CN101541886A - 水性热固性组合物 - Google Patents
水性热固性组合物 Download PDFInfo
- Publication number
- CN101541886A CN101541886A CNA2007800420186A CN200780042018A CN101541886A CN 101541886 A CN101541886 A CN 101541886A CN A2007800420186 A CNA2007800420186 A CN A2007800420186A CN 200780042018 A CN200780042018 A CN 200780042018A CN 101541886 A CN101541886 A CN 101541886A
- Authority
- CN
- China
- Prior art keywords
- aminoresin
- urethane resin
- aqueous thermosetting
- thermosetting composition
- alcohol
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 30
- 229920003180 amino resin Polymers 0.000 claims abstract description 63
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 238000009833 condensation Methods 0.000 claims abstract description 5
- 230000005494 condensation Effects 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 2
- 238000004519 manufacturing process Methods 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 25
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 21
- 239000011347 resin Substances 0.000 abstract description 21
- -1 amino compound Chemical class 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 150000003077 polyols Chemical class 0.000 abstract description 4
- 239000012948 isocyanate Substances 0.000 abstract description 3
- 229920005862 polyol Polymers 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 150000002513 isocyanates Chemical class 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000011230 binding agent Substances 0.000 abstract 1
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 230000006866 deterioration Effects 0.000 abstract 1
- 239000000976 ink Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 239000004848 polyfunctional curative Substances 0.000 abstract 1
- 239000013615 primer Substances 0.000 abstract 1
- 239000002987 primer (paints) Substances 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 150000001299 aldehydes Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 5
- 206010018612 Gonorrhoea Diseases 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229960002887 deanol Drugs 0.000 description 4
