AU7258400A - Emulsion resins such as urethane silicone acryl emulsions and production method therefor and dispersions thereof - Google Patents
Emulsion resins such as urethane silicone acryl emulsions and production method therefor and dispersions thereof Download PDFInfo
- Publication number
- AU7258400A AU7258400A AU72584/00A AU7258400A AU7258400A AU 7258400 A AU7258400 A AU 7258400A AU 72584/00 A AU72584/00 A AU 72584/00A AU 7258400 A AU7258400 A AU 7258400A AU 7258400 A AU7258400 A AU 7258400A
- Authority
- AU
- Australia
- Prior art keywords
- compounds
- polymerizable
- vinyl monomers
- react
- production method
- 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.)
- Abandoned
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- 239000000839 emulsion Substances 0.000 title claims description 96
- 239000011347 resin Substances 0.000 title claims description 79
- 229920005989 resin Polymers 0.000 title claims description 79
- -1 acryl Chemical group 0.000 title claims description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 229920001296 polysiloxane Polymers 0.000 title claims description 25
- 239000006185 dispersion Substances 0.000 title claims description 15
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title description 24
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 99
- 239000000178 monomer Substances 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 61
- 229920002554 vinyl polymer Polymers 0.000 claims description 61
- 229920002635 polyurethane Polymers 0.000 claims description 54
- 239000004814 polyurethane Substances 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 29
- 239000000470 constituent Substances 0.000 claims description 24
- 239000012948 isocyanate Substances 0.000 claims description 24
- 230000001804 emulsifying effect Effects 0.000 claims description 21
- 150000004756 silanes Chemical class 0.000 claims description 18
- 150000002513 isocyanates Chemical class 0.000 claims description 17
- 125000000524 functional group Chemical group 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 125000003827 glycol group Chemical group 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011435 rock Substances 0.000 claims description 2
- 101100411639 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) mus-41 gene Proteins 0.000 claims 1
- 101150081777 RAD5 gene Proteins 0.000 claims 1
- 101100411620 Schizosaccharomyces pombe (strain 972 / ATCC 24843) rad15 gene Proteins 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 34
- 238000000576 coating method Methods 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000011109 contamination Methods 0.000 description 17
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 12
- 239000003990 capacitor Substances 0.000 description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- 239000003505 polymerization initiator Substances 0.000 description 10
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 9
- 239000003995 emulsifying agent Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 150000002829 nitrogen Chemical class 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 150000002334 glycols Chemical class 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 4
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 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
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 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 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- OGBWMWKMTUSNKE-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CCCCCC(OC(=O)C(C)=C)OC(=O)C(C)=C OGBWMWKMTUSNKE-UHFFFAOYSA-N 0.000 description 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- UHAMPPWFPNXLIU-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)pentanoic acid Chemical compound CCCC(CO)(CO)C(O)=O UHAMPPWFPNXLIU-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-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
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940095095 2-hydroxyethyl acrylate Drugs 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- QNRSQFWYPSFVPW-UHFFFAOYSA-N 5-(4-cyanobutyldiazenyl)pentanenitrile Chemical compound N#CCCCCN=NCCCCC#N QNRSQFWYPSFVPW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical class OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJBYJZCUFFYSGA-UHFFFAOYSA-N prop-2-enoyl fluoride Chemical compound FC(=O)C=C HJBYJZCUFFYSGA-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical class C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
Description
AUSTRALIA
Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Applicant(s): ROCK PAINT CO., LTD.
Invention Title: EMULSION RESINS SUCH AS URETHANE SILICONE ACRYL EMULSIONS AND PRODUCTION METHOD THEREFOR AND DISPERSIONS THEREOF The following statement is a full description of this invention, including the best method of performing it known to me/us: oooo oo o oo ooooo oo
IN
SPECIFICATION
TITLE OF THE INVENTION Emulsion resins such as urethane silicone acryl emulsions and production method therefor and dispersions thereof s BACKGROUND OF THE INVENTION The present invention relates to urethane acryl emulsion resins, production methods therefore, and dispersions using said resins, and production methods for urethane silicone acryl emulsion resins having the respective characteristic features of urethane, silicone, and acryl. If the to emulsion resins in accordance with the present invention is used as resins for use in water dispersion such as water coatings, its coatings may possess improved weather resistance, contamination resistance, chemical resistance, etc. They are usable as different kinds of dispersions such as paints, coating agents, etc.
Referring to the methods of preparing water resins is known a urethane acryl emulsion resin, which urethane resins and acryl resins have been chemically combined with each other, and which has been improved in the stability of emulsion and the transparency of coating which is liable to make an issue with the so-called blending system (Patent Application Laid Open 2. No.2-86610). Furthermore, the emulsion resin was disclosed that has the carbonyl group and hydrazide group as contained in ketones or aldehydes, which have been built therein as a crosslinker, and a high solvent resistance due to the crosslinking performed after the formation of coatings (Patent Application Laid Open No.7-233347). One of the examples is a urethane 1.5 acryl emulsion resin obtained by water-dispersing self-emulsifying urethane resins beforehand in the reaction vessel, and dripping emulsions into which polymerizable vinyl monomers has been water-emulsified together with initiators into said reaction vessel. There is a method of forming crosslinking coatings by providing said urethane acryl emulsion resins with Ao the carbonyl and hydrazide groups as in Ketone or aldehyde. Additionally, a method is known of emulsion polymerizing silane compounds having the .polymerizable vinyl group with polymerizable vinyl monomers for improvement of the weather resistance and toughness (Patent Application Laid Open No.11-1233 2 However, said methods often essentially need the use of emulsifying agents for the purpose of dispersing polymerizable vinyl 2 monomers or reactive silane compounds in water, preventing contamination of reaction device, and improving the stability of emulsion resins obtained.
