CA2561429A1 - Removable protective coating - Google Patents
Removable protective coating Download PDFInfo
- Publication number
- CA2561429A1 CA2561429A1 CA002561429A CA2561429A CA2561429A1 CA 2561429 A1 CA2561429 A1 CA 2561429A1 CA 002561429 A CA002561429 A CA 002561429A CA 2561429 A CA2561429 A CA 2561429A CA 2561429 A1 CA2561429 A1 CA 2561429A1
- Authority
- CA
- Canada
- Prior art keywords
- protective coating
- weight
- protective
- agent
- binder
- 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
Links
- 239000011253 protective coating Substances 0.000 title claims abstract description 72
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 57
- 239000011230 binding agent Substances 0.000 claims abstract description 47
- 239000003223 protective agent Substances 0.000 claims abstract description 32
- 239000000049 pigment Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 30
- 230000001681 protective effect Effects 0.000 claims description 19
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000002562 thickening agent Substances 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 3
- 239000010428 baryte Substances 0.000 claims description 3
- 229910052601 baryte Inorganic materials 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
- 239000010440 gypsum Substances 0.000 claims description 3
- 229910052602 gypsum Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- -1 polyethylene terephthalate Polymers 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 4
- 239000002318 adhesion promoter Substances 0.000 claims 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims 2
- 235000019445 benzyl alcohol Nutrition 0.000 claims 2
- 239000000463 material Substances 0.000 claims 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims 2
- 150000004756 silanes Chemical class 0.000 claims 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- 125000005270 trialkylamine group Chemical group 0.000 claims 2
- 229920000515 polycarbonate Polymers 0.000 claims 1
- 239000004417 polycarbonate Substances 0.000 claims 1
- 229920000139 polyethylene terephthalate Polymers 0.000 claims 1
- 239000005020 polyethylene terephthalate Substances 0.000 claims 1
- 229920000098 polyolefin Polymers 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002585 base Substances 0.000 description 9
- 230000005855 radiation Effects 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 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 5
- 238000005266 casting Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920001285 xanthan gum Polymers 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000004815 dispersion polymer Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000003898 horticulture Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000000230 xanthan gum Substances 0.000 description 2
- 235000010493 xanthan gum Nutrition 0.000 description 2
- 229940082509 xanthan gum Drugs 0.000 description 2
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- NSMXQKNUPPXBRG-SECBINFHSA-N (R)-lisofylline Chemical compound O=C1N(CCCC[C@H](O)C)C(=O)N(C)C2=C1N(C)C=N2 NSMXQKNUPPXBRG-SECBINFHSA-N 0.000 description 1
- JWDYCNIAQWPBHD-UHFFFAOYSA-N 1-(2-methylphenyl)glycerol Chemical compound CC1=CC=CC=C1OCC(O)CO JWDYCNIAQWPBHD-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- 241000023308 Acca Species 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241001103870 Adia Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229930186657 Lat Natural products 0.000 description 1
- 101100323108 Mus musculus Amot gene Proteins 0.000 description 1
- 101100384355 Mus musculus Ctnnbip1 gene Proteins 0.000 description 1
- 241000282337 Nasua nasua Species 0.000 description 1
- 240000008881 Oenanthe javanica Species 0.000 description 1
- 101150025786 PCLO gene Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XDXHAEQXIBQUEZ-UHFFFAOYSA-N Ropinirole hydrochloride Chemical class Cl.CCCN(CCC)CCC1=CC=CC2=C1CC(=O)N2 XDXHAEQXIBQUEZ-UHFFFAOYSA-N 0.000 description 1
- 241000212342 Sium Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241001504505 Troglodytes troglodytes Species 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229940072293 axid Drugs 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
- 230000001680 brushing effect Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- SGXXNSQHWDMGGP-IZZDOVSWSA-N nizatidine Chemical compound [O-][N+](=O)\C=C(/NC)NCCSCC1=CSC(CN(C)C)=N1 SGXXNSQHWDMGGP-IZZDOVSWSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention relates to a protective coating which is removable with a removing agent comprising a strong base, which protective coating comprises a pigment, a weak base and a binder, the binder being a polymer having a weight-average molecular weight of 10,000-100,000 and an acid value of 40-250. The invention further relates to a protective agent and a method for forming the protective coating.