- 239000012972 dimethylethanolamine Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 3
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 3
- 231100000716 Acceptable daily intake Toxicity 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920003275 CYMEL® 325 Polymers 0.000 description 3
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 3
- 150000001912 cyanamides Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000006166 lysate Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 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 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 241000779819 Syncarpia glomulifera Species 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 125000005574 norbornylene group Chemical group 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 239000001739 pinus spp. Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011027 product recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 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 2
- 229940036248 turpentine Drugs 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-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
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- ADYVCZCQSVYNPQ-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1C(C)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1C(C)C1=CC=CC=C1 ADYVCZCQSVYNPQ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- ZHNUHDYFZUAESO-OUBTZVSYSA-N aminoformaldehyde Chemical compound N[13CH]=O ZHNUHDYFZUAESO-OUBTZVSYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- KTHXBEHDVMTNOH-UHFFFAOYSA-N cyclobutanol Chemical compound OC1CCC1 KTHXBEHDVMTNOH-UHFFFAOYSA-N 0.000 description 1
- QCRFMSUKWRQZEM-UHFFFAOYSA-N cycloheptanol Chemical compound OC1CCCCCC1 QCRFMSUKWRQZEM-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- VAANPXCUKADPPX-UHFFFAOYSA-N formaldehyde;2-methylpropan-1-ol Chemical compound O=C.CC(C)CO VAANPXCUKADPPX-UHFFFAOYSA-N 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 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