As a result, coatings obtained from these resins may not be provided with the desired weather resistance and contamination resistance because emulsifying agents are interposed between emulsion particles. An example of the urethane acryl emulsion resins using no emulsifying agent has been reported (Patent Application Laid Open No.6-287259), in which emulsion resins, the amount of acrylic components which can be formulated is small, and sometimes, such a resin as the resin intended for coating is difficult to to design.
On the other hand, for the application, the coatings for use in the buildings, and in particular the outer walls are needed to be maintained unspoiled in the appearance. Water acryl silicone coatings or water acryl fluorine coatings which are excellent in weather resistance and CS contamination resistance are in use from the view point of environmental contamination and health protection of painting workers.
For example, in the event of water acrylic silicone, its functions of weather resistance and contamination resistance are expressed by a high energy in siloxane bond and the chemical reaction and hydrophilic nature that the silanol group has.
However, the fact is that silicone constituents which have been introduced in order to provide the functions of weather resistance and contamination resistance may crosslink to each other to a high degree in the emulsion particles, and the fusion and cross-linking of the emulsion :"particles become insufficient, whereby flagile and easily breakable coatings are formed, and not only the weather resistance and contamination resistance but also the performance of coatings, all of which are to be fully expected, are not obtainable.
In this view, the present invention is intended to provide emulsion resins i 3c which may form coatings having a high weather resistance, contamination resistance, toughness, and flexibility and methods of producing same.
Particularly, the object of the present invention is to provide methods of producing emulsion resins of urethane silicone acryl, wherein no emulsifying agent is necessitated, no retension and elimination of solvent during the production process are necessary, and the production process can be simplified, and besides the obtained emulsion resins are very highly stable.
1 fl 3 BRIEF SUMMARY OF THE INVENTION Having studied diligently in view of said tasks, the inventors of the present invention have completed the present invention by the following processes, wherein emulsion resins which are very stable in polymerization, and in which a small amount of agglomerates have been formed, and the rate of residues of unreacted monomers is low may be obtained by emulsion polymerizing polyurethane vinyl compounds having the emulsifying ability as reactive polyurethane macromonomers with polymerizable vinyl monomers in water, or more desirably, by emulsion polymerizing the 1o reactive polyurethane macromonomers with a mixture of polymerizable vinyl monomers and reactive silane compounds in water, and the obtained emulsion resins have been determined to show the natures that are good in the mechanical stability and shelf stability. Also the present invention was completed by finding out that the coatings formed with the present emulsion resins possess excellent physical properties necessary for coating binders, such as contamination resistance, weather resistance, and chemical resistance, etc.
The first invention in accordance with claim 1 provides a production method for emulsion resins characterised in that it comprises a first process .20o of allowing glycolic constituents having two hydroxy groups and at least one hydrophilic group contained in one molecule and polymerizable vinyl monomers having the functional group that may react with isocyanate to 'i react with isocyanate compounds to obtain polymerizable polyurethane vinyl compounds having the emulsifying ability, and a second process of ZS emulsifying said polymerizable polyurethane vinyl compounds and polymerizable vinyl monomers by means of the emulsifying ability of said polymerizable polyurethane vinyl compounds to polymerize both the compounds in water.
Said production method is intended to emulsifying said polymerizable ,30 polyurethane vinyl compounds themselves and polymerizable vinyl monomers using the excellent emulsifying ability of the polymerizable polyurethane vinyl compounds so as to polymerize both the compounds in water. Any other emulsifying agent is not needed essentially. As a result, no emulsifying agent such as surface-active agents is substantially interposed S" between emulsion particles. Emulsion resins thus obtained are good in stability to ensure that the weather resistance and contamination resistance
'S
of resin coatings will be improved. And said production avoids the necessity of retention and removal of solvent so that procedure steps can be simplified.
The glycolic constituents involving hydrophilic groups are essential in that it may furnish polymerizable polyurethane vinyl compounds with the emulsifying ability. Likewise, the glycolic constituents can be used in conjunction with glycolic constituents wanting hydrophilic groups.
The second invention in accordance with claim 2 provides the production method for the emulsion resin as defined in claim 1 characterised in that the second process includes the following steps.
That is, the second process comprises a step of obtaining any one of a non-aqueous mixture of polymerizable polyurethane vinyl compounds (4) having the emulsifying ability and polymerizable vinyl monomers which have been blended beforehand under the condition of non-aqueous system; and a non-aqueous mixture of polymerizable polyurethane vinyl compounds Is having the emulsifying ability, polymerizable vinyl monomers and silane compounds having the reactive functional group in at least any one of the end and side chain which have been blended in advance under the condition of non-aqueous system, and a step of polymerizing the obtained non-aqueous mixture in water.
4 In many conventional production methods for emulsion resins, it was i" customary for polymerizable vinyl monomers to be added to polymerizable polyurethane vinyl compounds which had been emulsified by emulsifying agents. With the second invention according to claim 2, .i however, the compositions of the non-aqueous mixture are emulsified by the emulsifying ability of the polymerizable polyurethane vinyl compound and the blending operation is performed in advance under the condition of non-aqueous system, so that in the event of the emulsification of nonaqueous mixture, the reactive silane compounds become incorporated into the polymerizable polyurethane vinyl compounds immediately. This makes it possible to instantly create a core/shell-typed double structure in which unstable substances and water may be prevented from getting in contact with each other. And besides, in the present invention, the core/shell-typed double structure is not a mere plain one, wherein polymerization reaction may occur mutually among said substances 3" so that emulsions in which said substances are strongly combined with each other may be obtained.