Description
Tir.le: ~:ernovable protective aoatinc~
xhis invex~tiaxt relates Go a remvvab3.e protective acating, and to a protective agent and a method for forming such coating.
In horticulture, many .plants are grown in ~ greenhouses. ~ltusr they ~:an benefit from optimized conc~it~.ons, such as temperature, nmaunt of light, humidity and the like. However. a problem here is that the plants being grown axe exposed. under waxen, sunny weather condi.tacnsr to a Lax-ga art~nunt of radiation, which might 1.0 disturb the living caxzditions and grtawth of the plants, algid might even reuse them to burn. To obviate this problem, it~
is customary in horticulture to protect the planGS during the spring and the summ~:r against they adverse effect of uz.due radiation cy providing the transparent surfaces of la tYie greezzhc~use with a protective coating.
one of the chief requirements to ba met Jay such a prratective casting ~.s that sufficient prvteCtion #rom light.
anti heat is achieved. Ta meet this requi.remerit, the prcreGtive coating, should contain a pigment, such as cha~.k 20 or titanium oxide. A further important requirement is that the protective agent from which the protective coating is fozmed exhihits suffic:3ent adhesion to the surface of a greer,'zouse~ When its adhesive str~eragth is too Sow, the , coa~:ing wall not be resistant to weather influences and it 2S will be necessary tc~ restore the coating sevezal times per season .ox to rPplaaa~ it. When adhesion i.s too strong., it requires much effort to remove the coating at the end of the seasax~, In European patent apgla.cation 0 428 X37, it is 3c3 pzcpc~sed to use a prat.Prtive agent based on a polymeric binder anc3 pigments, >suc:h as aluminum pigments, titanium pig;~~r~ts or calcium c~~rbc~r_ate. No particular requirement$
are set with regard to the nature o~ the pc~lymexic binder.
In practice, it has be~ea f.~und that many palymera.c 35 binders impart too high an adhesive strength to the °
'-"~"'--'-""'~°' " ~'CA 02561429 2005-03-15'-' "' z prcteotive agent. This ma.l:es it particularly labor-irstensi.ve tca remove the pa:c~tective coating; at ttze end of the r~easori ardjoz~ ret~xixes the use of aggressive chemicals; , which is undesira.tle on trxe ground of health and envir'cnmertal corasidsratiar~.
EuxopepatenC appli.catioz~ 0 478 OG'7 disclase~ a methac~ fc~r app~.ying a pxatecti.ve ccaating to a greenhouse, which casting provides pxoteGtion against sa~.ar radiation.
~ thin layer of a gxatective agent is applied to a suri~ace, ' ie arid after a rhernical c;~nversioa, a stab~.e caatir~g is ckaained. 2'~s t'emove txse c:aar:;.ng at the end of the seast~n, the coating :~s treated w:vth a szr:ipping agent, which .. . xeiv,es 't~:e stability and the water-resistance of the ~:oata.r~g. ~'he surface can subsequently be easily c3.eaned by rinsing with water.
The protective a~~~nt ezsed according to this European patent appl~.catxon is based an an inorganic pigment sad a ~:ol.ymer~ c bznr~~:r. fhe single example shown the use of cale:iz:~:~ c:arJ~oraate as pigment and a partially esterified 2a atrpc?lrmew Gf styxer~e and maJ.eic acid anhydride as binder.