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- MKQLBNJQQZRQJU-UHFFFAOYSA-N morpholin-4-amine Chemical compound NN1CCOCC1 MKQLBNJQQZRQJU-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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Abstract
本发明涉及一种含有氨基树脂(A)和聚氨酯树脂(B)的水性热固性组合物,所述氨基树脂(A)是由氨基化合物(a)、醛(b)、醇(c)加成脱水缩合得到的,所述聚氨酯树脂(B)是由异氰酸酯(d)、多元醇(e)及具有2个以上羟基的羟基羧酸(f)聚合得到的。本发明的水性热固性组合物在1个固化剂中含有氨基树脂和聚氨酯树脂,并且能够不相互破坏地维持各自的树脂性能。另外,由于在水中的分散性良好且储存稳定性也优异,所以在各种涂料、油墨、粘合剂、涂布材料、粘合剂、底涂层剂等的应用中有用。
Description
技术领域
本发明涉及一种含有氨基树脂(A)和聚氨酯树脂(B)的水性热固性组合物。
背景技术
目前,作为热固化涂料组合物,通常已知使用氨基甲醛树脂作为交联剂的树脂组合物。近年,从大气污染、环境保护的观点考虑,出于减少涂膜干燥时释放的有机溶剂的目的,向用水即可稀释的涂料的转变的研究逐渐盛行。另外,人们谋求一种水可溶性、且具有高性能的水性热固性组合物。
聚氨酯树脂因其机械物性、对基材的耐磨性、柔软性、耐溶剂性等优异的性质,被广泛用于涂料、油墨、粘合剂、涂布剂、纤维处理剂等。另一方面,氨基树脂因外观特性、耐气候性、机械物性等优异而被用于涂料、油墨、粘合剂、涂布剂、纤维处理剂等。这些发挥了氨基树脂和聚氨酯树脂的优异特性的涂料具有非常高的性能,目前为止分别作为不同的2组分固化剂组合进行配合。
将此2组分形成为1组分时,聚氨酯树脂和氨基树脂由于其相溶性不同,故难以均匀且稳定地储存,因此,根据各用途,必须添加稳定化剂、相溶化剂等第3成分。但是,这些第3成分对各用途中的性能产生影响,聚氨酯树脂、氨基树脂各自本来具有的性能难以呈现。
在解决上述问题时,作为固化性优异、且耐水性、耐碱性、加工性及硬度等也优异的氨基树脂技术,有专利文献1、2。其中记载了一种可水性化的固化剂,即,在氨基树脂的制造过程中配合聚氨酯树脂作为氨基树脂的原料,作为氨基树脂骨架的一部分,聚氨酯树脂被包含在结构中。但是,在上述例子中,由于氨基或羧酸等亲水基作为必须结构被导入聚氨酯树脂骨架末端,因此使耐水性降低,同时作为氨基树脂特征的多核体结构在氨基甲酸酯结构链段被分散,作为氨基树脂本来特征的外观特性或高硬度等难以呈现。并且,聚氨酯树脂仅是为了水性化而使用的,本来优良的聚氨酯树脂的强韧性等不充分。
专利文献1:特开平6-329876
专利文献2:特开平6-239949
发明内容
本发明的目的在于,在以聚氨酯树脂、氨基树脂为必须成分的水性热固性组合物中将目前为止作为2组分固化剂进行使用的相溶性不同的氨基树脂、聚氨酯树脂作为1组分固化剂进行提供。另外,还提供一种涂膜物性、粘合性并且机械物性优异的、适用于各种涂料·涂布剂·粘合剂等的水性热固性组合物及其制造方法。
本发明人等反复进行了各种研究,结果发现了一种含有氨基树脂(A)和聚氨酯树脂(B)的水性热固性组合物,所述氨基树脂(A)是由氨基化合物(a)、醛(b)、醇(c)加成脱水缩合得到的,所述聚氨酯树脂(B)是由异氰酸酯(d)、多元醇(e)及具有2个以上羟基的羟基羧酸(f)聚合得到的。
另外,所述水性热固性组合物,作为多元醇(e),至少含有重均分子量为500以上的多元醇,优选含有重均分子量为500以上的多元醇。
进而,所述水性热固性组合物,聚氨酯树脂(B)的末端官能基团为能够与氨基树脂反应的羟基,且至少1个该羟基与氨基树脂(A)反应。另外,所述水性热固性组合物,氨基树脂(A)被碳原子数1~8的醇(c)烷基醚化。
上述水性热固性组合物的制造方法是使氨基树脂(A)和聚氨酯树脂(B)反应的制造方法。进而,所述水性热固性组合物的制造方法,反应溶剂使用与醇(c)不同种类的醇(C)。另外,所述水性热固性组合物的制造方法,在氨基树脂(A)和聚氨酯树脂(B)反应后,用有机或者无机的碱性化合物(d)中和。
进而,本发明提供一种含有上述水性热固性组合物的涂料·涂布剂·粘合剂。需要说明的是,此处,所谓水性是指“溶于水、或还包含部分未溶物质的状态”。
本发明的水性热固性组合物在1个固化剂中含有氨基树脂和聚氨酯树脂,并且能够不相互破坏地维持各自的树脂性能。另外,由于在水中分散性良好且储存稳定性也优异,所以在各种涂料、油墨、粘合剂、涂布材料、粘合剂、底涂层剂等的用途中有用。
具体实施方式
以下,详细地说明本发明,但以下所述的技术特征的说明是本发明的实施方案的代表例,本发明并不限定于这些内容。
[氨基树脂(A)]
本发明的氨基树脂(A)是由氨基化合物(a)、醛(b)、醇(c)、加成脱水缩合得到的。