The third invention in accordance with claim 3 provides the production 'I 1 method for emulsion resins as defined in claim 1 or 2 characterised in that at least one spieces of said polymerizable vinyl monomers is polymerizable silane compound. In addition to said method of introducing silane as reactive silane compound the introduction method for silane 3 that can be used is a method of introducing silane by using polymerizable vinyl monomers having the silyl group, one of the polymerizable vinyl monomers The fourth invention in accordance with claim 4 provides the production method for emulsion resins as defined in any one of claims 1 to 3 oa characterised in that said glycolic constituent having two hydroxy groups and at least one hydrophilic group contained in one molecule is at least one spieces selected from the group consisting of a glycolic constituent whose hydrophilic group is of an ionic type which may bring about hydrophilic nature by subsequent neutralization and a glycolic constituent whose 1S hydrophilic group is of a nonionic type.
The fifth invention in accordance with claim 5 provides the production method for emulsion resins as defined in any one of claim 1 to 4 characterised in that the glycolic constutuents having two hydroxy groups and at least one hydrophilic group contained in one molecule and the 1. glycol group free of hydrophilic group are used together.
The sixth invention in accordance with claim 6 provides a production method for emulsion resins as defined in any one of claims 1 to characterised in that said polymerizable polyurethane vinyl compounds (4) having the emulsifying ability is polymerizable polyurethane vinyl S compound having at least one molecular polymerizable vinyl monomer contained in one molecule of the polyurethane compound as obtained by allowing said glycolic constituent to react with diisocyanate compound in the range of OH group/NCO group 1.0 1.2 1.0 2.0 and then, allowing polyurethane compounds of terminal isocyanate thus obtained to 3. o react with polymerizable vinyl monomers having the functional group which can react with isocyanate. Said polymerizable polyurethane vinyl compounds may be polymerized with polymerizable vinyl monomers in water as the reactive urethane micromonomers.
The seventh invention in accordance with claim 7 provides the production method for emulsion resins as defined in any one of claims 2 to 6 characterized in that the weight ratio of the total of the polymerizable vinyl monomers and reactive silane compounds to the polymerizable 'I 9.
polyurethane vinyl compounds is 100 to 2000 part by weight to 100 part by weight, and the weight ratio of the polymerizable vinyl monomer to the silicone compound having the functional group formed at any one of the end and the side chain ranges from 50 50 to 100 0.
The eighth invention in accordance with claim 8 provides emulsion resins synthesized by permitting the polymerizable polyurethane vinyl compounds having the emulsifying ability as obtained by allowing the glycolic constituents having two hydroxy groups and at least one hydrophilic group contained in one molecule and the polymerizable vinyl monomers (2) o0 having the functional group which may react with isocyanate to react with the isocyanate compounds to polymerize with polymerizable vinyl monomers in water.
The ninth invention in accordance with claim 9 provides emulsion resin dispersions consisting of the emulsion resins and water solvent in which it is \S dispersed. That is, the ninth invention in accordance with claim 9 provides dispersions for use in water paints, coating agents or adhesives containing the emulsion resins as defined in claim 8 as the base.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Zo The production process of emulsion resins in accordance with the present invention comprises a process (thereafter referred to as the first process) of synthesizing polymerizable polyurethane vinyl compounds and a process (thereafter referred to as the second process) of polymerizing said polymerizable polyurethanevinyl compounds with polymerizable vinyl 55 monomers or a mixture of polymerizable vinyl monomers and reactive silane compounds in water.
The first process is intended to produce polymerizable polyurethane vinyl compounds by allowing glycolic constiutents having two hydroxy groups and at least one hydrophilic group contained in one molecule and .i 3oS polymerizable vinyl monomers having the functional group which may react with isocyanate to react with isocyanate compounds At this time, it is desirable to obtain polymerizable polyurethane vinyl compounds with at least one molecule of polymerizable vinyl monomer contained in one molecule of the polyurethane compound by steps of making 3s said glycolic constituents react with diisocyanate compounds in the range of OH group/NCO group 1.0:1.2 1.0:2.0 to obtain polyurethane compounds of terminal isocyanate, and then allowing the polyurethane I 7 compounds thus obtained of terminal isocyanate to react with polymerizable vinyl monomers having the functional group which may react with isocyanate.
Specifically, for example, a process is arranged such that hydrophilic glycol such as glycol, polyethylene glycol having carboxy group, sulfonic acid group, tertiary amino group is made to react with diisocyanate compounds and then single-functional compounds which may react with polymerizable vinyl monomers having the functional group that may react with isocyanate, and isocyanates such as butanol are used to allow the glycols to react diisocyanate compounds until the isocyanate groups completely disappear, thus resulting in synthesis of the polymerizable polyurethane vinyl compounds Additionally, the polymerizable polyurethane vinyl compounds can also be synthesized by reaction of isocyanate compounds having the polymerizable vinyl group with said glycol In the event of the reaction through isocyante into urethane may be used known catalyst for use in preparation of urethane such as dibutyltindilaurate or dioctyltindilaurate, if necessary. If obtained polymeric polyurethane vinyl compounds are so high in viscosity that they are inferior in workability, the polymerizable vinyl monomer that will not virtually react with isocyanate may be added as reactive diluent. However, the present invention is not limited to these processes, and may be embodied by means of other methods.
Next, the glycol having two hydroxy group and at least one hydrophilic group contained in one molecule for use in the first process will s be described. This specific glycol to be used has ionic or nonionic groups.
The hydrophilic group is an ionic group which will bring about hydrophilic nature through neutralization. Examples of the glycol with ionic group are glycol having the carboxylic group, sulfonic acid group or tertiary amino group, specifically, 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic .i 3o acid, 2,2-dimethylol butyric acid, 2,2-dimethylol valerianic acid, 1,4butanediol-2-sodium sulfonate, N-methyldiethanolamin, etc. Glycol with carboxy group is preferable in particular. The group such as polyoxyethylene can be enumerated as an example of the nonionic hydrophilic group.
