。又、３０ｍｅｑ／ｇを超えるとポリウレタン合成時の反応速度が著しく低下して生産性が悪化する。 As for the molecular weight of the obtained hydrophilic polyurethane resin, the weight average molecular weight (measured by GPC, standard polystyrene conversion) is preferably in the range of 10,000 to 500,000. Moreover, 0.05-30 meq / g is preferable and, as for content of the hydrophilic functional group in hydrophilic polyurethane resin, More preferably, it is 0.1-25 meq / g. If it is less than 0.05 meq / g, the orientation of the polysiloxane segment, the perfluoroalkyl group-containing segment or the hydrophobic low molecular weight polymer chain on the substrate surface is lowered, and slipperiness, water repellency and the like are lowered. On the other hand, if it exceeds 30 meq / g, the reaction rate at the time of polyurethane synthesis is remarkably lowered and the productivity is deteriorated.
上記の原料成分のうち該ポリシロキサン化合物（Ｄ）も該パーフルオロアルキル基含有化合物（Ｅ）も使用しない場合のポリウレタン樹脂の構造式は、下記の一般式（１）で表される。一般式（１）中の上記の化合物（Ａ）〜（Ｃ）から誘導される単位Ａ〜Ｃの含有割合（ａ〜ｃの値）は、ジイソシアネート化合物と反応した上記各化合物（（Ａ）〜（Ｃ））の量から算出される。 The structural formula of the polyurethane resin when neither the polysiloxane compound (D) nor the perfluoroalkyl group-containing compound (E) is used is represented by the following general formula (1). The content ratio (values of ac) of the units A to C derived from the compounds (A) to (C) in the general formula (1) is the above-mentioned respective compounds ((A) to (C)).
全原料成分（（Ａ）〜（Ｅ））が２個の活性水素含有基を有する場合の本発明の親水性ポリウレタン樹脂の構造は、前記の単位（Ａ〜Ｃ）とポリシロキサンセグメント含有単位（Ｄ）又はパーフルオロアルキル基含有セグメント含有単位（Ｅ）がランダムにウレタン結合及び／又はウレア結合で結合した下記の一般式（２）で表される。又、これらのセグメント生成原料が１個の活性水素含有基を有する場合には、親水性ポリウレタン樹脂の構造は、前記の単位（Ａ〜Ｃ）がランダムに前記の結合で結合した分子鎖の末端にポリシロキサンセグメント含有単位（Ｄ′）及び／又はパーフルオロアルキル基含有セグメント含有単位（Ｅ′）が前記の結合で結合した下記の一般式（３）で表される。一般式（２）又は（３）中の単位の含有割合（ａ〜ｅの値）は、ジイソシアネート化合物と反応した上記各化合物（（Ａ）〜（Ｅ））の量から算出される。 The structure of the hydrophilic polyurethane resin of the present invention in the case where all the raw material components ((A) to (E)) have two active hydrogen-containing groups has the above units (A to C) and polysiloxane segment-containing units ( D) or a perfluoroalkyl group-containing segment-containing unit (E) is represented by the following general formula (2) in which the units are randomly bonded by urethane bonds and / or urea bonds. In addition, when these segment generation raw materials have one active hydrogen-containing group, the hydrophilic polyurethane resin has a structure in which the units (A to C) are randomly bonded to the end of the molecular chain by the bond. The polysiloxane segment-containing unit (D ′) and / or the perfluoroalkyl group-containing segment-containing unit (E ′) are represented by the following general formula (3) bonded with the above bond. The content ratio of units in the general formula (2) or (3) (values of a to e) is calculated from the amount of each compound ((A) to (E)) reacted with the diisocyanate compound.