氨基化合物(a)
本发明中使用的氨基化合物(a)可以举出尿素、三聚氰胺、苯胍胺或者其它三嗪化合物的氨基化合物。其中,从物性方面考虑,优选三聚氰胺。
醛(b)
本发明中使用的醛(b)可以使用甲醛、乙醛、丙醛、苯甲醛等,但因经济性原因,优选甲醛。
醇(c)
本发明中使用的醇(c)可以使用下式CnH2n+1 OH(8≥n≥1)表示的醇,醇可以为直链,也可以为支链。
其中,从经济性、涂膜性能方面考虑,优选4≥n≥1。
氨基树脂(A)的常用制造方法如下所述。以氨基化合物(a)的摩尔比为1时醛(b)的摩尔比为3~7、醇(c)的摩尔比为4~10的比率,以醇(c)作为反应溶剂使上述原料溶解,进而,以酸作为催化剂,将醇(c)烷基醚化,得到氨基树脂。然后,通过减压蒸馏操作除去部分过量残留的未反应醇(c),调整为规定的不挥发成分。此时,如果醇(c)在常压下的沸点为200℃以上,则减压蒸馏操作中必须的加热导致氨基树脂(A)发生自交联,因此,作为醇(c)的碳原子数优选为8以下。
[聚氨酯树脂(B)]
本发明的聚氨酯树脂是作为异氰酸酯(d)、多元醇(e)及具有2个以上羟基的羟基羧酸(f)的共聚物得到的。
异氰酸酯(d)
本发明中使用的异氰酸酯(d),例如可以举出1,4-丁二异氰酸酯、1,6-己二异氰酸酯、2,4,4-三甲基己二异氰酸酯、2,8-二异氰酸甲酯基己酸酯等脂肪族异氰酸酯类、3-异氰酸甲酯基-3,5,5-三甲基环己基异氰酸酯、甲基环己基-2,4-二异氰酸酯、异佛尔酮二异氰酸酯、降冰片烯二异氰酸酯等脂环族二异氰酸酯类、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯(1,5-naphthenediisocyanate)、二苯基甲基甲烷二异氰酸酯、四烷基二苯基甲烷二异氰酸酯、4,4-二苄基二异氰酸酯、1,3-苯二异氰酸酯等芳香族二异氰酸酯类、氯化二异氰酸酯类、溴化二异氰酸酯类。或者可以使用作为与水的加成物的多异氰酸酯化合物等的1种或者2种以上的混合物。
多元醇(e)
本发明中使用的多元醇(e)可以举出在通常聚氨酯树脂的制造中使用的公知的多元醇类,例如二甘醇、丁二醇、己二醇、新戊二醇、双酚A、环己烷二甲醇、三羟甲基丙烷、丙三醇、季戊四醇、聚乙二醇、聚碳酸酯多元醇、环己烷二甲醇、聚丙二醇、聚酯型多元醇、聚己酸内酯、聚四亚甲基醚二醇、聚硫醚多元醇、聚缩醛多元醇、聚丁二烯多元醇、呋喃二甲醇等的2种或者3种以上的混合物。此时,为了使作为所期待的聚氨酯树脂性能的柔软性和强韧性呈现出来,优选使用1种以上的以聚苯乙烯换算分子量计重均分子量为500以上10000以下的多元醇。上述多元醇类可以根据目的、用途适当地选择,容易地设计硬质、软质等必要的物性。
具有2个以上羟基的羟基羧酸(f)
本发明中使用的具有2个以上羟基的羟基羧酸(f)只要是向聚氨酯树脂分子中支链状地赋予羧酸的物质即可,可以使用任意物质,为了增加聚氨酯树脂中的羧酸含量,优选支链状地具有至少1个羧基的碳原子数3~10的低分子量物质,例如优选2,2-二羟甲基丙酸或2,2-二羟甲基丁酸等。
聚氨酯树脂(B)的常用制造方法如下所述。一边在甲苯等有机溶剂中加热多元醇(e)和具有2个以上羟基的羟基羧酸(f),一边使其溶解,待完全溶解使溶解液的温度降至50℃以下。接下来,为了防止由反应热导致温度过度升高,一边将温度保持在50℃以下,一边经2小时至3小时滴入异氰酸酯(d),得到聚氨酯树脂。此时,多元醇(c)和具有2个以上羟基的羟基羧酸(f)的羟基的摩尔比总计为1时,通过使异氰酸酯(d)具有的异氰酸酯基的摩尔比为0.5~0.9,能够得到羟基位于末端结构的聚氨酯树脂(B)。
此处,作为本发明的聚氨酯树脂制造中使用的溶剂,可以使用通常聚氨酯树脂制造中使用的有机溶剂。例如可以举出甲基乙基酮、甲基异丁基酮、乙酸乙酯、异丙醇、甲苯、二甲苯、乙酸异丁酯、乙酸丁酯、丙酮、二甲基甲酰胺、N-甲基-2-吡咯烷酮、二甘醇二甲醚等。
[水性热固性组合物的制造方法]
本发明的水性热固性组合物的制造方法为,使异氰酸酯(d)、多元醇(e)及具有2个以上羟基的羟基羧酸(f)进行聚氨酯化反应时,制造在聚合物分子两末端具有羟基的聚氨酯树脂(B),进而使其与由氨基化合物(a)、醛(b)、醇(c)加成脱水缩合得到的氨基树脂(A)反应。(以下将此处得到的树脂称为复合化树脂(R))
本发明的氨基树脂(A)和聚氨酯树脂(B)反应时,相对于反应中使用的氨基树脂和聚氨酯树脂的总量100重量份,氨基树脂(A)的使用量为30~97重量份。低于30重量份时,无助于与主剂的固化反应的聚氨酯树脂(B)的末端羟基过剩,耐水性降低。为97重量份以上时,未反应的氨基树脂过剩,反应后的水性化变得困难。优选为50~85重量份。
另一方面,本发明的氨基树脂(A)和聚氨酯树脂(B)反应时,相对于反应中使用的氨基树脂和聚氨酯树脂的总量100重量份,聚氨酯树脂(B)的使用量为3~70重量份的范围。低于3重量份时,所期待的挠性降低,超过70重量份时,导致耐水性、涂膜硬度降低。优选为15~50重量份。
