NZ618667B2 - Low-odour (meth)acrylic reaction resins - Google Patents
Low-odour (meth)acrylic reaction resins Download PDFInfo
- Publication number
- NZ618667B2 NZ618667B2 NZ618667A NZ61866712A NZ618667B2 NZ 618667 B2 NZ618667 B2 NZ 618667B2 NZ 618667 A NZ618667 A NZ 618667A NZ 61866712 A NZ61866712 A NZ 61866712A NZ 618667 B2 NZ618667 B2 NZ 618667B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- weight
- meth
- reactive resin
- cold plastic
- component
- Prior art date
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 110
- 239000011347 resin Substances 0.000 title claims abstract description 110
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 title abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 30
- 229940074076 glycerol formal Drugs 0.000 claims abstract description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 16
- 150000002148 esters Chemical class 0.000 claims abstract description 15
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- VTDOEFXTVHCAAM-UHFFFAOYSA-N 4-methylpent-3-ene-1,2,3-triol Chemical compound CC(C)=C(O)C(O)CO VTDOEFXTVHCAAM-UHFFFAOYSA-N 0.000 claims abstract description 3
- RNVYQYLELCKWAN-UHFFFAOYSA-N Solketal Chemical compound CC1(C)OCC(CO)O1 RNVYQYLELCKWAN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920003023 plastic Polymers 0.000 claims description 35
- 239000004033 plastic Substances 0.000 claims description 35
- 239000003999 initiator Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 29
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 20
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000945 filler Substances 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 150000002978 peroxides Chemical class 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- 239000004971 Cross linker Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 229920000193 polymethacrylate Polymers 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 239000011324 bead Substances 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- 239000001023 inorganic pigment Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Incidol Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical group CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- 125000004430 oxygen atoms Chemical group O* 0.000 claims description 3
- 150000001241 acetals Chemical class 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 230000002335 preservative Effects 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 description 30
- 239000003795 chemical substances by application Substances 0.000 description 22
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 17
- 239000000470 constituent Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 17
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 15
- OXCNCSRAUQIXSP-UHFFFAOYSA-N N,N-dihydroxy-4-methyl-2-propylaniline Chemical compound CCCC1=CC(C)=CC=C1N(O)O OXCNCSRAUQIXSP-UHFFFAOYSA-N 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- -1 glycerol acetal Chemical class 0.000 description 12
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 9
- GYVGXEWAOAAJEU-UHFFFAOYSA-N N,N,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 9
- 239000006254 rheological additive Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000003381 stabilizer Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 230000035852 Tmax Effects 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- XFKFBBVGUXNVOU-UHFFFAOYSA-N (4,5-dihydroxy-2-methylpent-2-en-3-yl) 2-methylprop-2-enoate Chemical compound OCC(O)C(=C(C)C)OC(=O)C(C)=C XFKFBBVGUXNVOU-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-Butanediol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N Di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- JFZVSHAMRZPOPA-UHFFFAOYSA-N 1-[N-(2-hydroxypropyl)-4-methylanilino]propan-2-ol Chemical compound CC(O)CN(CC(C)O)C1=CC=C(C)C=C1 JFZVSHAMRZPOPA-UHFFFAOYSA-N 0.000 description 1
- JUVSRZCUMWZBFK-UHFFFAOYSA-N 2-[N-(2-hydroxyethyl)-4-methylanilino]ethanol Chemical compound CC1=CC=C(N(CCO)CCO)C=C1 JUVSRZCUMWZBFK-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N 2-hydroxyethyl 2-methylacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L Barium sulfate Chemical class [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N Dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N Itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N Methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N N-methylidenehydroxylamine Chemical class ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N P-Toluenesulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N Phosphite Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 206010062080 Pigmentation disease Diseases 0.000 description 1
- 239000004698 Polyethylene (PE) Substances 0.000 description 1
- 229920001228 Polyisocyanate Polymers 0.000 description 1
- 229920001451 Polypropylene glycol Polymers 0.000 description 1
- 239000004823 Reactive adhesive Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N Triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 Vinyl ester Polymers 0.000 description 1
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N butyl 2-methylprop-2-enoate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 125000004432 carbon atoms Chemical group C* 0.000 description 1
- CGUUOQGBKYXSHJ-UHFFFAOYSA-N carbonic acid;2-methylprop-2-enoic acid Chemical class OC(O)=O.CC(=C)C(O)=O CGUUOQGBKYXSHJ-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 101700000038 mpas Proteins 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003287 optical Effects 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 230000002110 toxicologic Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/40—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
Abstract
Disclosed are (meth)acrylic reaction resins containing reactive cyclically substituted esters of (meth)acrylic acid selected from the group consisting of glycerol formal(meth)acrylate, trimethylolpropane formal(meth)acrylate and isopropylideneglycerol (meth)acrylate (Solketal methacrylate). The cyclically substituted esters of (meth)acrylic acid above substitute methyl methacrylate (MMA), which constitutes the main part of the odour an thus results in an odourless/low odour resin. ically substituted esters of (meth)acrylic acid above substitute methyl methacrylate (MMA), which constitutes the main part of the odour an thus results in an odourless/low odour resin.
Description
Low-odour (meth)acrylic reaction resins
Field of the invention
The present invention relates to an innovative (meth)acrylic reactive resin which cures
with low odour or odourlessly. The present invention relates more particularly to reactive
resins comprising high-boiling, reactive (meth)acrylic monomers from the group of the
polar, cyclically substituted esters of (meth)acrylic acid, more particularly glycerol acetal,
ketal or carbonate methacrylates. These new components are used as substitutes for
MMA, which represents the major part of the odour nuisance in the existing, prior-art
reactive resin systems. Using these new components it is possible to obtain resin
formulations which have glass transition temperatures similar to, and properties
comparable with, MMA-based resins. The innovative reactive resins are able in addition
to exhibit more rapid curing than prior-art MMA-based systems. Reactive resins for the
purposes of the invention are reactive monomer mixtures or mixtures of monomers and
polymers that when used as a 2-component system can be readily cured.