A pxraec2.ive coati.rrg fox-med from the agent described in ~P~~.-G ~'~B ~~'7 p~:cwzcs to be ixisuffi.ci~eatly reaa.atant to weat~ser ~.nf2uencea. Such a er~at~.ng must be fre~taentJ.y res;:oa:ed or even be re-apgJ.ied several times i.n the course ~5 of are seascan. It is assumed that the instability of the cs:aeing is due Lc 8e~xac~ataon of the polymer chains of the hinder by, fox irzsLance. UV radiation, 1'h:is degradat~.c~n shorter~s the chaa_ns of the binder, thereby reducing tha adhesive stze:ae~th of the,proteative coating. The adverse 3D effect of degradation of the polymer cha~.ns of the binder a a~.l the grater in r_he above~mentioned capoly;raar of at;jx'ene arid ma~.eic acid anhydride because the, chains c~f "hat polymer are aa.teady chart as it ie.
E~uxopean patent application b 5~3 3~? diacJ.oses ~
3S coat ing bases oat a c.apc~iymex of an a, ~-et'h~rlenically ;.~.r~eaturated caxbc~xyla.r- aClC~r another a,~~ezh~~~.enical~.y wv W ;~.:~o ur~sat~:rated raonrarrex and ~.n arrphiphil,»c monorsier. Tn the e~caanpl~a of the app3.icat:.ari, the Coating descr~bed was tented o.n steel pSates. '.Che prope~-tlea that are deemed to a pe re:Levant are drying t~ima, resistance to a~c~.d rain and to r~,xst rxs metallic powders, and xemr7:=abi~.ity by an aqueous.
k~as»c solution.
European paterst appl~.catiar~ D 578 498 xelate~r to a speci.fxc acrylic pc3ymex~ of improved heat resistance and pxrsaessabf.i»ty. xhe p~al~m~e:x has a number-average molecular '.0 wea.g~3t of 3" 30~ to 1, God, C~QS, s~ g~,ass tranaitiorx temperature of ~ 84°C or hic~h~r, and a molecular wea.ght c~la.strxbut~.on of 5 ox leN~. The intended uses of ~ the -- . p.oi~~mca are ir~tcr alza :acr.~lac xu3~ber~s, pressure-serisitiva adiaes~.ves, dispersants, adr~itzves to asphalt, coatings,.
z5 fiber procees~.ng agents, and impra~~ers for r_esirla and water ~.nlcs ' 7;t i~t an abject of the pxespnt invention to pzcwide a pr.otccti~=e er~ai:inc~ wr~ich affords prc~tec.taon against (solar) x°adiatzon and has an adhesive strength such that 20 tre a3~ave-descritaed disadvantages from the prior art do not ~arcuw. What i.s furthr~r contemplated is that the protective wo~~tixag can be easily xe~mtwed at the moment when it is no ic~rtgex c9esi~~wdr Tt has been fou~~td that these objects are achxev~ed 23 ~rhen a paor.ect~.ve coating is formed from a protective agent wh.ch comprises a pigment and a specific bindr~r>
l-.Ycardixy3y, th~e~ ir:,rention reXates to a protective cca,t.ing ,al~xch i9 recne~vab~.e wat.h a,xemavir~g agent cdmpr~.sa.ng a etra-cng base and a ccm~alex former, whieh prote~;~tive. cc~atzrxg ~C~ camp?-a.ses a pigment and a binder, the ba.ndtrr being a pclo~t~r Having a we»ght-average molecular weight of 10,G~~-1~0,0~~ arid an acid value of 90-250.
SuxpYisin.ga~.~, a protective coating aGcordizzg the :i.rwentibn has been found to have excel~.ent adhesive pov~ex .
~5 The coating is sufficiently stable to afford prolax~ged pxotect~.on against, x.~dzatic~z~, withorat requiring irxterim CA 0256142 9 2005-03-15~' regair. Fux~Cher, the coat.i.ng is eminently xes3staz~t to various 'weather iafluencca, sa.ch as rain, frost and W
radiation. ~not.~ex gzeat advarxtage of a protective coating , acGOrdinc~ to the invention is that it can be removed in a 5 marsxzex~ that is nctf particularly ~.abor-intensive nor , res~uxras chemica9.s that affect the environment: unacceptabay ond/or Gnnstxtute health hazards.