此时,通过将与氨基树脂(A)中所含的作为烷基醚原料的醇(c)不同的醇(C)作为氨基树脂和聚氨酯树脂的反应溶剂,能够高效率地进行反应化。
本发明中在氨基树脂(A)和聚氨酯树脂(B)的反应阶段,作为反应溶剂添加的醇类(C),例如可以举出异丙醇、2-丁基醇、叔丁醇、环丁醇、环戊醇、环己醇、2,3-二甲基-2,3-丁二醇(pinacol)、环庚醇、2-乙基-1-己醇、双丙酮醇等仲醇、叔醇、或者与氨基树脂制造时使用的醇(c)的亲水程度不同的醇类。作为使用量,相对于反应中使用的氨基树脂和聚氨酯树脂的总量100重量份为10~60重量份,少于10重量份时,反应过量地进行,引起粘度增加,为60重量份以上时,其稀释率高,使反应难以进行。较优选为20~40重量份。
进而,根据需要,可以用碱性化合物(d)中和上述复合化树脂(R),作为碱性化合物(d),作为无机碱性化合物,可以举出氢氧化钠、氢氧化钾等碱金属的氢氧化物或者氨,或者作为有机碱性化合物,可以举出以单乙醇胺、二甲基乙醇胺、三乙醇胺等为代表的链烷醇胺类、氨基吗啉等胺类。
实施例
以下,为了更具体地说明本发明,给出实施例、比较例进行说明,但本发明并不限定于这些实施例。
制造例1(氨基树脂A-1)
给出氨基树脂的制造例。向装有温度计、搅拌机、回流冷却管及溶剂副产物回收装置的反应器中加入196份低聚甲醛(含有92%甲醛)、126份三聚氰胺、519份正丁醇,一边搅拌一边加入10%磷酸水溶液,调节反应液的pH至5.0。加热至回流温度,使其溶解。然后加热,将反应液温度保持在90℃继续反应4小时,然后加入三乙基胺,调节体系内的pH至7.0。冷却至70℃,在减压下一边将体系内温度保持在70℃以下一边将过量的正丁醇除去到体系外,使树脂的不挥发成分为70%。所得的氨基树脂是MS相溶性12、气泡粘度Z4的烷基醚化度高的疏水性氨基树脂。
制造例2(氨基树脂A-2)
使用与制造例1相同的装置,改变氨基化合物(a)、醛(b)、醇(c)的量、摩尔比,制造氨基树脂。
氨基树脂A-3
作为比较例,使用作为三聚氰胺类氨基树脂的、日本CytecIndustries Inc.(株)制“CYMEL325”。
以下,A-1、A-2、A-3如表1所示。
[表1]
A-1 | A-2 | A-3 | ||
(a) | 三聚氰胺 | 126 | 126 | - |
(b) | 92%低聚甲醛 | 196 | 163 | - |
(c) | 正丁醇 | 519 | 445 | - |
不挥发成分/% | 70 | 65 | 80 | |
MS相溶性 | 12 | 6 | 1 |
不挥发成分:根据JIS K5407-4-3-1进行测定
MS相溶性:在试验管中取1g氨基树脂清漆,在20℃下滴入矿油精(mineral spirit)至不能读出6号铅字的浊度,测定此时的矿油精滴定量。MS相溶性值高时,氨基树脂为疏水性。
制造例3(聚氨酯树脂B-1)
向装有温度计、搅拌机、冷却管、氮(空气)导入管的2000ml四颈烧瓶中加入40份DMBA、25份NPG、15份PPG、45份甲苯,一边导入氮气一边搅拌,将内温升至110℃,溶解内容物。然后,一边将内温升至135℃一边除去溶剂甲苯,加入75份MEK,降低内温至35度。待内温降低至35℃,一边将内温保持在55℃以下一边经2小时滴入60份TDI,得到聚氨酯树脂。
制造例4~7(聚氨酯树脂B-2~8)
使用与制造例3相同的装置,改变异氰酸酯(d)、多元醇(e)及具有2个以上羟基的羟基羧酸(f)的种类、摩尔比,得到聚氨酯树脂(B-2~8)。
制造例8(聚氨酯树脂B-9)
为了与NCO封端聚氨酯树脂比较,使用相同的装置进行合成。加入二羟甲基丙酸100份、1,6-己二异氰酸酯、MEK,在氮气下将内温升至80℃,反应3小时。然后,冷却至60℃,加入25%氨水溶液,反应1小时,得到聚氨酯树脂。
以下,所得聚氨酯树脂B-1~6如表2所示。
[表2]
B-1 | B-2 | B-3 | B-4 | B-5 | B-6 | B-7 | B-8 | B-9 | ||
(d) | TDIHDINBDI | 60 | 60 | 60 | 60 | 100 | 60 | 60 | 60 | 75 |
(e) | NPCPPG-1PPG-2PCDolPCLDolPTG | 2535 | 2535 | 2535 | 2535 | 2535 | 2535 | 2535 | 2535 | |
(f) | DMPADMBA | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 |
溶剂 | MEK | 75 | 75 | 75 | 75 | 75 | 75 | 75 | 75 | 50 |
NH3 | 11 |
表中简称的含义如下所示。
TDI:甲苯二异氰酸酯
HDI:1,6-己二异氰酸酯
NBDI:降冰片烯二异氰酸酯
NPG:新戊二醇