本発明においては上記の原料を用いた水酸基以外の親水性官能基含有ポリウレタン樹脂の製造方法は特に限定されず、従来公知のポリウレタンの製造方法を用いることができる。例えば、好ましい方法は、分子内に活性水素を含まない有機溶剤の存在下、又は不存在下に、前記の低分子量ポリマー、分子鎖中に少なくとも１個の水酸基以外の親水性基と２個の活性水素含有基とが同一分子内に共存する化合物、高分子ポリオール、２個の活性水素含有基を有するポリシロキサン及び／又はパーフルオロアルキル基含有化合物と、ジイソシアネート化合物を、低分子ジオールもしくは低分子ジアミンを鎖伸長剤として、イソシアネート基と活性水素含有官能基との当量比が、通常、１．０となる配合で、ワンショット法、又は多段法により、通常、２０〜１５０℃、好ましくは６０〜１１０℃で、イソシアネート基がほとんどなくなるまで反応させることで本発明のポリウレタン樹脂を得ることができる。
本発明の親水性官能基含有ポリウレタン樹脂は、未架橋状態の使用においても耐汚染性、耐水性、耐磨耗性、耐粘着性、低表面摩擦係数、耐熱ブロッキング性等の性能を発揮するが、架橋剤により架橋構造体とすることで更に耐溶剤性等を付与することができる。
In the present invention, the method for producing a hydrophilic functional group-containing polyurethane resin other than a hydroxyl group using the above raw materials is not particularly limited, and a conventionally known method for producing a polyurethane can be used. For example, a preferred method is that in the presence or absence of an organic solvent containing no active hydrogen in the molecule, the low molecular weight polymer, at least one hydrophilic group other than a hydroxyl group and two A compound in which an active hydrogen-containing group coexists in the same molecule, a high molecular polyol, a polysiloxane having two active hydrogen-containing groups and / or a perfluoroalkyl group-containing compound, a diisocyanate compound, a low molecular diol or a low molecular weight With diamine as a chain extender, the equivalent ratio of isocyanate group to active hydrogen-containing functional group is usually 1.0, and usually 20 to 150 ° C., preferably 60, by the one-shot method or multistage method. The polyurethane resin of the present invention can be obtained by reacting at ˜110 ° C. until almost no isocyanate groups are present.
The hydrophilic functional group-containing polyurethane resin of the present invention exhibits performances such as stain resistance, water resistance, abrasion resistance, adhesion resistance, low surface friction coefficient, heat blocking resistance, etc. even when used in an uncrosslinked state. Further, solvent resistance and the like can be imparted by forming a crosslinked structure with a crosslinking agent.
本発明の親水性ポリウレタン樹脂の架橋方法は、ポリウレタン樹脂中のウレタン基及び／又はカルボキシル基等の親水性官能基の反応性を用いた架橋方法を用いることができる。
ウレタン基を用いて架橋する方法として、ポリイソシアネート架橋剤による架橋が挙げられるが、ポリイソシアネート架橋剤としては、従来から使用されている公知のものが使用でき特に限定されない。例えば、２，４−トルイレンジイソシアネートの二量体、トリフェニルメタントリイソシアネート、トリス−（ｐ−イソシアネートフェニル）チオフォスファイト、多官能芳香族イソシアネート、多官能芳香族脂肪族イソシアネート、多官能脂肪族イソシアネート、ブロック化多官能脂肪族イソシアネート、脂肪酸変性多官能脂肪族イソシアネート、ブロック型ポリイソシアネート、ポリイソシアネートプレポリマー等が挙げられる。
As the crosslinking method of the hydrophilic polyurethane resin of the present invention, a crosslinking method using the reactivity of a hydrophilic functional group such as a urethane group and / or a carboxyl group in the polyurethane resin can be used.
As a method of crosslinking using a urethane group, crosslinking with a polyisocyanate crosslinking agent can be mentioned, but as the polyisocyanate crosslinking agent, conventionally known ones can be used and are not particularly limited. For example, dimer of 2,4-toluylene diisocyanate, triphenylmethane triisocyanate, tris- (p-isocyanatephenyl) thiophosphite, polyfunctional aromatic isocyanate, polyfunctional aromatic aliphatic isocyanate, polyfunctional aliphatic Examples include isocyanates, blocked polyfunctional aliphatic isocyanates, fatty acid-modified polyfunctional aliphatic isocyanates, block-type polyisocyanates, and polyisocyanate prepolymers.