Prior art
Reducing the volatile component of a reactive resin of the kind used as a coating
material, casting resin, for trafficway marking or as a floor coating, and hence reducing
the odour nuisance caused when this formulation is applied, has been a goal of
development for a relatively long time. Presently in use as reactive resins are systems
based on reactive monomer mixtures or on a mixture of polymers and monomers,
usually (meth)acrylate-based. The monomers here generally comprise a mixture of di-
or trifunctional crosslinkers and standard components such as MMA. (Meth)acrylates,
more particularly acrylates or methacrylates with small alkyl radicals, are monomers
which possess a high vapour pressure, and hence their odour is easily perceived. When
operating with acrylates it is necessary to comply with corresponding MAC levels.
Reactive resins of these kinds are described in EP 0 973 835, for example.
DE 1 769 792 contains a reactive resin having a MMA fraction of between 30% and
70% by weight. DE 19 826 412 describes a cold-curing reactive (meth)acrylate resin
whose odour is reduced by virtue of a relatively high fraction of vinylaromatics or vinyl
esters. Even a reactive resin of this kind, however, still gives off a disruptive odour, and
its long-term adhesion is reduced compared with that of established systems. EP 2 054
453 describes reactive resins which as well as 30% to 50% by weight of MMA contain
up to 15% by weight of urethane (meth)acrylates. Systems of this kind as well have a
relevant residual odour during application.
One alternative to pure (meth)acrylate systems are reactive resins comprising the use
of unsaturated polyesters, as described in EP 0 871 678, for example. EP 0 871 676
describes the transfer of the same unsaturated bicyclic groups with a proton which is
additionally easily abstractable from the polyesters to other polymers such as
polyolefins or else polymethacrylates. These systems as well, however, contain
predominantly very volatile monomer constituents.
WO 98/40424 describes 2- and 3-component formulations based on unsaturated
polyesters in unsaturated ethylenic compounds or based on methacrylic polymers in
methacrylic monomers. These systems as well have the same disadvantageous
properties in terms of developing odour.
Problem
The problem addressed by the present invention is that of providing a reactive resin
which on application exhibits development of odour that is reduced significantly relative
to the prior art. A particular problem addressed by the present invention is that of
providing a reactive resin system which in toxicological and environmental aspects as
well represents an improvement over the prior art.
A further problem is that of providing 2-component systems based on the reactive resins
of the invention, for use, for example, as trafficway marking or floor coating, which
should be able to be used widely and to be formulated flexibly and have a relatively long
shelf life.
One particular problem is that of providing a reactive resin which enables trafficway
markings that are at least as long-lived as those of the prior art and which have good
retroreflection properties, good day and night visibility, a high, stable whiteness and a
good grip, even when the trafficway is wet, or long-lived floor coatings having good
surface properties, cohesion and adhesion to the substrate.
Further problems not explicitly identified will become apparent from the overall context
of the subsequent description, claims and examples.
Solution
The problems are solved by the provision of an innovative reactive resin, more
specifically by provision of a (meth)acrylate-based reactive resin comprising monomers
having cyclic radicals which contain at least 2 oxygen atoms.
The reactive resin of the invention comprises the following ingredients:
a) 0.5% to 30% by weight of crosslinker(s), preferably dimethacrylates,
b) 5% to 99.5%, preferably to 96%, by weight of an ester of (meth)acrylic
acid with an alcohol having a cyclic radical containing at least two
oxygen atoms,
c) 0%, preferably 3.5% to 90%, by weight of further (meth)acrylates and/or
components copolymerizable with (meth)acrylates,
d) 0% to 5% by weight of either accelerator or initiator and
optionally other auxiliaries.
Component a), the crosslinkers, comprises, more particularly, polyfunctional
(meth)acrylates such as allyl (meth)acrylate. Particularly preferred are di- or tri-
(meth)acrylates such as, for example, 1,4-butanediol di(meth)acrylate, tetraethylene
glycol di(meth)acrylate, triethylene glycol di(meth)acrylate or trimethylolpropane
tri(meth)acrylate. The crosslinker fraction is with more particular preference between 2%
and 20% by weight and with very particular preference between 3% and 15% by weight.
Component b) comprises in particular an ester of (meth)acrylic acid with an acetal, ketal
or carbonate of glycerol, substituted glycerol or unsubstituted or substituted
trimethylolpropane. More particularly, component b) comprises monomers of the
general structural formulae (1) or (2):
Component b) comprises more preferably glycerol formal(meth)acrylate,
trimethylolpropane formal(meth)acrylate or isopropylideneglycerol (meth)acrylate
(Solketal methacrylate).
In a composition particularly suitable for road markings, the reactive resin may further
comprise 1% to 60% by weight of a component e), which comprises one or more
prepolymers, preferably poly(meth)acrylates or polyesters.
The further monomers of component c) that are present in the reactive resin are more
particularly compounds selected from the group of the (meth)acrylates, such as, for
example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethyl-
hexyl (meth)acrylate, hydroxyethyl (meth)acrylate, stearyl (meth)acrylate, benzyl
(meth)acrylate or lauryl (meth)acrylate. In component c) here it is also possible for there
to be monomers which are miscible with (meth)acrylates, such as itaconic acid,
methacrylamides, 1-alkenes or styrenes. The reactive resin preferably contains not
more than 10% by weight, more preferably not more than 5% by weight and very
preferably not more than 2% by weight of (meth)acrylates having radicals of between 1
and 6 carbon atoms.