PPG-1:重均分子量1000的聚丙二醇
PPG-2:重均分子量2000的聚丙二醇
PCDol:重均分子量1000的聚碳酸酯二醇
PCLDol:重均分子量1000的聚己酸内酯二醇
PTG:重均分子量1000的聚亚丁基醚二醇
DMPA:2,2-二羟甲基丙酸
DMBA:2,2-二羟甲基丁酸
NH3:25%氨水溶液
MEK:甲基乙基酮
制造例9~14(氨基树脂和聚氨酯树脂的复合树脂R-1~9)
向装有温度计、搅拌机、回流冷却管及溶剂副产物回收装置的反应器中加入100份制造例1和2中得到的氨基树脂A-1、20份聚氨酯树脂B-1、30份IPA,将内温升至90℃,复合化反应3小时。然后,加入3份N,N-二甲基氨基乙醇,用15份水稀释。在减压下除去多余的有机溶剂,最终得到制造例9的氨基树脂和聚氨酯树脂的复合化树脂(R)。进而,使用相同的反应装置,改变氨基树脂的种类、聚氨酯树脂的种类及醇的种类,得到制造例10~13的复合化树脂(R)。以下,分别将上述制造例中得到的氨基树脂和聚氨酯树脂的复合化树脂(R)依次表示为R-1、R-2、R-3、R_4、R-5、R-6、R-7、R-8、R-9。
以下,所得的复合化树脂R-1~9如表3所示。
[表3]
R-1 | R-2 | R-3 | R-4 | R-5 | R-6 | R-7 | R-8 | R-9 | ||
A | A-1A-2A-3 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
B | B-1B-2B-3B-4B-5B-6B-7B-8 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
C | 异丙醇2-丁醇叔丁醇双丙酮醇 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
二甲基乙醇胺 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | |
水 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | |
水溶性液体的性状 | 外观不挥发成分(%)气泡粘度pH稳定性水稀释性 | 透明55Z7○○ | 透明56Z17.2○○ | 透明59Z1Z26.5○○ | 透明57Z27.1○○ | 透明56Z37.6○○ | 透明60Z27.8○○ | 透明57Z27.5○○ | 透明61Z17.5○○ | 透明59Z1Z27.4○○ |
外观:通过目视进行判定
不挥发成分:根据JIS K5407-4-3-1进行测定
气泡粘度:根据JIS K5400-4-5-1进行测定
稳定性:以室温下三个月后的外观进行判定
○:在分离、透明性方面无变化,×:分离、白浊
水稀释性:○:分散于任意比例的水中,×:白浊、沉淀
比较制造例1~3
作为比较制造例1,采用制造例3的聚氨酯树脂。另外,使用与制造例8~13相同的装置,加入100份“CYMEL 325”、20份聚氨酯树脂B-1、30份双丙酮醇以及15份水,在室温下搅拌,作为比较制造例2。相同地向100份“CYMEL 325”中加入15份水进行搅拌,作为比较制造例3。
比较制造例4
使用与制造例9~14相同的装置,加入126份三聚氰胺、450份甲醛-异丁醇溶液(甲醛40%、异丁醇50%、水10%)、及219份异丁醇,一边搅拌一边缓缓加热,将内温保持在90℃下60分钟。将此三聚氰胺和甲醛的异丁醇溶解液作为A-4。然后,加入50份制造例8中制造的聚氨酯树脂,一边除去共沸的水分一边将内温升至93℃,反应5小时。反应结束后在减压下进行脱溶剂操作,加入丁基溶纤剂,调节至不挥发成分为70%。向另外准备的与制造装置相同的装置中加入100份调节至不挥发成分为70%的树脂,用三乙基胺调节pH7后,在40℃下经2小时滴入60份水,结果形成乳白色的水性液体。再进行减压脱溶剂操作,浓缩不挥发成分至51.0%。以此树脂为比较制造例4。
比较制造例5
使用与比较制造例4相同的装置,加入126份三聚氰胺、130份92%低聚甲醛、20份水、256份正丁醇,一边搅拌一边缓缓地加热,将内温保持在90℃下60分钟。此三聚氰胺和醛的正丁醇溶解液为A-5。然后,加入25份制造例8中制造的聚氨酯树脂,一边除去共沸的水分一边将内温升至93℃,反应4小时。反应结束后用二甲基乙醇胺调节pH至7.5,在减压下进行脱溶剂操作,加入丁基溶纤剂,调节至不挥发成分为70%。在另外准备的与制造装置相同的装置中加入100份将不挥发成分调至70%的树脂,用二甲基乙醇胺调整pH7后,在40℃下经2小时滴入60份水,结果形成乳白色的水性液体。再次进行减压脱溶剂操作,将不挥发成分浓缩至51%。以此树脂为比较制造例5。以上制造例的结果如表4所示。对各树脂的稳定度进行评价的结果如表5所示。
[表4]
外观:通过目视进行判定
不挥发成分:根据JIS K5407-4-3-1测定
气泡粘度:根据JIS K5400-4-5-1测定