The protective ccating according to the invention ca.n be applied to suxfat~es of different raaterials.
to Prefexablg, Ghe surface is a substantially transparent surface, such as axe outuide surface of a gxeenhauge, ft~x instazxce a hc~rticultura~. greer~t~ouse. Typica~.~.y, the surface ._ , w~.ll. be made of glass o;r plsst:i.c. Conver~tiotzal.ly used plasta~.s are, for ir~stamce, pokycarbor~ates, polyoiefins, 15 fsclyathy2~ne t~rephthaXate and polyesters.
,~s stated, the protective coating acaarding to the invention comprises a pigment and a bint3er. Preferably, the pigment is present in art amount of 30-95% by weight, more pxeyerably of 40-85~ by weigh~G, based ort the weight of the ~.o prafiective ccsatixrg. The: binder is preferably. present: in an atnau-ut of 4-60% by vreight, more preferab7.y of fi-45% by weight, based on the we:aght of the protective coating. It has hees~ found that, a )~rotecti~lE Coating containiF~g these coinpaner~ts in these am~~unts hag both rpti.mum protective 25 action and optimum adhesive strength.
As pa.r~ment, any substance can bs used that can ?~e suitably dispersed in a protective agent: from which the protective aoatzng according to the ~.nvent~.on is formed, and which impax'ts to L_he coating the desired protective 3~ acaiar~ against '(solar radiation. Preferably, a pigment a.s used wh::ah yields a white protective cs~ating. Suitable x~igmants are se~.ected fxvm the group of calcium cazbanate, titanium axid~a, a sixicate, such as magnesium or a~.uminuat silicate, gypsum, baryte, and combiaatiorrs thereof.
35 ~epend~.ng on the desired ~Sropezties of the pxot:ective coating, Ghe skilled person w~.ll be abJ.e to suitably select:
CA 02561429 2005-03-15'"""""
Yf V TW rr.7vu the pigmexxt. ~'itanium oxide has a ver~r high covering power, 5o that only s relatively small quantity thereof a.s needed.
As a consequence, the xati.a between binder and pigment is more favorable, when much binder with respect to the 5 pi~net~t can be used,, the weather resistance of Ghe pxot~e4tive coating is better. The advantage of the use of calcium carbo:tate ie that a proteatxve coating based chereor~ becomes slightly transparent in damp weather, so chat the light ~.nteasity within a greenhvuae xd~usts itself ? 0 to the weuthe.'~~~. 4"D1',ld5.C10iIa, further, calcium carbonate is aza cconorwir:al.ly attractive :natural product and ugon removal gives x~.ttle, if any, visual or other Gontaminaci:an of the _ . environment.
An important constituent of the protective coating ZS according to the invention as the polymeric binder. This cnr~stituent should be selected such that a suffica.ent adhesion of the coating to a.surface is obtainarl, while yet the coating ca.n be easi?y removed at any desired time.
According to the i.rwent,ion, as binder, a pa~.ymer as used 20 ~rhich has a weight-average molecular weight of 10, ood-laU,1700 and a.n aGid ve;.lue of 90-250.
'?'he weight-a~~erage molecular weight of the tinder shou~.d not he too low. A low weight-average molecular weic7ht is raoxmal.ly indicative of shore po~.ymex chains, 25 ~~rh.zch wia_1 entai ~, a poG~rex binding effect in the protective agent to be used. Mnzerver, the degzadatzon of ttxe binder under the influence of (W) radiation has mate effect when short cha:ir~~s axa broken than when long chains are broken.