カルボキシル基を用いて架橋する方法として、エポキシ系架橋剤、カルボジイミド系架橋剤、金属錯体系架橋剤等、従来から使用されている公知のものが使用でき特に限定されない。例えば、エポキシ系架橋剤としては、「エピコート」（油化シェルエポキシ社製）等の従来公知の市販されているエポキシ樹脂を使用することができる。又、カルボジイミド系架橋剤としては、「カルボジライト」の商品名（日清紡社製）の市販品を入手して使用することができる。金属錯体系架橋剤としては、チタン有機化合物系、「オルガチックス」の商品名（松本製薬工業社製）で市販されているジルコニウム有機化合物系が入手可能であり、アルミニウム、クロム、コバルト、銅、鉄、ニッケル、バナジウム、亜鉛、インジウム、カルシウム、マグネシウム、マンガン、イットリウム、セリウム、ストロンチウム、パラジウム、バリウム、モリブデニウム、ランタン等の錯体や、「ナーセム」の商品名（日本化学産業社製）で市販のスズのアセチルアセトン錯体を入手して使用できる。 As a method of crosslinking using a carboxyl group, known ones that have been conventionally used such as an epoxy-based crosslinking agent, a carbodiimide-based crosslinking agent, and a metal complex-based crosslinking agent can be used and are not particularly limited. For example, as the epoxy-based crosslinking agent, conventionally known commercially available epoxy resins such as “Epicoat” (manufactured by Yuka Shell Epoxy Co., Ltd.) can be used. Moreover, as a carbodiimide type crosslinking agent, the commercial item of the brand name (made by Nisshinbo) of "carbodilite" can be obtained and used. As the metal complex-based crosslinking agent, titanium organic compound-based, zirconium organic compound-based commercially available under the trade name of “Orgatyx” (manufactured by Matsumoto Pharmaceutical Co., Ltd.) are available, and aluminum, chromium, cobalt, copper, Commercially available under the complex name of iron, nickel, vanadium, zinc, indium, calcium, magnesium, manganese, yttrium, cerium, strontium, palladium, barium, molybdenium, lanthanum, etc., and "Narsem" (Nippon Kagaku Sangyo Co., Ltd.) Tin acetylacetone complexes can be obtained and used.
以下に製造例、実施例及び比較例を挙げて本発明を更に具体的に説明するが、本発明はこれらの例に限定されるものではない。又、以下の文中の「部」は重量部、「％」は重量％を示す。 Hereinafter, the present invention will be described more specifically with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples. In the following text, “parts” represents parts by weight, and “%” represents% by weight.
製造例（含フッ素ジオール）
実施例８で使用する含フッ素ジオール（Ｅ）を特開２０００−３２９０３８号公報に記載の方法で以下のようにして合成した。
撹拌機、還流凝縮器、温度計、窒素ガス導入管を備えた窒素置換した反応容器中で、イソホロンジイソシアネート２２．２部を酢酸エチル５０部に溶解した。得られた溶液を６０℃に加温してよく攪拌しながら、４６．４部の粉末状の２−（パーフルオロオクチル）エタノールを徐々に添加し、添加終了後８０℃で３時間反応させ、パーフルオロオクチル基含有片末端イソシアネート化合物を得た。 次いで、反応容器中でジエタノールアミン１０．５部を酢酸エチル１０部に１０℃以下の温度で攪拌しながら混合、溶解し、この溶液に上記反応混合物を徐々に滴下する。滴下とともに発熱するので、内温が２０℃を超えないように徐々に滴下する。反応の進行とともに不均一溶液は均一となる。滴下終了後、室温（２５℃）で２時間反応を続ける。反応終了後、反応液中にトルエンを加えて反応生成物を析出させ、乾燥して含フッ素ジオール（Ｅ）を得た。
Production example (fluorinated diol)
The fluorine-containing diol (E) used in Example 8 was synthesized by the method described in JP 2000-329038 A as follows.
In a nitrogen-substituted reaction vessel equipped with a stirrer, reflux condenser, thermometer, and nitrogen gas inlet tube, 22.2 parts of isophorone diisocyanate was dissolved in 50 parts of ethyl acetate. While the obtained solution was heated to 60 ° C. and stirred well, 46.4 parts of powdery 2- (perfluorooctyl) ethanol was gradually added, and after completion of the addition, reacted at 80 ° C. for 3 hours, A perfluorooctyl group-containing one-terminal isocyanate compound was obtained. Next, 10.5 parts of diethanolamine is mixed and dissolved in 10 parts of ethyl acetate at a temperature of 10 ° C. or lower in a reaction vessel, and the reaction mixture is gradually added dropwise to this solution. Since it generates heat with the dropping, it is gradually dropped so that the internal temperature does not exceed 20 ° C. As the reaction proceeds, the heterogeneous solution becomes homogeneous. After completion of dropping, the reaction is continued at room temperature (25 ° C.) for 2 hours. After completion of the reaction, toluene was added to the reaction solution to precipitate a reaction product and dried to obtain a fluorinated diol (E).