Examples of the glycols having nonionic hydrophilic group are polyethylene 3s glycols such as tetroethylene glycols, pentaethylene glycols, etc. whose preferable molecular weight is under 1000. They may be used separately or collectively except that alkali-reactive group can not be used together with amino group.
The glycol to be used in the first step can be used especially with glycols free of ionic or nonionic hydrophilic group. Examples of such glycols are ethylene glycol, propyelene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4s cyclohexanedimethanol, polypropylene glycol, polytetramethylene glycol, polycaprolactondiol, condensate produced by union of ethylene glycol with adipic acid, condensate produced by union of neopenthyl glycol and adipic acid, etc.
Examples of the polymerizable vinyl monomers having the functional to group which may react with isocyanate and being used in the first process are 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2hydroxyethyl acrylate, 4-hydroxybutyl acrylate, polycaprolacton modified methacrylate, etc.
Examples of usable single-functional compounds which may react with is isocyanate as aforementioned butanol etc. are mononol components such as methanol, ethanol, propanol, 2-propanol, isobutanol, hexysanol, benzyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; monoamine components such as ethylamine, propylamine, butylamine, p diethylamine, dipropylamine, dibutylamine, 7 -aminopropyl trimethoxy silane, 7 -aminopropyl ethoxy silane, etc. Even if there exist one or more groups that can react with isocyanate, no chain extension does not occur virtually, and constituents which may act as a stopper is also usable.
.i Hydroxyacetic acid, ethanolamine, diethanolamine, etc. can be enumerated 2 by way of example. Referring to diol constituents such as ethylene glycol, diethylene glycol, 1,4-butadiol, 1,6-hexanediol, propylene glycol, dipropylene glycol, etc., it is possible that they are allowed to perform chemical reaction under the condition that the ratio of NCO to OH is one to more than two, where too many OH group exists. These constituents that can react with So isocyanate as set forth may be used separately or collectively.
Moreover, the diisocyanate used in the first process involves aromatic series, aliphatic series, and alicyclic diisocyanate, more speficifically, 2,4tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylene diisocyanate, a a a a '-tetramethyl xylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, etc.
The second process is a process of emulsion polymerizing in water a mixture of the polymerizable polyurethane vinyl compounds having the emulsifying ability as synthesized in said first process as a reactive urethane macromonomer and polymerizable vinyl monomers or a mixture of said polymerizable vinyl monomers and reactive silane compounds so as to obtain the intended emulsion resins.
Examples of polymerized vinyl monomers that can be used in the second process are methacrylate ester group, ester group of their acrylic acids or amide group such as methyl methacrylate, ethyl methacrylate, 2hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, propyl o methacrylate, butyl methacrylate, hexyl methacrylate, siclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate etc.; styrene, vinyltoluene, vinyl acetate, vinyl propionate,etc., and compounds having two or more polymerizable vinyl groups contained in one molecule thereof such as ethylene glycol dimethacrylate, 1,4-butane dioldimethacrylate, 1,6is hexane dioldimethacrylate, compounds having over three vinyl groups contained in one molecule thereof like methacrylic acids or ester acrylate like ester acrylate such as ester acrylate, divinylbenzene, trimethylolethane, trimethylolpropane, pentaerythritol, and polymerizable vinyl monomers having the silyl group such as 7 -methacryloyl propyltrimethoxysilane, 7 .o methacryloyl propylmethyl dimethoxysilane, polydimethylsiloxane modified vinyl compounds etc., can be also used.
The reactive silane compound used in the second process is the alkoxysilane group free of polymerizable vinyl group, such as reactive silanes having the combination of carbon and silicon like tetramethoxysilane, tetraethoxysilane, and oligomers of these compounds, methyltrimethoxysilane, methyltriethoxysilane.
Priparatory to the second process for emulsion polymerization, the aforementioned polymerizable vinyl monomers or polymerizable vinyl monomers and reactive silane compounds are held mixed with the 3t polymerizable polyurethane vinyl compounds in non-aqueous system. In particular, in case of the hydrolyzable silane compounds, said mixing in non-aqueous system is preferable in order to avoid direct touch of these compounds with water as much as possible at any subsequent emulsion polymerization process. This specific mixing method may decrease excessive hydrolysis and combination of the hydrolyzable silane in the emulsion polymerization process and stain of the reaction device which may be caused by the combined silane. It is assumed that such an effect is attributed to the \0 arrangement of said mixing method such that the polymerizable vinyl monomers or the polymerizable vinyl monomers and reactive silane compounds is (are) mixed with the polymerizable polyurethane vinyl compounds having the emulsifiable ability in advance in non-aqueous F system, and such a non-aqueous mixture is introduced into water for emulsification, where the emulsified elements will instantly grow into a core/shell-typed double structure which contains hydrolyzable silanes formed at the core side, and polymerizable polyurethane vinyl compounds having the emulsifiable ability formed at the shell side, thereby to improving the stability of the core constiutents in the water. Moreover, prior to emulsion polymerization of said mixture as produced in non-aqueous system, said mixture may be dispersed in water so as to adjust emulsificatfion beforehand.
However, if the polymerizable polyurethane vinyl compound having is the emulsifiable ability is of an ionic type, it is necessary to neutralize it before use. When the ionic species is carboxy group or sulfonic group, examples of such a type of the polyurethane vinyl compound are amine compounds such as triethylamine, trimethylamine, N-methyl morpholine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine; -o ammonia; or sodium hydroxide, potassium hydroxide as inorganic base.