Too high a weight-average molecular weight also entai~.s 34 d:a.sadvantagea. Often, the viscosity a,f the protective agent wili be ton high when, the ehai.ns of the binder are tvo lung. The agent is then difficu3.t to apply to a surface. ~t is preferred that the weight-average rnalecular weight of the poix~nexic binder lies between 15,004, preferab3.y 35 ~0,0~0, a~3d 75,oQc3, preferably 50,000. xhe weight-average molacular~ weight. can be suitably determined with gel.
CA-02561429 2005-03-15' ~'""
~~ y»«. .....,........_ pexmeaticsrs chrcamatograp~:y (CPC) . This techniques which is kryos~fn per se, cyan be c:a6ried out in this connect~.na in a manner lcno~m to these skilled in the art,. using. for ' iriatat~ce, tetrahvdxofuran as solvent and polystyrene se external standard.
Aa~,r~.ther rec~uaremez~t to he satisfied by the k~index a~~cording to the invez~ta on is that it have an acid vr~l.ue of 4th to 2~t~. 'the acid value is connected with the average nxmber of free said scoops per chain of the polymeric 1D binder. This value is ~xeferably 60-160. The ac~.d value can be dete~n~.r.ed key tit~~catiart with patass~.um hydrcxide, with the end poarat-.being det~:nni.ned potentiometrica.~.l~r. The acid - _ valm~: then corresponds co the number of milligrams of paGac~sium hydroxide use3 in the titration per gram o~ the 1~ polymeric b~.ader.
pc5lymer whwch, according t4 the invention, is suitaJ~le for xxse as b~,nder in a protective agent preferably has a p~alydi.spersity of a value of ~ to s, preferably of 3 to 5, Tha term 'polydiepexsity~ used herein means the ratio 2~ between *~he weight-average arid the number-average mo.leculax weight ' CM"li~,) . The number-average molecular weight, like the weight.-average molecular weight, aan be deterrna.ned using GF~C.
~:referabxy. the binder has a glass transition x~ c,em~7erature between 10 and 60°C, with a psrtacular preference far the range between. 20 and 50~C. It has teen fauxzd that a protective Coating based on a polymer satisfying this xeyuixement exhibits particularly suitable adhesion to a surface of a greerhause. It has also been 30 found that using, as a binder, a polymer haring a glass 4rans~.tion temperat~uxe within the range mentioned yields a protective age:~t that has good handling properties and 3s easy i:o apply to form t7:e protective coating.
As binder, both hornopalymers and copolymers can be ~.5 used. The nature of the manomeza in the binder as of ?ess impnrta:ce than tra parameters already mentioned.
CA 02561429 2005-03-15 ~~
The binder i.s preferably a vinyl, polymer. The use c~f a vir7yl.polymer as binder yields an exceptionally suitab~.e protective coating. ~uitahxe monomers arse, fox instance, vinyl aromatic monomers, such as a.~methylstyrene and ~ styrene, a~:rylonitrile, n~thacxyloniGrile, acrylamide3 vinyl acEtaC.e, via~yl chaoxa~de, phe»oxyethyl acxylaxe,.
a~ultitunctxona~. acryiates, such as hexanediol da.methyl acx~ylate, glycol dimethyl acrylate, divinyl benzene and esters of r~et~-~acrylic acid ax acrylic acid, or mixeux~es of 1~ these esters. Exae~les of suit~.ble esters comprise alkyl esz.ers, where the alkyl group can contain arora x to 24 carbon atoms, alk4xy alkyl esters, such as butoxy ethyl.
acxy? a.te and butoxy aak~yl. methaczylate, and hydroxy al3c~r3.