It is also possible, furthermore, to use macromolecular monomers such as
mono(meth)acrylates of polyethers, for example polyethylene glycols or polypropylene
glycols. Alternative macromolecular monomers as component c) are represented by
urethane (meth)acrylates. Urethane (meth)acrylates in the context of this invention are
understood to be compounds having (meth)acrylate functionalities which are linked to
one another via urethane groups. They are obtainable, for example, through the
reaction of hydroxyalkyl (meth)acrylates with polyisocyanates and polyoxyalkylenes
which have at least two hydroxyl functionalities. One commercially available example,
prepared from polyols, isocyanates and hydroxy-functional methacrylates, is Ebecryl
210-5129 from UCB Chemicals. A reactive resin of the invention may comprise between
% and 30% by weight of the above-described urethane (meth)acrylates.
Component c) is selected specifically, in proportion and composition, in line,
advantageously, with the desired technical function.
The monomer fraction of the reactive resin is more particularly between 10% and 85%
by weight for systems composed exclusively of monomers, and preferably between
% and 60% by weight for systems known as MO-PO systems, of the kind described
below.
In an alternative embodiment which is especially suitable as road marking or floor
coating, the reactive resin further comprises component e). In these systems, known as
MO-PO systems (monomer-polymer systems), therefore, in addition to the stated
monomers, there are also polymers, identified for the purpose of distinctiveness in the
context of this patent as prepolymers, preferably polyesters or poly(meth)acrylates. The
prepolymers are used for improving the polymerization properties, the mechanical
properties, the adhesion to the substrate and the optical requirements imposed on the
resins. The prepolymer fraction of the reactive resin in this embodiment is between 10%
and 60% by weight, preferably between 15% and 40% by weight. Both the polyesters
and the poly(meth)acrylates may contain additional functional groups for imparting
adhesion or for copolymerization in the crosslinking reaction, such as, for example, in
the form of double bonds. Preferably, however, with a view to improved colour stability
on the part of the trafficway marking, the prepolymers contain no double bonds.
The said poly(meth)acrylates are generally composed of the same monomers as
already listed above for the monomers in the resin system. They can be obtained by
solution, emulsion, suspension, bulk or precipitation polymerization, and are added as
pure substances to the system.
Said polyesters are obtained in bulk via polycondensation or ring-opening addition
polymerization, and are composed of the building blocks known for these applications.
These reactive resins of the invention are used as a basis for producing formulations
which make up one of optionally two to three components of a cold plastic likewise of
the invention. In this case there are two preferred embodiments. The first is a pure
monomer system. These formulations comprise, in accordance with the invention, the
following components:
% to 99% by weight of the reactive resin of the invention, comprising at least
0.1% by weight of one or more accelerators or initiators d), and
0.1% to 5% by weight of a mixture comprising one or more accelerators or
initiators f), where component d) comprises an initiator and at the same time
component f) comprises an accelerator, or component d) comprises an
accelerator and component f) comprises an initiator.
In the second embodiment, which is a MO-PO system, the cold plastic has the following
components:
9% to 45% by weight of the reactive resin of the invention, preferably comprising
at least 0.1% by weight of one or more accelerators or initiators d),
0.1% to 5% by weight of a mixture comprising one or more initiators or
accelerators f),
0% to 15% by weight of an inorganic pigment, preferably titanium dioxide, and
% to 90% by weight of glass beads, organic or further mineral fillers, where
component d) comprises an initiator and at the same time component f)
comprises an accelerator, or alternatively component d) comprises an
accelerator and component f) comprises an initiator.
In both embodiments, initiators and accelerators are separate prior to mixing, in different
components of the cold plastic.
In variants of both embodiments, two reactive resins of the invention are mixed with one
another in a weight ratio between 1:1 and 4:1, with one reactive resin comprising
component d) and the other reactive resin comprising component f).
Serving as initiators d) and f) - more specifically, polymerization initiators - are
peroxides. In some circumstances it may be advantageous to use a mixture of different
initiators. Preference is given to using peroxides such as dilauroyl peroxide, dibenzoyl
peroxide, tert-butyl peroctoate, di-tert-butyl peroxide (DTBP), di-tert-amyl peroxide
(DTAP), tert-butyl peroxy(2-ethylhexyl)carbonate (TBPEHC) and other peroxides which
decompose at a high temperature, as radical initiators. For reactive resins for
application, for example, for trafficway markings, dilauroyl peroxide or dibenzoyl
peroxide are particularly preferred. Generally speaking, the peroxide in the second
component is admixed with a diluent, as for example with a phthalate such as dibutyl
phthalate, with an oil or with another plasticizer. The cold plastic of the invention, as a
sum of the first and second components and also, optionally, the third component,
comprises between 0.1% and 7% by weight, preferably between 0.5% and 6% by
weight and very preferably between 1% and 5% by weight of the initiator or of the
mixture of the initiator and the diluent.
One particular embodiment of a redox initiator system for reactive resins is the
combination of peroxides and accelerators g), more particularly amines. Said amines
include, for example, tertiary, aromatically substituted amines, such as more particularly
N,N-dimethyl-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine or N,N-bis(2-hydroxy-
propyl)-p-toluidine. The reactive resin of the invention may comprise up to 7%,
preferably up to 5% and very preferably up to 3% by weight of an accelerator.