Highly volatile bases are preferable in terms of the aspect of water S"resistance of paint films. If the ionic species is amine, said compound (4) includes acetic acid, propionic acid, hydrochloric acid, etc. The neutralization method based on neutralizers involves, for example, a method s of adding said compounds direct to said mixture produced in non-aqueous system (a mixture of polymerizable polyurethane vinyl compounds (4) having the emulsifiable ability and polymerizable vinyl monomers or a mixture of said compounds said monomers and reactive silane compounds and a method of emulsifying said mixture produced in non- .i aqueous system after addition of neutralizer to water.
For the purpose of adjusting emulsion resins such as urethane silicone acryl emulsion using said dispersed solution, polymerizable vinyl monomers and reactive silane compounds are added to the dispersed solution, and the reslutant is adjusted for prior emulsion by the use of a homogenizer.
Then, the adjusted substance is dripped into a flask containing water and polymerization initiator, in which it may undergo polymerization.
Preferably, the ratio of polymerizable polyurethane vinyl compounds (4)
S
II
having the emulsifiable ability to polymerizable vinyl monomers reactive silane compounds is 100 100 100 2000, the ratio of to is 50 50 100 0, and for easy dispersion in water, the ratio of to is 100 500 100 1000.
Both water-soluble polymerization initiator and oil polymerization initiator may be used as the polymerization initiator. It is preferable that the amount of polymerization initiator to the weight of polymerizable vinyl monomers be 0.2% to When less than the polymerizable vinyl monomers may remain unreacted, and if the percentage exceeds said range, to no emulsion resin that is excellent in shelf stability may be obtained.
As usable polymerization initiators are there azo-system polymerization initiator such as azobisisobutyronitrile, azobisvaleronitrile; peroxides such as benzoyl peroxide, t-butyl peroxy-2-ethyl hexnoate, di-2ethylhexylperoxydincarbonate, ammonium persulfate, sodium persulfate, potassium persulfate, etc. These compounds may be used in conjunction with reducing agents as redox polymerization initiators. Examples of the reducing agents are ascorbic acid, sodium ascorbate, sorbic acid, methasodium bisulfite, methapotassium bisulfite, ferric chloride, Rongalite, etc.
20 The water-soluble polymerization initiator is taken into solution in water of a reaction vessel before use or dripping, or dissolved in water dispersion of vinyl monomer. The oil polymerization initiator may be used which has been dissolved into vinyl monomer.
The polymerization temperature for emulsion resin is preferably less than 100' C, and with the redox system, polymerization can be executed at a temperature in the vicinity of 500 C.
The emulsion resin in accordance with the present invention may be prepared by blending additives, assistants, or other resinous constituents, as needed, as well as aforementioned constituents. The emulsion resin as 3a obtained is dispersed in aqueous solvent (water or water and water-soluble solvent), and then, compounded with constituents as pigment, dye, aggregate, or different kinds of additives depending on the intended use, whereby it may be utilised as aqueous dispersion. Such an aqueous dispersion can be used as coating agents or adhesives, and in conjunction with other resins or aqueous dispersions.
EXAMPLES
Now the present invention will be described with reference to the following examples, but the invention is not limited to the examples being illustrated.
EXAMPLE 1 [ADJUSTMENT METHOD FOR EMULSIFIABLE POLYMERIZABLE POLYURETHANE VINYL COMPOUND s Dimethylol propionic acid (50.0g), butylene adipate of 500 molecular weight (184.0g), isophorone diisocyanate (247.0g), and dibutyltinlaurate (0.05g) are put into a 2L flask equipped with a nitrogen gas introduction tube, a thermometer, a capacitor, and an agitator, and these compounds were allowed to react at an internal temperature of 800 C under the io atmosphere of nitrogen for four hours. Furthermore, they were heated and agitated for one hour, and then, it was determined through IR spectrum that no absorption of NCO having a wavelength of 2240 cm'' had been decreased.
2-hydroxyethyl metacrylate (47.75g) and butanol (27.25g) were added to the resultant, and the mixture was allowed to react for three hours. After it was Is determined by IR spectrum that the absorption of NCO having a wavelength of 2240cm- had disappeared, methyl methacrylate (556.05g) was added and dissolved uniformly until polymerizable polyurethane vinyl compounds (4)-1 having the emulsifiable ability and 50% methylmethacrylate have been obtained.
.6 EXAMPLE 2 [ADJUSTMENT METHOD FOR EMULSIFIABLE :'POLYMERIZABLE POLYURETHANE VINYL COMPOUND Dimethylol propionic acid (50.0g), 1,6-hexandiol (43.4g), isophorone '*diisocyanate (247.0g), and dibutyltindilaurate (0.05g) were put into a 2L flask equipped with a nitrogen gas introduction tube, a thermometer, a 2s capacitor, and an agitator, and these compounds were allowed to react at an internal temperature of 80' C under the nitrogen atmosphere for four hours, followed by heating and agitation processes for one hour, and it was determined through IR spectrum that no absorption of NCO having a wavelength of 2240cm 1 had decreased. Then, 2-hydroxyethyl methacrylate so (47.75g) and butanol (27.25g) were introduced and made to react for three hours. After the determination by IR spectrum of disappearance of absorption of NCO having a wavelength of 2240cm- 1 methyl methacrylate (415.45g) was added and dissolved uniformly until polymerizable polyurethane vinyl compounds having the emulsifiable ability and 3S methyl methacrylate have been obtained.
COMPARATIVE EXAMPLE 1 [ADJUSTMENT METHOD FOR EMULSIFIABLE POLYMERIZABLE POLYURETHANE COMPOUND V «1 (comparison)-1] Dimethylol propionic acid (50.0g), 1,6-hexanediol (43.4g), isophorone diisocyanate (247.0g), and dibutyltinlaurate (0.05g) were put into a 2L flask equipped with a nitrogen gas introduction tube, a thermometer, a capacitor, and an agitator, and allowed to react at an internal temperature of 80 C under the nitrogen atmosphere for four hours, followed by heating and agitation processes for one hour, and then it was determined by IR spectrum that no absorption of NCO having a wavelength of 2240cm- 1 had decreased.