esters. An acrylic acid or methacrylic acid ester can 1~5 a~ccunt far up to °o% of the polymer. when acrylaniLxile or aerylamide is present in the vinyl polymer,, these monornere w~.ll typically be pxes4nt in the polymer in an apt of less than 10 to ~.5~ by weight. Styrene arzd vinyl acetate, x~e5pectively. ~Y acca~,rrt fc~r up to 30 and ~O~k by weight of ~t the pol~~mer. Other suitable monomers are acid mon~acnerr tech as acrylic acid. methacryTic acid, malefic acid, fumaric acid. cxvtonic acs,d, itaconic acid. aconitic acid and semi~esters ther~af, and c~al,eiC ae~.d anhydride and the like. These acid mano~nexs cars be prESerit in amounts of up ~~ to 5~~ by weight. ~arL.~.et~larly suitable monomers art methyl mett:acxyl ate, butyl acrylate, ~-ethy7.hexy7. aczylate, ethyl a~:rylate, styrene, meGhacrylic acid and acrylic acid.
Furtherr ~.t is possible that the polymer a.s wholly crr partly crossli.nkect. ~3.igzbls as crosslinking manamers 3~ axe methylolacry?amide, rnethyl.olmethacxylamide and the Nike. These exosslinkirxg tnc5nomers wiil typicalJ.y a.ccaunt Tc~x r:~at mare than 5~ by weight of the polymer.
In addition to a pigment, a weak base and a binder, a prc:tective coaCi~~g according to Che invention can further 35 comprise a few other components.
""~"wCA 02561429 2005-03-15 . .....,.:"....,.~...~.
Thus, it, is adva:~tageous to include an adhesion pramatex in the,,protective coating. The adhesaion of the , coating ro a surface will be improved by the pa~esence at an acihesi.on prt~mote.r, while tha Ease of removing the 5 protec~:ive casting is ha3-dly, if at all, affected.
~ependa.ng cry the rnateria:t of Ghe surface on which a projective caatirsg is to be provided, the skilled person Wihl ;oe able ~:o selec.G a suitable adhesion promoter_ Pre,fera~ly, the adrission prornt~ter must be water-salable axed 10 cantairr ass amino 5xoup.. ~'ox use on glass suxfaceg, it is recommended tc~ use a silane, such as y-aminopropyltriethoxy silarae, y-arninvpropyltririethoxy silarra, . °~- ta~~~r.3-,yl.smi.na)propyltx~i.methoxy silane, y-am~.ncpxopy~,nethyldiet!rc:xy sflane, y- (2--aminoeGhyl-3-1~ amyxapxopy~7.> triethc~xy silane and y- (2-ama.noethyl-3~-amv~opzopyl)methyldimeth,acy silarra. An adhesion prnrnoter will typically tie present iri the protective agent in an amount c~f O.CS to 1~ by weight, preferably from 0.l to Q.3~r by weight, based can the weight of the protective coating.
~.lnoiPher constituent yielding advantages is a pigment di~~i.der. ~'he presence of such a substance pxavents aggregwtion c-f p5gment upon drying of the protective agenC
~~hich has been applied in diluted foam fvx forming thc~
protective coating. A p~.grnent dzvidex can be present ire 25 amc~urats of fxcrn o.1 to U.5# by weight, based on. the weight of the _t~ratecaive ct~atimg. The nature of the pxgmezlt dzwider dgpsnds on the a;ature of the pagme:~t present in the protective coating. Thus, sodium hexametaphosphate is higl-~l~,r s~.zitalaae wren calcium carbonate ie used as pigment.
30 '~r:en t~.tanium dioxide is used as pigment, for instance a po4yrr;erac mu~.t'_fexnc~ionaT surfactant, such as set-Ad FA
E;oi~ (m-ai?able ~'rom the firan of HMIs AG) can be used excellei.tly as a pigment divider.
Ta optit~ti~e t:~e viscosity of the protective agent 35 f~sr fcrmiag a p:rcwective coating according to the invention, a tjhickener can be included. The optimum 'y'"-~-'""~-~--"' """'CA 02561429 2005-03-15--~~
visca$i.ty c~f t:"xe prcstecti°ae agen t. depends on the method by which the ccsatng is applied to a suxfacs.. I~ a suxface is br~.~shed with a ;protective agent, n highex viscosity wi31 b~
desi.xable t?:an ~ahan a surface is sprayed with a protective agent. ~'uxtner, the viscosity must be sufficient ts~ obtaia~
a thx~:k caati:~g. on the basis of his corn.rnon profeasiona3 kr~nwlc~dge, the a.killed ~~:raon wilt be able to deCexmine which viscosity i~ most ~~u~-table in any given case.