In an alternative embodiment of a 3-component system, suitable more particularly for
trafficway markings, the accelerator is present in the second component, for example in
a diluent, and the initiator, for example the peroxide, is part of the reactive resin of the
invention. The third component comprises, for example, glass beads and any adhesion
promoters required. Alternatively, the accelerator is part of the reactive resin and the
initiator or initiators are part of a second or third component of the reactive resin.
The components of the cold plastics described can be mixed before or during
application.
In addition there may be other auxiliaries present, such as stabilizers, examples being
UV stabilizers, inhibitors, chain transfer agents or waxes. The individual components
may also comprise other auxiliaries such as defoamers, rheological additives, flow
control assistants, wetting agents and/or dispersants, a grippy (slip-resistant) filler, and
anti-settling agents. It is also possible, especially for trafficway markings, for glass
beads, added for the purpose of improving the reflection, to be present in one of the
components of the cold plastic or to be scattered on additionally during application.
In addition, depending on utility, colorants and fine and/or coarse fillers may be added to
the formulations.
For the field of use of the formulations as trafficway markings or surface markings,
auxiliaries and additives added are preferably colorants. Particularly preferred are white,
red, blue, green and yellow inorganic pigments, particular preference being given to
white pigments such as titanium dioxide.
Fine fillers used are from the group of the calcium carbonates, barium sulphates,
quartzes, finely ground quartzes, precipitated and fumed silicas, pigments and
crystobalites. Coarse fillers used are quartzes, crystobalites, corundums and aluminium
silicates.
As auxiliaries and additives it is additionally possible to use chain transfer agents,
plasticizers, paraffins, stabilizers, inhibitors, waxes and/or oils.
The paraffins are added in order to prevent inhibition of polymerization by atmospheric
oxygen. For this purpose it is possible to use two or more paraffins having different
melting points, in different concentrations.
As chain transfer agents it is possible to use all of the compounds known from radical
polymerization. Preference is given to using mercaptans such as n-dodecyl mercaptan,
but also polyfunctional mercapto compounds such as pentaerythritol tetrathioglycolate.
As plasticizers it is preferred to use esters, polyols, oils, low molecular mass polyethers
or phthalates.
It is also possible to use conventional UV stabilizers. The UV stabilizers are preferably
selected from the group of benzophenone derivatives, benzotriazole derivatives,
thioxanthonate derivatives, piperidinolcarboxylic ester derivatives or cinnamic ester
derivatives.
From the group of the stabilizers and/or inhibitors it is preferred to use substituted
phenols, hydroquinone derivatives, phosphines and phosphites.
The following components may also optionally be present in formulations for trafficway
marking:
wetting, dispersing and flow control assistants are preferably used that are selected
from the group of alcohols, hydrocarbons, glycol derivatives, derivatives of glycolic
esters, acetic esters and polysiloxanes, polyethers, polysiloxanes, polycarboxylic acids
and saturated and unsaturated polycarboxylic acid amine amides.
As rheological additives it is preferred to use polyhydroxycarboxamides, urea
derivatives, salts of unsaturated carboxylic acid esters, alkylammonium salts of acidic
phosphoric acid derivatives, ketoximes, amine salts of p-toluenesulphonic acid, amine
salts of sulphonic acid derivatives, and aqueous or organic solutions or mixtures of the
compounds. It has been found that rheological additives based on fumed or precipitated
silicas, including, optionally, silanized silicas, having a BET surface area of
-700 nm /g are particularly suitable.
Defoamers used are preferably selected from the group of alcohols, hydrocarbons,
paraffin-base mineral oils, glycol derivatives, derivatives of glycolic esters, acetic esters
and polysiloxanes.
These formulation freedoms show that the reactive resin of the invention or the cold
plastic of the invention comprising the reactive resin can be formulated and additized for
each specific application.
The possible uses for the cold plastics of the invention are multifarious. For instance,
such cold plastics are suitable especially for the production of trafficway markings,
trafficway repair compositions, intumescent coatings or floor coatings. Their use in the
production of cobblestones is also possible.
Cold plastics without solid formulating ingredients such as fillers can also be used, for
example, as a floor coating, casting resin, architectural preservative, coating material or
laminating material - for orthopaedic resins, for example - and also for producing
prepregs. Use as reactive adhesives is another possibility.
Surprisingly it has been found that the reactive resins of the invention and also the cold
plastics produced from them are distinguished by very good properties such as long life,
mechanical properties, abrasion resistance, optionally whiteness or pigmentation, and
grip, all of which are at least as good as in prior-art systems. Furthermore, however, the
systems of the invention are distinguished relative to the prior art by particularly low
development of odour and release of volatile constituents. The co-formulation of
component b) makes it possible, where further monomers are selected, to do entirely
without, in particular, highly odorous monomers such as ethyl acrylate, without impairing
the other properties of the cold plastic.
The system can also be optimized in respect of the applications by selecting appropriate
monomers, prepolymers, additives and/or adhesion promoters. Accordingly, the
systems of the invention can be variably optimized and used for a wide variety of
applications. For road markings, for example, the marking of surfaces of asphalt,
concrete or natural stone is entirely possible.
The systems of the invention can be employed flexibly in terms of the application
technology as well. The reactive resins and cold plastics of the invention can be applied
by spraying, casting or extrusion processes.
The examples given below are given for better illustration of the present invention, but
are not such as to restrict the invention to the features disclosed therein.
Examples
Materials used:
Polymer components used were Degalan LP 64/12 and Degalan LP 66/02 (both from
Evonik Röhm). These are suspension polymers containing methyl methacrylate and
n-butyl methacrylate in different proportions and having weight-average molar masses
M of between 30 000 and 90 000 g/mol (determined by SEC against PMMA
standards).