Then, butanol (54.5g) was added and made to react for three hours. After the O) determination by IR spectrum of disappearance of the absorption of NCO having a wavelength of 2240cm 1 methyl methacrylate (394.95g) was added and dissolved uniformly until polymerizable polyurethane compounds having the emulsifiable ability and 50% methyl methacrylate (comparison)- 1 have been obtained.
EXAMPLE 1-1 [ADJUSTMENT METHOD FOR URETHANE
ACRYL
EMULSION RESIN USING Demineralized water (250.0g) was put into a 2L flask equipped with a nitrogen gas introduction tube, a thermometer, a capacitor, and an agitator, and heated at a temperature of 80 C for replacement of nitrogen.
o Demineralized water (301.4g), trimethylamine and then a mixture of (212.5g), styrene (80.0g), 2-ethylhexyl acrilate (50.0g), and n-butyl methacrylate (55.5g) were put into a 1L flask so as to adjust emulsion of urethane acryl monomers. The resultant and demineralized water (40.0g) in which sodium persulfate (2.0g) had been dissolved were dripped with the same speed into the reaction flask over four hours. Then, the dripped compositions were allowed to age at 80° C for three hours until the urethane acrylic emulsion resins had been obtained.
EXAMPLE 1-2 [ADJUSTMENT METHOD FOR URETHANE SILICONE ACRYL EMULSION RESIN USING o Bo Demineralized water (250.0g) is put into a 2L flask equipped with a nitrogent gas introduction tube, a thermometer, a capacitor, and an agitator, and heated at a temperature of 80 C for substitution of nitrogen.
Additionally, a mixture of demineralized water (301.4g), triethylamine (8.6g), and then, (212.5g), stylene (80.0g), 2-ethylhexyl acrylate (30.0g), nbutyl methacrylate (35.5g), 7 -methacryloilpropyl trimethoxysilane (20.0g), and methyltrimethoxysilane (20.0g) was put into a 1L flask for adjustment of emulsion of urethane silicone acryl monomers. The resultant and demineralized water (40.0g) in which sodium persulfate (2.0g) had been dissolved were dripped at the same speed into a reaction flask over four hours. And then, the dripped compositions were allowed to age at 80' C for three hours until urethane silicone acryl emulsion resins had been obtained.
EXAMPLE 2-1 [ADJUSTMENT METHOD FOR URETHANE ACRYL EMULSION RESIN USING Demineralized water (250.0g) was put into a 2L flask equipped with a nitrogen gas introduction tube, a thermometer, a capacitor, and an agitator, o1 and heated at a temperature of 80° C for substitution of nitrogen, and additionally, a mixture of demineralized water (301.4g), triethylamine (8.6g), and then, (158.7g), stylene (80.0g), 2-ethylhexyl methacrylate (60.0g), and n-butyl methacrylate (99.3g) was put into a 1L flask for adjustment of emulsion of urethane acryl monomers. The resultant and demineralized water (40.0g) in which sodium persulfate (2.0g) had been dissolved were dripped at the same speed into a reaction flask over four hours. And then, the dripped compositions were allowed to age at 800 C for three hours until urethane acryl emulsion resin had been obtained.
EXAMPLE 2-2 [ADJUSTMENT METHOD FOR URETHANE SILICONE 20 ACRYL EMULSION RESIN USING Demineralized water (250.0g) was put into a 2L flask equipped with a nitrogen gas introduction tube, a thermometer, a capacitor, and an agitator, and heated at a temperature of 80" C for substitution of nitrogen, and additionally, a mixture of demineralized water (301.4g), triethylamine (8.6g), and then, (158.7g), stylene (80.0g), 2-ethylhexyl acrylate (40.0g), nbutyl methacrylate (79.3g), 7 -methacryloil propyltrimethoxysilane (20.0g), and methyl trimethoxysilane (20.0g) was put into a 1L flask for adjustment of emulsions of urethane silicone acryl monomer. The resultant and demineralized water (40.0g) in which sodium persulfate (2.0g) had been o oo 3o dissolved were dripped at the same speed into a reaction flask over four hours. And then, the dripped compositions were allowed to age at 80' C for three hours until urethane silicone acryl emulsion resins had been obtained.
COMPARATIVE EXAMPLE 1-f JADJUSTMENT METHOD FOR URETHANE ACRYL EMULSION RESIN USING (COMPARISON)-1] Demineralized water (250.0g) was put into a 2L flask equipped with a nitrogen gas introduction tube, a thermometer, a capacitor, and an agitator, I) and heated at a temperature of 80° C for substitution of nitrogen, and additionally, a mixture of demineralized water (301.4g), triethylamine (8.6g), and then, (comparison)-l (150.9g), stylene (80.0g), 2-ethylhexyl acrylate (62.0g), and n-butyl methacrylate (105.1g) was put into a IL flask for adjustment of emulsions of urethane acryl monomer. The resultant and demineralized water (40.0g) in which sodium persulfate (2.0g) had been dissolved were dripped at the same speed into a reaction flask over four hours. And then, the dripped compositions were allowed to age at 80° C for three hours until urethane acryl emulsion resins ((comparison)l-l) had been to obtained.