~x~a;rples of thickeners c~;mprise organic arid inorganic 14 thickeners, such as hydroxyethyl cellulose, magneeiu~n all~ma.rtum siaic.ate and oombixzations thereof . The amouxrt of the thi-ckezser will be tuned to the desired viscosity and t~~ip.~',:ca~.ly be batweerx 1 Qnd 5~ by we~.ght, based on the weight ref the pratecti~re coating.
l~ '~v k~e c:~ntioned as othex add~.ti,c~na7. cc~z~stituents of the protective coating axe dispexsants, detergents, an;.ifoam agents, yreserv°ing agents and Che like.
~t wii~. be clear that the invention also xelates to a protective agent for Forming a ~rrotective coating as ZD descxibed shave. Tree protective agent w~.ll conraa,n watex, in addition to Lhe g~ratective coaxing constituents already mE:ntiozxed. zf the protective agent coratains~ calcium cax-t:ondte as pigment, iC will contain such an amot;nt of .
water Chat ~he above-mentioned cons~:ituc~nts of the 25 pxctect=°~re cr_.atir~g in the ratios specified, axe diluted 1,~-~ t.imeb. If titaniL~m oxide is used as pigment, that dzlllt~.orl is a factax of 5-1~ times. It is are advantage of tae vr:~renLiori that no vc~3atil~e axgani.c sr~lventg need tc~ b~:
~.aed .
3d '~refexably, there is also a weak ~aase present in the protects: ve ~:gant accordizig to the znventian. It provides fax neutzG7ization of fYee acid groups pxesent in one or r~c~xe cc~pf~r~er~ts of the agent . Tt has alga been found that the pxes~:nas oaf trze w~:ak base leads to impxc~ve~3 f~ 3m 35 foz-~ration of t:ae protective agesnt upon d~,~zng, when a pror.eLzi.ve coating ~.s being formed. Preferably, the ~ueak "'~~CA 02561429 2005-03-15 1 ~D
base is selected from the group of ammonia. monoy di- and trxall~ylarnines, with the alkyl ~3ro9ap captaining from 1 tra a cax;~-on atoms. Particularly preferred ig ammonia. .
The weak base zs pr~af~rably present in an amount of 0.2-5%. by weight, mare preferably c~f t~.~-3% by wea-ght, based cn the weight of the protective agent.
As stated, the application of the protective age»t tv fcnr a prcteGtive ccati.ng can occur in different ways.
Fc~ssib;le Ways include spraying, brushing and the like. The pratective aet~ion of the coating will be hardly, if at a21, affected by the rnanner of appliCatian.
When an the course of time, for instance at the end _ of the eeason, the protective cvatxng is to be removed, the casting aceordi.r~g to the ino~entinn is treated with a .
xwmaving agent;, ::cmprising a stror=.g base and a complex fcz~mer. The wemaving agent renders the binder in the protQCtwve coating water-soluble.
~'he strong k~ase ig preferably preserxt in the z~movirxc~ agent r n an amourti: df from 2 to 1U% by weight, zQ more preferably of frcm 2 to ~% by weight, based on the weight of the xemaving agent. Suitable strong bases axe, fc~r instance, alkali metal hydroxides Such as sodium hydraa.icie, potassium hydr«xide and lithium hydroxide.
PreferabJ.y, sodium hydroxide is used.