The pot life was ascertained by determining the time taken for the material, after stirred
incorporation of the curing agent, to warm up by itself from room temperature (20-22°C)
to 32°C.
The viscosities of the reactive resin mixtures were measured using a Brookfield DV2,
spindle 2, at 12 revolutions per minute.
For the determination of the t , the time used was that taken by 20 g of resin in a PE
beaker with a diameter of 45 mm to reach the maximum temperature (T ) in the
course of curing.
For the determination of the VOC levels, a gravimetric measurement was carried out in
agreement with ASTM D2369-10, method E.
Example 1
94 parts by weight of glycerol formal methacrylate and 1 part by weight of 1,4-butane-
diol dimethacrylate are admixed with 0.06 part by weight of Topanol-O, 0.5 part by
weight of Sasolwax 5603 and 1.5 parts by weight of N,N-dihydroxypropyl-p-toluidine
and the constituents are mixed with vigorous stirring at 63°C until they have all
dissolved. The resin is subsequently left to cool to 23°C with stirring. For curing, the
resin is admixed with 2 per cent by weight of curing agent powder (50% BPO in
dicyclohexyl phthalate), stirred for a minute and then applied in a film thickness of about
2 mm to a metal surface.
Example 2
94 parts by weight of isopropylideneglycerol methacrylate, 1 part by weight of
triethylene glycol dimethacrylate are admixed with 0.06 part by weight of Topanol-O,
0.5 part by weight of Sasolwax 5603 and 1.5 parts by weight of N,N-dihydroxypropyl-
p-toluidine and the constituents are mixed with vigorous stirring at 63°C until they have
all dissolved. The resin is subsequently left to cool to 23°C with stirring. For curing, the
resin is admixed with 2 per cent by weight of curing agent powder (50% BPO in
dicyclohexyl phthalate), stirred for a minute and then applied in a film thickness of about
2 mm to a metal surface.
Example 3
84 parts by weight of glycerol formal methacrylate, 9 parts of glycerol formal acrylate
and 5 parts by weight of 1,4-butanediol dimethacrylate are admixed with 0.06 part by
weight of Topanol-O, 0.6 part by weight of Sasolwax 5603 and 1.5 parts by weight of
N,N-dihydroxypropyl-p-toluidine and the constituents are mixed with vigorous stirring
at 63°C until they have all dissolved. The resin is subsequently left to cool to 23°C with
stirring. For curing, the resin is admixed with 2 per cent by weight of curing agent
powder (50% BPO in dicyclohexyl phthalate), stirred for a minute and then applied in a
film thickness of about 2 mm to a metal surface.
Example 4
56 parts by weight of glycerol formal methacrylate, 37 parts of glycerol formal acrylate
and 5 parts by weight of 1,4-butanediol dimethacrylate are admixed with 0.06 part by
weight of Topanol-O, 0.6 part by weight of Sasolwax 5603 and 1.5 parts by weight of
N,N-dihydroxypropyl-p-toluidine and the constituents are mixed with vigorous stirring
at 63°C until they have all dissolved. The resin is subsequently left to cool to 23°C with
stirring. For curing, the resin is admixed with 2 per cent by weight of curing agent
powder (50% BPO in dicyclohexyl phthalate), stirred for a minute and then applied in a
film thickness of about 2 mm to a metal surface.
Example 5
56 parts by weight of glycerol formal methacrylate, 37 parts of glycerol formal
methacrylate and 5 parts by weight of 1,4-butanediol dimethacrylate are admixed with
0.06 part by weight of Topanol-O, 0.6 part by weight of Sasolwax 5603 and 1.5 parts by
weight of N,N-dihydroxypropyl-p-toluidine and the constituents are mixed with
vigorous stirring at 63°C until they have all dissolved. The resin is subsequently left to
cool to 23°C with stirring. For curing, the resin is admixed with 2 per cent by weight of
curing agent powder (50% BPO in dicyclohexyl phthalate), stirred for a minute and then
applied in a film thickness of about 2 mm to a metal surface.
Example 6
84 parts by weight of glycerol formal methacrylate, 9 parts of glycerol formal
methacrylate and 5 parts by weight of 1,4-butanediol dimethacrylate are admixed with
0.06 part by weight of Topanol-O, 0.6 part by weight of Sasolwax 5603 and 1.5 parts by
weight of N,N-dihydroxypropyl-p-toluidine and the constituents are mixed with
vigorous stirring at 63°C until they have all dissolved. The resin is subsequently left to
cool to 23°C with stirring. For curing, the resin is admixed with 2 per cent by weight of
curing agent powder (50% BPO in dicyclohexyl phthalate), stirred for a minute and then
applied in a film thickness of about 2 mm to a metal surface.
Table 1: Cure behaviour of cold plastics without prepolymers, in different mixtures of
comonomers, to illustrate the adjustability of the hardness of the cured material:
Example Pot life Tmax tmax Surface ShoreD
[min] [°C] [min] tack-free
3 4 166.0 6.00 yes 76
4 3 185.0 4.50 yes 71
3.25 189.0 4.75 yes 33
6 3 194.0 4.25 yes 16
Example 7
34 parts by weight of isopropylideneglycerol methacrylate, 19 parts of 2-ethylhexyl
acrylate, 9 parts by weight of hydroxypropyl methacrylate and 8.5 parts by weight of
triethylene glycol dimethacrylate are admixed with 0.06 part by weight of Topanol-O,
19 parts by weight of Degalan LP 66/02, 7 parts by weight of Degalan LP 64/12, 0.9 part
by weight of Sasolwax 5603 and 1.5 parts by weight of N,N-dihydroxypropyl-p-
toluidine and the constituents are mixed with vigorous stirring at 63°C until they have all
dissolved. The resin is subsequently left to cool to 23°C with stirring. For curing, the
resin is admixed with 2 per cent by weight of curing agent powder (50% BPO in
dicyclohexyl phthalate), stirred for a minute and then applied in a film thickness of about
2 mm to a metal surface.