実施例１〜９及び比較例１〜３
攪拌機、還流冷却管、温度計、窒素吹き込み管、マンホールを備えた反応容器を窒素ガスで置換した後、表１〜３に記載の片末端に２個の活性水素含有基を含有する低分子量ポリマー成分（Ａ）と２個の活性水素含有基と１個のカルボキシル基を両有する成分（カルボン酸ジオール）（Ｂ）、ポリオール成分（Ｃ）、鎖伸長剤（Ｆ）及び溶剤を所定量加え、均一に溶解させ、溶液濃度を３０％に調節した。場合により、さらに２個の活性水素含有基を有するポリシロキサン成分（Ｄ）又は含フッ素ジオール（Ｅ）を所定量加えた。続いてジイソシアネートを所定量（全活性水素含有基と等モルとなる量）加えて８０℃で反応を行い、赤外吸収スペクトルで２，２７０ｃｍ-1の遊離イソシアネート基による吸収が認められなくなるまで反応を行った。ポリウレタンの原料組成、性状等を表１〜３に示す。重量平均分子量はＧＰＣで測定した（標準ポリスチレン換算）。
得られたポリウレタン樹脂は、２，２７０ｃｍ-1の遊離イソシアネート基による吸収は認められず、１，０９０ｃｍ-1に−Ｓｉ−に基づく吸収帯、１，７１５ｃｍ-1にカルボキシル基に基づく吸収帯（親水性基がカルボキシル基の場合）、パーフルオロアルキル基は６６３ｃｍ-1、１２０３ｃｍ-1、１１４９ｃｍ-1の吸収帯から確認された。又、低分子量ポリマーの含有率は、その仕込み量から換算して求めた。パーフルオロアルキル基の含有率は、含フッ素ジオール（Ｅ）に含まれるパーフルオロオクチル基の含有率を仕込み量から求めた。ポリシロキサンの含有率は活性水素含有ポリシロキサン化合物が全てシロキサンとして仕込まれる量から換算して求めた。カルボキシル基の含有率（ｍｅｑ／ｇ）は、活性水素基と親水性基を両有する化合物の仕込み量から換算して求めた。
Examples 1-9 and Comparative Examples 1-3
A low-molecular-weight polymer containing two active hydrogen-containing groups at one end shown in Tables 1 to 3 after substituting a reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen blowing tube and manhole with nitrogen gas Add a predetermined amount of component (A), component having two active hydrogen-containing groups and one carboxyl group (carboxylic acid diol) (B), polyol component (C), chain extender (F) and solvent, The solution was uniformly dissolved and the solution concentration was adjusted to 30%. In some cases, a predetermined amount of polysiloxane component (D) or fluorine-containing diol (E) having two active hydrogen-containing groups was further added. Subsequently, a predetermined amount of diisocyanate (an amount that is equimolar with all active hydrogen-containing groups) is added and the reaction is carried out at 80 ° C., and the reaction is continued until no absorption by free isocyanate groups of 2,270 cm −1 is observed in the infrared absorption spectrum. Went. Tables 1 to 3 show the raw material composition and properties of polyurethane. The weight average molecular weight was measured by GPC (standard polystyrene conversion).
The obtained polyurethane resin, absorption by free isocyanate groups of 2,270Cm -1 is not observed, the absorption band based on -Si- on 1,090Cm -1 absorption band based on the carboxyl group 1,715cm -1 ( when the hydrophilic group is a carboxyl group), perfluoroalkyl groups 663cm -1, 1203cm -1, was confirmed from the absorption band of 1149cm -1. Moreover, the content rate of the low molecular weight polymer was calculated | required in conversion from the preparation amount. The content rate of the perfluoroalkyl group was obtained from the charged amount of the perfluorooctyl group contained in the fluorine-containing diol (E). The content of polysiloxane was determined by conversion from the amount of all active hydrogen-containing polysiloxane compounds charged as siloxane. The carboxyl group content (meq / g) was determined by conversion from the charged amount of the compound having both active hydrogen groups and hydrophilic groups.
（注）
・Ａ−２：Ｒ＝ｎ−ブチル基、平均分子量２，０００、Ｔｇ＝−５４℃
・Ａ−３：Ｒ＝イソブチル基、平均分子量２，０００、Ｔｇ＝−３１℃
・Ａ−４：Ｒ＝２−エチルヘキシル基、平均分子量２，０００、Ｔｇ＝−８５℃
（ｎは上記平均分子量となる整数。）
（Ｂ）：
・Ｂ−１：ジメチロールプロパン酸
・Ｂ−２：ジメチロールブタン酸
（Ｃ）：
・ＰＣＤ：ポリカーボネートジオール（ダイセル化学工業社製、プラクセルＣＤ２２０、平均分子量２，０００）
（Ｄ）：
・Ｄ：ポリシロキサンジオール（信越化学社製、ＫＦ−６００３、平均分子量５，１００）
（Ｅ）
・Ｅ：製造例の含フッ素ジオール
（Ｆ）：
・Ｆ：１，４−ブタンジオール
アノン：シクロヘキサノン
架橋剤：多官能芳香族イソシアネート（住友バイエル社製、スミジュールＬ）
(note)
A-2: R = n-butyl group, average molecular weight 2,000, Tg = −54 ° C.