COMPARATIVE EXAMPLE 1-2 [ADJUSTMENT METHOD FOR URETHANE SILICONE ACRYL EMULSION RESIN USING (COMPARISON)-1] Demineralized water (250.0g) was put into a 2L flask equipped with a nitrogen gas introduction tube, a thermometer, a capacitor, and an agitator, and heated at a temperature of 80° C for substitution of nitrogen, and additionally, a mixture of demineralized water (301.4g), triethylamine (8.6g), and then, (comparison)-1 (150.9g), stylene (80.0g), 2-ethylhexyl acrylate (42.0g), n-butyl methacrylate (85. 7 -methacryloil propyltrimethoxysilane (20.0g), and methyl trimethoxysilane (20.0g) was S* put into an 1L flask for adjustment of emulsions of urethane silicone acryl monomer. The resultant and demineralized water (40.0g) in which sodium persulfate (2.0g) had been dissolved were dripped at the same speed into a reaction flask over four hours. And then, the dripped compositions were 2s allowed to age at 80° C for three hours until urethane silicone acryl emulsion resins ((comparison)-1-2) had been obtained.
COMPARATIVE EXAMPLE 2-1 [ADJUSTMENT METHOD FOR ACRYL EMULSION
RESIN]
o0" Demineralized water (250.0g) was put into a 2L flask equipped with a 3 nitrogen gas introduction tube, a thermometer, a capacitor, and an agitator, and heated at a temperature of 80° C for substitution of nitrogen, and additionally, demineralized water (310.0g), dodecyl benzensulfonsodium and polyethylene glycol modified methacrylate (20.0g) were put into a 1L flask equipped with a homogenizer, and the homogenizer was put into .3 motion. Stylene (80.0g), 2-ethylhexyl acrylate (90.0g), n-butyl methacrylate (99.2g), and methyl methacrylate (106.3g) were added to the mixture in the 1L flask, and then, the homogenizer was made to run for five minutes for adjustment of emulsions of acryl monomer. The resultant and demineralized water (40.0g) in which sodium persulfate (2.0g) had been dissolved were dripped at the same speed into a reaction flask over four hours. And then, the dripped compositions were allowed to age for three hours until acryl emulsion resins ((comparison)-2-l) had been obtained.
COMPARATIVE EXAMPLE 2-2 [ADJUSTMENT METHOD FOR SILICONE ACRYL EMULSION RESIN] Demineralized water (250.0g) was put into a 2L flask equipped with a nitrogen gas instruction tube, a thermometer, a capacitor, and an agitator, to and heated at a temperature of 80° C for substitution of nitrogen, and additionally, demineralized water (310.0g), dodecyl benzensulfonsodium and polyethylene glycol modified methacrylate (20.0g) were put into a 1L flask equipped with a homogenizer, and the homogenizer was put into motion. Stylene (80.0g), 2-ethylhexyl acrylate (70.0g), n-butyl methacrylate (79.2g), methyl methacrylate (106.3g), 7 -methacryloil propyltrimethoxysilane (20.0g), and methyl trimethoxysilane (20.0g) were added to the mixture in the 1L flask, and then, the homogenizer was made to run for five minutes for adjustment of emulsions of acryl monomer. The resultant and demineralized water (40.0g) in which sodium persulfate had been dissolved were dripped at the same speed into a reaction flask over four hours. And then, the dripped compositions were made to age at 800 C for three hours until silicone acryl emulsion resins ((comparison)- 2 2 had been obtained.
EVALUATION METHOD The amount of agglomerates in the synthesizing process for emulsion resin was inspected for the purpose of evaluation of the performance of the emulsion resins as obtained in accordance with the examples and comparative examples, and the water resistance, oil resistance, and contamination resistance for the purpose of evaluation of the coatings, and ooo o o the results are shown in the table 1. The coatings, which had been produced by applying 5% butyl cellosolve to the emulsions as a coat producing agent and regulating the amount of the resultant by the use of a 15 mil doctor blade on a glass plate, and held at the room temperature for five days, was subjected to test.
Referring to the evaluation of agglomerates, the emulsion resins agglomerated after synthesized was judged in terms of its amount. A substantially nil; B only a few; C some few D quite a few.
\1 Referring to the water resistance, the coatings as formed was immersed in water at 25" C for 48 hours, and the external appearance of the coatings was evaluated visually in the following four ratings. A no change; B slightly whitened; C ordinarily whitened; D partially melted.
With regard to the oil resistance, the coatings were immersed in salad oil at 25° C, and the external appearance of the coatings after a lapse of 12 hours was evaluated through viewing and touch in the four ratings. A no tack and no change; B slightly tacky; C tacky and partially melted; D considerably tacky and mostly melted.
As regards the contamination resistance, 5% carbon water was applied to the coatings, and after dried at 40° C for two hours, the carbon was eliminated by water stream, and the degree of contamination was evaluated visually in the four ratings. A rarely contaminated; B slightly contaminated; C contaminated; D considerably contaminated.
TABLE 1 Emulsifying Emulsion Water Oil Contaminatio Agglomerates Agent Number Resistance Resistance n Resistance Example 1 1 1 B B B A 1 B A A B Example 2 2 1 A B B A 2 A A A A Comparative (Comparison) C C C B Example 1 1 1 (Comparison) C B B C -1-2 Dodecyl (Comparison) Benzensulfon 2 1 C D C C sodium Polyethylene (Comparison) glycol -2-2 D C B
D
modified methacrylate The present invention as defined in claims 1 to 7 provides a production method for emulsion resin which may form excellent coatings in weather resistance, contamination resistance, toughness, and flexibility. In particular, the production method in accordance with the present invention needs no emulsifying agent, and requires no retention or removal of solvent c r g during the manufacturing process so as to simplify the procedures, and emulsions obtained by this method is very good in stability.
Especially, the invention defined in claims 2 and 3 may provide urethane silicone acryl emulsion resin which not only has the respective different characteristic features of urethane, silicone, and acryl but also may remove any harmful effects involved in the introduction of silicone as in the conventional emulsion resins.