Example 8
34 parts by weight of glycerol formal acrylate, 35 parts of n-butyl acrylate and 2 parts by
weight of 1,4-butanediol dimethacrylate are admixed with 0.06 part by weight of
Topanol-O, 25 parts by weight of Degalan LP 66/02, 0.5 part by weight of Sasolwax
5603, 1.5 parts by weight of N,N-dihydroxypropyl-p-toluidine and 0.4 part by weight
of N,N-dimethyl-p-toluidine and the constituents are mixed with vigorous stirring at 63°C
until they have all dissolved. The resin is subsequently left to cool to 23°C with stirring.
For curing, the resin is admixed with 2 per cent by weight of curing agent powder (50%
BPO in dicyclohexyl phthalate), stirred for a minute and then applied in a film thickness
of about 2 mm to a metal surface.
Example 9
37 parts by weight of glycerol formal methacrylate, 37 parts of 2-ethylhexyl acrylate and
2 parts by weight of triethylene glycol dimethacrylate are admixed with 0.07 part by
weight of Topanol-O, 20 parts by weight of Degalan LP 64/12, 1.5 parts by weight of
Sasolwax 5603, 0.7 part by weight of N,N-dihydroxypropyl-p-toluidine and 0.3 part by
weight of N,N-dimethyl-p-toluidine and the constituents are mixed with vigorous stirring
at 63°C until they have all dissolved. The resin is subsequently left to cool to 23°C with
stirring. For curing, the resin is admixed with 2 per cent by weight of curing agent
powder (50% BPO in dicyclohexyl phthalate), stirred for a minute and then applied in a
film thickness of about 2 mm to a metal surface.
Example 10
parts by weight of glycerol formal methacrylate, 39 parts of 2-ethylhexyl methacrylate
and 2.5 parts by weight of triethylene glycol dimethacrylate are admixed with 0.07 part
by weight of Topanol-O, 20 parts by weight of Degalan LP 64/12, 1.5 parts by weight of
Sasolwax 5603, 0.7 part by weight of N,N-dihydroxypropyl-p-toluidine and 0.8 part by
weight of N,N-dimethyl-p-toluidine and the constituents are mixed with vigorous stirring
at 63°C until they have all dissolved. The resin is subsequently left to cool to 23°C with
stirring. For curing, the resin is admixed with 2 per cent by weight of curing agent
powder (50% BPO in dicyclohexyl phthalate), stirred for a minute and then applied in a
film thickness of about 2 mm to a metal surface.
Example 11
37 parts by weight of glycerol formal methacrylate, 33 parts of 2-ethylhexyl acrylate,
parts of 2-hydroxyethyl methacrylate and 2 parts by weight of triethylene glycol
dimethacrylate are admixed with 0.07 part by weight of Topanol-O, 17 parts by weight of
Degalan LP 66/02, 3 parts by weight of Degalan LP 64/12, 1.4 parts by weight of
Sasolwax 5603, 0.7 part by weight of N,N-dihydroxypropyl-p-toluidine and 0.3 part by
weight of N,N-dimethyl-p-toluidine and the constituents are mixed with vigorous stirring
at 63°C until they have all dissolved. The resin is subsequently left to cool to 23°C with
stirring. For curing, the resin is admixed with 2 per cent by weight of curing agent
powder (50% BPO in dicyclohexyl phthalate), stirred for a minute and then applied in a
film thickness of about 2 mm to a metal surface.
Example 12
37 parts by weight of glycerol formal methacrylate, 33 parts of 2-ethylhexyl acrylate,
parts of 2-hydroxypropyl methacrylate and 2 parts by weight of triethylene glycol
dimethacrylate are admixed with 0.07 part by weight of Topanol-O, 17 parts by weight of
Degalan LP 66/02, 3 parts by weight of Degalan LP 64/12, 1.4 parts by weight of
Sasolwax 5603, 0.7 part by weight of N,N-dihydroxypropyl-p-toluidine and 0.3 part by
weight of N,N-dimethyl-p-toluidine and the constituents are mixed with vigorous stirring
at 63°C until they have all dissolved. The resin is subsequently left to cool to 23°C with
stirring. For curing, the resin is admixed with 2 per cent by weight of curing agent
powder (50% BPO in dicyclohexyl phthalate), stirred for a minute and then applied in a
film thickness of about 2 mm to a metal surface.
Example 13
43 parts by weight of glycerol formal methacrylate, 33 parts of 2-ethylhexyl acrylate,
parts of 2-hydroxypropyl methacrylate and 2 parts by weight of triethylene glycol
dimethacrylate are admixed with 0.07 part by weight of Topanol-O, 17 parts by weight of
Degalan LP 66/02, 3 parts by weight of Degalan LP 64/12, 1.5 parts by weight of
Sasolwax 5603, 0.7 part by weight of N,N-dihydroxypropyl-p-toluidine and 0.3 part by
weight of N,N-dimethyl-p-toluidine and the constituents are mixed with vigorous stirring
at 63°C until they have all dissolved. The resin is subsequently left to cool to 23°C with
stirring. For curing, the resin is admixed with 2 per cent by weight of curing agent
powder (50% BPO in dicyclohexyl phthalate), stirred for a minute and then applied in a
film thickness of about 2 mm to a metal surface.