A-3: R = isobutyl group, average molecular weight 2,000, Tg = −31 ° C.
A-4: R = 2-ethylhexyl group, average molecular weight 2,000, Tg = −85 ° C.
(N is an integer with the above average molecular weight.)
(B):
B-1: dimethylolpropanoic acid B-2: dimethylolbutanoic acid (C):
PCD: Polycarbonate diol (Daicel Chemical Industries, Plaxel CD220, average molecular weight 2,000)
(D):
D: Polysiloxane diol (manufactured by Shin-Etsu Chemical Co., Ltd., KF-6003, average molecular weight 5,100)
(E)
E: Fluorine-containing diol (F) in Production Example:
F: 1,4-butanediolanone: cyclohexanone crosslinking agent: polyfunctional aromatic isocyanate (Sumitomo Bayer, Sumidur L)
各実施例及び比較例で得られた各塗料を、厚さ６μｍのポリエチレンテレフタレートフィルム（東レ製）の表面に、グラビア印刷により乾燥後の厚みが１μｍになるように塗布した後、乾燥機中で溶剤を乾燥させた。実施例８及び比較例３の塗量を用いた場合は、塗布観察後４０℃のオーブンにて７２時間熟成させて塗膜を形成させた。各塗膜について下記の方法で接着性、滑り性、ブリード、熱によるブロッキング性及び撥水性を評価した。結果を表４、５に示す。 Each paint obtained in each Example and Comparative Example was applied to the surface of a 6 μm thick polyethylene terephthalate film (manufactured by Toray) so that the thickness after drying would be 1 μm by gravure printing, and then in a dryer. The solvent was dried. When the coating amounts of Example 8 and Comparative Example 3 were used, a coating film was formed by aging in an oven at 40 ° C. for 72 hours after application observation. Each coating film was evaluated for adhesion, slipperiness, bleed, heat blocking property and water repellency by the following methods. The results are shown in Tables 4 and 5.
・接着性：碁盤目セロテープ剥離試験（クロスカット法）を行なって評価した。
・滑り性：塗膜の滑り性を指触により判定し、滑りのあるものを○、滑らないものを×とした。
・ブリード：塗膜表面へのブリード物の有無を目視にて観察し、ブリードが認められないものを○、ブリードが認められたものを×とした。
・熱によるブロッキング性：塗膜表面に６μｍ厚のＰＥＴフィルムを重ね合わせ、ヒートシーラー（テスター産業社製）にて圧力１ｋｇ／ｃｍ2、温度２３０℃にて圧着を行なって評価した。熱によるブロッキングのないものを○、ブロッキングしたものを×とした。
・撥水性：塗膜表面と水との接触角を接触角計（協和界面科学社製ＣＡ−ＤＴ・Ａ型）で測定し、表面接触角が９０°以上のものを○、９０°未満のものを×とした。
-Adhesiveness: A cross-cut cello tape peeling test (cross cut method) was performed for evaluation.
-Sliding property: The slipping property of the coating film was judged by touch, and the case with slipping was judged as "good" and the case without slipping as "poor".
-Bleed: The presence or absence of a bleed material on the surface of the coating film was visually observed.
Blocking property by heat: A PET film having a thickness of 6 μm was superposed on the surface of the coating film, and evaluation was performed by pressure bonding with a heat sealer (manufactured by Tester Sangyo Co., Ltd.) at a pressure of 1 kg / cm 2 and a temperature of 230 ° C. What did not block by heat was set as (circle), and what blocked was set as x.
Water repellency: Measure the contact angle between the coating surface and water with a contact angle meter (CA-DT • A type manufactured by Kyowa Interface Science Co., Ltd.). The thing was made into x.
Claims (4)
The method for producing a hydrophilic functional group-containing polyurethane resin according to claim 3, wherein a polysiloxane compound having at least one active hydrogen-containing group and / or a perfluoroalkyl group-containing compound is further added to the component and reacted.
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| JP4552133B2 (en) * | 2005-03-30 | 2010-09-29 | 東洋紡績株式会社 | Conductive roll having polyurethane resin as surface layer and electrophotographic apparatus using the same |
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