Furthermore, the invention as defined in claims 4 to 7 may provide the production methods for emulsion resin which may achieve the )O aforementioned performances more reliably.
The present invention as defined in claim 8 may provide emulsion resins which may form coatings excellent in weather resistance, contamination resistance, toughness, and flexibility. Especially, the production of said resins needs no emulsifying agent, and requires no retention or removal of IS solvent during the production process so as to simplify the procedures, and may have an effect that the emulsion resins obtained are highly stable.
Furthermore, the invention as defined in claim 9 may provide excellent dispersions of emulsion resin which may form coatings provided with high oo weather resistance, contamination resistance, toughness, and flexibility.
20 It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.
•s For the purposes of this specification it will be clearly understood that the word "comprising" means "including but not limited to", and that the word "comprises" has a corresponding meaning.
oo
Claims (9)
1. A production method for emulsion resins characterised in that it comprises a first process of allowing the glycolic constituents having two hydroxy groups and at least one hydrophilic groups contained in one molecule and polymerizable vinyl monomers having a functional group which may react with isocyanate to react with isocyanate compounds to obtain polymerizable polyurethane vinyl compounds having the emulsifying ability, and a second process of emulsifying said polymerizable polyurethane vinyl compounds and polymerizable vinyl monomers by means of the emulsifying ability of said polymerizable polyurethane vinyl compound to polymerize both the compounds in water.
2. The production method as defined in claim 1 characterised in that the second process comprises a step of obtaining either a non-aqueous mixture prepared in advance by mixing the polymerizable polyurethane vinyl compounds having the emulsifying ability with the polymerizable vinyl monomers under the condition of non-aqueous system, or a non-aqueous \\melb0l\home$\.khoo\.ip\P-t\p40765 SPECI.doc 2R/12/00 S '1 4 mixture prepared in advance by mixing the polymerizable vinyl compounds having the emulsifying ability the polymerizable vinyl monomers and silane compounds having the reactive functional group formed in at least any one of the end and the side chain under the condition of non-aqueous system, and a step of polymerizing the obtained non-aqueous mixture in water.
3. The production method as defined in claim 1 or 2 characterised in that at least one spieces of the polymerizable vinyl monomers is a plymerizable silane compound.
4. The production method as defined in any one of claims 1 to 3 characterised in that the glycolic constituents(l) having two hydroxy groups and at least one hydrophilic group contained in one molecule is at least one selected from groups consisting of a glycolic constituent whose hydrophilic group is of an ionic type that may bring hydrophilic nature due to subsequent neutralization and a glycolic constituent whose hydrophilic group is of a nonionic type. 0*0
5. The production method as defined in any one of claims 1 to 4 characterised in that the combination of the glycolic constituent having two hydroxy groups and at least one hydrophilic group contained in one molecule and a glycol group free of hydrophilic group is in use.
6. The production method as defined in any one of claims 1 to characterised in that said polymerizable polyurethane vinyl compounds (4) having said emulsifying ability is produced by allowing said glycolic constituents to react with diisocyanate compounds in the range of OH 5 group/NCO group 1.0:1.2 1.0:2.0, and then, allowing the obtained polyurethane compounds of the terminal isocyanate to react with the polymerizable vinyl monomers having the functional group which may react with isocyanate.
7. The production method as defined in any one of claims 2 to 6, wherein the total part by weight of the polymerizable vinyl monomers and the reactive silane compounds to 100 parts by weight of the polymerizable polyurethane vinyl compounds is 100 to 2000 in weight ratio, and the 1- 4 weight ratio of the polymerizable vinyl monomers to the silicone compounds having the reactive functional group formed in at least any one of the end and side chain is in the range of 50 50 to 100 0.
8. An emulsion resin characterised in that polymerizable polyurethane vinyl compounds having the emulsifiable ability as obtained by allowing the glycolic constituents having two hydroxy groups and at least one hydrophilic group contained in one molecule and polymerizable vinyl monomers having the functional group which may react with isocianate to react with isocyanate compounds the polymerizable vinyl monomers and cilane compounds having the reactive functional group formed at least any one of the end and side chain are polymerized in water, whereby a core/shell-typed structure having the cilane compounds contained in the to core side and the polymerizable polyurethane vinyl compounds provided at the shell side is formed, and the cilane compounds and polymerizable polyurethane vinyl compounds are polymerized.
9. A emulsion resin dispersion wherein the emulsion resins as defined in claim 8 are dispersed in a water solvent. Dated this 29th day of Deceber 2000. ROCK PAINT CO., LTD. 5 By their Patent Attorneys GRIFFITH HACK Fellows Institute of Patent and STrade Mark Attorneys of Australia I Dated this 29th day of Decenber 2000. rad5 By their Patent Attorneys
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU72584/00A AU7258400A (en) | 2000-12-29 | 2000-12-29 | Emulsion resins such as urethane silicone acryl emulsions and production method therefor and dispersions thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU72584/00A AU7258400A (en) | 2000-12-29 | 2000-12-29 | Emulsion resins such as urethane silicone acryl emulsions and production method therefor and dispersions thereof |
Publications (1)
| Publication Number | Publication Date |
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| AU7258400A true AU7258400A (en) | 2002-07-04 |
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ID=3755248
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| Application Number | Title | Priority Date | Filing Date |
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| AU72584/00A Abandoned AU7258400A (en) | 2000-12-29 | 2000-12-29 | Emulsion resins such as urethane silicone acryl emulsions and production method therefor and dispersions thereof |
Country Status (1)
| Country | Link |
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| AU (1) | AU7258400A (en) |
-
2000
- 2000-12-29 AU AU72584/00A patent/AU7258400A/en not_active Abandoned
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