Example 14
38 parts by weight of glycerol formal methacrylate, 33 parts of 2-ethylhexyl acrylate,
parts of 2-hydroxypropyl methacrylate and 1 part by weight of triethylene glycol
dimethacrylate are admixed with 0.07 part by weight of Topanol-O, 17 parts by weight of
Degalan LP 66/02, 3 parts by weight of Degalan LP 64/12, 1.5 parts by weight of
Sasolwax 5603, 0.3 part by weight of N,N-dihydroxypropyl-p-toluidine and 0.2 part by
weight of N,N-dimethyl-p-toluidine and the constituents are mixed with vigorous stirring
at 63°C until they have all dissolved. The resin is subsequently left to cool to 23°C with
stirring. For curing, the resin is admixed with 2 per cent by weight of curing agent
powder (50% BPO in dicyclohexyl phthalate), stirred for a minute and then applied in a
film thickness of about 2 mm to a metal surface.
Table 2: Cold plastics for demonstrating the adjustability of the reactivity and the
viscosity of the reactive resins of the invention and also the tack-free state of the cured
resins with different comonomers.
Example Pot life tmax Tmax Tack-
No. (min) (min) (°C) Visc. (mPas) free
1 5 8 150 <10 yes
2 9 13 104 <10 yes
8 6 6.5 109 150 yes
9 11 15 96 170 yes
5 7.7 101 185 yes
11 13 19 94 250 yes
12 12 15 98 270 yes
13 13 10 117 220 yes
14 17 12 131 210 yes
Example 15
The reactive resin obtained from Example 9 is processed with 10 parts by weight of
titanium dioxide (TR 92), 54.6 parts by weight of fine filler (Omyacarb 15 GU), 0.3 part
by weight of a dispersing assistant (TEGO® Dispers 670) and 0.1 part by weight of
rheological additive (Byk 410) with dispersing to form a trafficway marking paint.
In this processing operation, the resin is introduced to start with, a portion of the
rheological additive is incorporated with dispersion over a period of 5 minutes, followed
by the dispersing assistant, likewise over 5 minutes, and followed in turn by the titanium
dioxide and the fine filler, each for a further 10 minutes. Lastly, the remainder of the
dispersing assistant is incorporated.
For curing, the processed resin is admixed with 2 per cent by weight of curing agent
powder (50% BPO in dicyclohexyl phthalate), stirred for a minute and then knife-coated
in a film thickness of 1 mm onto a PET surface.
Example 16
The reactive resin obtained from Example 10 is processed with 10 parts by weight of
titanium dioxide (TR 92), 54.6 parts by weight of fine filler (Omyacarb 15 GU), 0.3 part
by weight of a dispersing assistant (TEGO® Dispers 670) and 0.1 part by weight of
rheological additive (Byk 410) with dispersing to form a trafficway marking paint.
In this processing operation, the resin is introduced to start with, a portion of the
rheological additive is incorporated with dispersion over a period of 5 minutes, followed
by the dispersing assistant, likewise over 5 minutes, and followed in turn by the titanium
dioxide and the fine filler, each for a further 10 minutes. Lastly, the remainder of the
dispersing assistant is incorporated.
For curing, the processed resin is admixed with 2 per cent by weight of curing agent
powder (50% BPO in dicyclohexyl phthalate), stirred for a minute and then knife-coated
in a film thickness of 1 mm onto a PET surface.
Comparative Example 1
34 parts by weight of methyl methacrylate, 35 parts of n-butyl acrylate and 1.6 parts by
weight of triethylene glycol dimethacrylate are admixed with 0.06 part by weight of
Topanol-O, 23 parts by weight of Degalan LP 66/02, 4 parts by weight of Degalan LP
64/12, 1.3 parts by weight of Sasolwax 5603, 0.6 part by weight of N,N-dihydroxy-
propyl-p-toluidine and 0.3 part by weight of N,N-dimethyl-p-toluidine and the
constituents are mixed with vigorous stirring at 63°C until they have all dissolved. The
resin is subsequently left to cool with stirring to 23°C. The reactive resin thus obtained is
processed with 10 parts by weight of titanium dioxide (TR 92), 54.6 parts by weight of
fine filler (Omyacarb 15 GU), 0.3 part by weight of a dispersing assistant (TEGO®
Dispers 670) and 0.1 part by weight of rheological additive (Byk 410) with dispersing to
form a trafficway marking paint.
In this processing operation, the resin is introduced to start with, a portion of the
rheological additive is incorporated with dispersion over a period of 5 minutes, followed
by the dispersing assistant, likewise over 5 minutes, and followed in turn by the titanium
dioxide and the fine filler, each for a further 10 minutes. Lastly, the remainder of the
dispersing assistant is incorporated.
For curing, the processed resin is admixed with 2 per cent by weight of curing agent
powder (50% BPO in dicyclohexyl phthalate), stirred for a minute and then knife-coated
in a film thickness of 1 mm onto a PET surface.
Table 3: Comparison of a conventional cold plastic for road markings with fillers, based
on MMA and other volatile comonomers, with resins of the invention, and also VOC
values:
Comparative
Example 15 Example 16
Example 1
Shore D after 24 h 40 44 42
Shore D after 3 d 44 45 42
Pot life [min] 10 2.5 4
Cure time [min] 30 25 35
1.9 (Comparative
VOC [% by weight]* 1.0 0.9
Example 2)
* The VOC values were carried out with the filler-free cold plastics. Specifically,
therefore, the cold plastic from Example 15 corresponds to the cold plastic from
Example 9, and the cold plastic from Example 16 corresponds to the cold plastic from
Example 10. Comparative Example 2 corresponds to Comparative Example 1 without
fillers.