稳定性:以室温下三个月后的外观进行判定
○:在分离、透明性方面无变化,×:分离、白浊
水稀释性:○:分散在任意比例的水中,×:白浊、沉淀
[参考制造例]
给出实施例中使用的主剂聚酯树脂的制造例。向装有搅拌机、温度计、回流冷却管、及氮气导入管的四颈烧瓶中加入270份间苯二甲酸、120份己二酸、285份新戊二醇、60份三羟甲基丙烷,在氮气流中加热至230℃,一边将水除去到体系外,一边使其反应约5小时,得到聚酯树脂。用乙二醇单丁基醚稀释此树脂使加热残余量为60%,得到树脂酸值30的聚酯树脂。
使用如上所述得到的氨基树脂和聚氨酯的复合化树脂,与水性聚酯树脂配合,涂料化。利用喷涂器将涂料以膜厚25μm为目标涂布在磷酸锌处理的钢板上,在60℃下凝固30分钟后,在140℃下烧成30分钟。评价结果如表5、表6所示。
[表6]
比较例1 | 比较例2 | 比较例3 | 比较例4 | 比较例5 | ||
复合化树脂 | 比较制造例1比较制造例2比较制造例3比较制造例4比较制造例5 | 25份 | 25份 | 25份 | 25份 | 67份 |
主剂 | 参考实施例 | 100份 | 100份 | 100份 | 100份 | 100份 |
涂膜特性 | 膜厚(μm)铅笔硬度棋盘格密合Du Pont(cm)杯突值(mm)弯曲性伸长率(%)强度(kgf/cm2)耐水溶性(60℃/48Hr)盐喷雾(salt spray)(100Hr) | 23B20/100354.52T32.9250.4×× | 涂料分离,故不能评价 | 252B0/100152.81T8.0410.2×× | 22B100/100253.02T16.0223.4×× | 23H100/100152.52T6.2201.3○× |
<试验方法及判定标准>
膜厚:采用kett制、COATING THICKNESS TESTER(LZ200W)
测定
铅笔硬度:按照JIS K5400-8-4。
棋盘格密合:按照JIS K5400-8-5-2,以胶带剥离后的密合部位的个数进行评价
杯突值(Erichsen):JIS K-5400-8-2
Du Pont:基于JIS K5400-8-3Du Pont式,使用荷重300g、前端1/2英寸R的冲击头,进行测定。
弯曲率:评价涂布板弯曲时的涂膜强度。0T表示未挟持0.3mm厚的板时无裂纹、具有最佳耐弯曲性能。1T为挟持1片0.3mm厚的板时无裂纹。2T表示必须用2片相同的板,弯曲条件变缓。
耐水性:在60℃水中浸渍48小时,取出,观察1小时后的白化状态。
○:无锈、无起泡,×:生锈、起泡
伸长率、强度:从基材上剥离涂膜,形成膜,利用INTESCO Model210型测定。2号哑铃、50mm/min
盐喷雾:在40℃下将5%食盐水雾化,100Hr耐久试验
○:无丝状锈层、无剥落、×:有丝状锈层、剥落
Claims (10)
1、一种水性热固性组合物,含有氨基树脂(A)和聚氨酯树脂(B),所述氨基树脂(A)是由氨基化合物(a)、醛(b)及醇(c)加成脱水缩合得到的,所述聚氨酯树脂(B)是由异氰酸酯(d)、多元醇(e)及具有2个以上羟基的羟基羧酸(f)聚合得到的。
2、如权利要求1所述的水性热固性树脂组合物,其特征在于,作为所述多元醇(e)至少包含重均分子量为500以上的多元醇。
3、如权利要求1或者2所述的水性热固性组合物,其中,聚氨酯树脂(B)的末端官能基团为能够与氨基树脂反应的羟基,并且至少1个所述羟基与氨基树脂(A)反应。
4、如权利要求1~3中任一项所述的水性热固性组合物,其中,氨基树脂(A)被碳原子数1~8的醇(c)烷基醚化。
5、一种权利要求1所述的水性热固性组合物的制造方法,使氨基树脂(A)与聚氨酯树脂(B)至少一部分反应。
6、如权利要求5所述的水性热固性组合物的制造方法,其中,反应溶剂使用与醇(c)不同种类的醇(C)。
7、如权利要求5或者6所述的水性热固性组合物的制造方法,其中,使氨基树脂(A)和聚氨酯树脂(B)至少一部分反应后,用有机或者无机的碱性化合物(d)中和。
8、一种含有权利要求1所述的水性热固性组合物的涂料。
9、一种含有权利要求1所述的水性热固性组合物的涂布剂。
10、一种含有权利要求1所述的水性热固性组合物的粘合剂。
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CN104910787A (zh) * | 2015-07-09 | 2015-09-16 | 邬际杰 | 一种抗腐蚀氨基树脂漆及其制备方法 |
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CN104910787A (zh) * | 2015-07-09 | 2015-09-16 | 邬际杰 | 一种抗腐蚀氨基树脂漆及其制备方法 |
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