WE
Claims (14)
1. (Meth)acrylate-based reactive resin, characterized in that the reactive resin has the following ingredients: a) 0.5% to 30% by weight of crosslinker(s), b) 5% to 99.5% by weight of an ester of (meth)acrylic acid with an alcohol having a cyclic radical containing at least two oxygen atoms, c) 0% to 90% by weight of other (meth)acrylates and/or components copolymerizable with (meth)acrylates, d) 0% to 5% by weight of accelerator or initiator and optionally other auxiliaries.
2. Reactive resin according to Claim 1, characterized in that the reactive resin has the following ingredients: a) 0.5% to 30% by weight of the crosslinker(s), said crosslinker(s) being dimethacrylate(s), b) 5% to 96% by weight of the ester of (meth)acrylic acid, said ester being an ester of (meth)acrylic acid with an acetal, ketal or carbonate of glycerol or trimethylolpropane, c) 3.5% to 90% by weight of the other (meth)acrylates and/or components copolymerizable with (meth)acrylates, d) 0% to 5% by weight of the accelerator(s) and optionally other auxiliaries.
3. Reactive resin according to Claim 1, characterized in that the reactive resin further comprises e) 1% to 60% by weight of prepolymers.
4. Reactive resin according to Claim 3, characterized in that the prepolymers e) are poly(meth)acrylates or polyesters.
5. Reactive resin according to Claim 1, characterized in that the component b) is glycerol formal(meth)acrylate, trimethylolpropane formal(meth)acrylate or isopropylideneglycerol (meth)acrylate (Solketal methacrylate).
6. Cold plastic, characterized in that AH26(10108070_1):RTK the cold plastic has the following components: 5% to 99% by weight of a reactive resin according to any of Claims 1 to 5, comprising at least 0.1% by weight of one or more accelerators or initiators d), 0.1% to 5% by weight of a mixture comprising one or more initiators or accelerators f), where component d) comprises an initiator and at the same time component f) comprises an accelerator, or component d) comprises an accelerator and component f) comprises an initiator, and initiators and accelerators are present separately from one another before the cold plastic is produced.
7. Cold plastic according to Claim 6, characterized in that the cold plastic has the following components: 9% to 45% by weight of a reactive resin according to any of Claims 1 to 5, comprising at least 0.1% by weight of one or more accelerators or initiators d), 0.1% to 5% by weight of a mixture comprising one or more initiators or accelerators f), where component d) comprises an initiator and at the same time component f) comprises an accelerator, or component d) comprises an accelerator and component f) comprises an initiator, and initiators and accelerators are present separately from one another before the cold plastic is produced, 0% to 15% by weight of a inorganic pigment, and 10% to 90% by weight of glass beads, organic or mineral fillers.
8. Cold plastic according to claim 7 wherein the inorganic pigment is titanium dioxide.
9. Cold plastic according to any one of Claims 6 to 8, characterized in that the initiators comprise one or more peroxides and the accelerators comprise one or more amines.
10. Cold plastic according to Claim 9, characterized in that the peroxide is dilauroyl peroxide and/or dibenzoyl peroxide and the amine is a tertiary, aromatically substituted amine.
11. Cold plastic according to any one of Claims 6 to 10, characterized in that the accelerator is part of the reactive resin according to any of Claims 1 to 5, and in that the initiator is not part of the reactive resin, but is instead a separate component of the cold plastic.
12. Cold plastic according to any one of Claims 6 to 11, characterized in that the components AH26(10108070_1):RTK are mixed before or during application.
13. Use of a cold plastic according to any one of Claims 6 to 12 for producing trafficway markings, trafficway repair compositions, intumescent coatings or floor coatings.
14. Use of a cold plastic according to Claim 6 as casting resin, architectural preservative, coating material or laminating material. Evonik Röhm GmbH By the Attorneys for the Applicant SPRUSON & FERGUSON Per: AH26(10108070_1):RTK
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102011109139A DE102011109139A1 (en) | 2011-08-02 | 2011-08-02 | Low-odor (meth) acrylic reaction resins |
DE102011109139.8 | 2011-08-02 | ||
PCT/EP2012/062790 WO2013017350A1 (en) | 2011-08-02 | 2012-07-02 | Low-odour (meth)acrylic reaction resins |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ618667A NZ618667A (en) | 2015-06-26 |
NZ618667B2 true NZ618667B2 (en) | 2015-09-29 |
Family
ID=
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2843484C (en) | Low-odour (meth)acrylic reaction resins | |
AU2010272714B2 (en) | Binding agent for producing road markings ready quickly for traffic | |
US9175171B2 (en) | Methacrylate resins for producing road markings | |
JP2014510160A (en) | Reactive resin with modified impact resistance | |
JP2013518155A (en) | Formulations for producing road markings that adhere to dry and wet concrete | |
EP2861661A1 (en) | Curing of reaction resins using asymmetric amines as accelerators | |
US20230257619A1 (en) | Curing of reaction resins using unsaturated peroxides as initiators and organic phosphites as accelerators | |
NZ618667B2 (en) | Low-odour (meth)acrylic reaction resins | |
KR20220021109A (en) | (Meth)acrylic reactive resin that cures with little or no odor | |
JP2965166B2 (en) | Resin composition for marking materials | |
JP2003105012A (en) | Resin composition and coating material |