Preferably p~'esent, in addition to the strong base, ' is a oomplex far~eer, pref_rably in an amount of 2 to 10% ~by weight, based ors the weight of the rEmoving agent. Tt hat ;peen found that e:~pecaally the use of the Grisodiurn salt of nitrilo-triacetic acid or the tetrasodium salt of ethylene 30 diamine tetrsacetc a;:id grea'~ly promotes the protective casting becoming soiuble. The use of Crisodium salt of nitrila-trla~e~:ic ar;ad is preferred. .'this substance is , ~.~operly an~~ rapidly biodegradable.
EspECia:Lly when a protecti~re coating provided on a 35 plastic is to be removed, it is found to be of great adwntac;e to tae a removing agent that furzhex comprises «;n az organic solvent. 1t is also possible to use an organic solveist separately, in additions to tha removing agent. The latter oFtion is adiantageous in that the axga.ttic solvent used does not necessarily need to be a?ka~.~:-reBisLant. A
great many solvents are eligible for use as a separate compaz~ent. ~xamgles include benxyl alcohol, tet.xahydrofuran, 1, 4-di.r~xane,~ dimethyl sulfaxide, higher alcohols, such as butanoJ, pentanal, hexanol, cyalahexanol and isomers thereof, and cyclahexanc~ne. Tha orga-ni.c solvent 1o effects a still easier; removal of the protective coating.
It is preferred to use the organic solvent in the removing agent. This is Z~ene~icial an particular to the s~mp3.icity of the procedure of removing the protective orating. In that case, an alkali-resistant organic solvent shr~uld be used. The amaun.t of arcranic solvent i8 preferably ~0-:30~ by weight, more preferabJ-y 1~-Z5~ by weight, based on the weight of the removing agent. particularly preferred is the use of benzyl alcoh~al, Ben~y1 alcohol is little vr~latiZe, little toxic to ~nan and an.imaXs and hardly 2~! camlauscib7-e, so that the health of hose working with the re~ntwing agent. is not put at xi&k. When benryl aycohol ends up in the envarQrment after the removal of the protective coz~t.~.rig, this dons n,ot yield unacr_egcsble coneamination.
In addition to the eonstatuesats mentioned, the removing agent may fuxtlzex contain a thickener, such as xanthan gum. Xanthan gun xcnders the removing agent highly pseudop3astic, so that ~.t i,s thin when being applied and tha,ck after being applied. Thin prdpr~xty p, rEVents r~he agent from f,'.owing off the surface too fast. Further, the 3D re-.r~cving agent may contain a substance reducing the s~uw-face eens:~na, ox an ec:~ulsif~er. For inatane~e, the sodium slit of ~:,decylk;erazenasuifo:u.c acis3 is suitable.
To xemave the pz.-catective coating, the coGtina is treated with the a'acve-described removing agent. yh-.a treatment comprises aui.tabl.y applying, a9 by spraying an pouring, the removing agent oneo the coating Gm he removed.
'T°ical?y, the removing agent is zsed in a S to ZO-fold c3ilutinn. After app~.icatian rf the removing agent, the surf~sce ran be rinsed with water. Tt is also possible tr ~ , allow the rain to wash things ofd. Thereafter, virtually all txacss of tfie protective coating will be.gone.
The irw~ention w~,l:l. presently be further e1 ucidated ire anci by the following e~samples.
E'xar~,n7.e 1,_Pr~~aration of a ~arotec~.ivp agex~t 1G~ Tn a reaction vessel, ,the follovair~g substaneess were added to each other in the order apecifa.ed~
wt . %
_, . w~ttex' 3~.9 alJ.yl ethc~xylate (non-ionic surfaet.arW) a.z '' S unt i foam ac~enC Q . 3 3Cr'6 salutiQn of sodium hexametaphos~rhate 0.6 ommc~na.a s~oluCiolx '~,'S% 1.5 polymer dispersion ~) 19.~
~vnelv divi~3ed calcium carbonate 4~3 'D
Ttze mi,x~ture obtained was stirxed °or 20 minutes under high.
sk:raar canditic~ns .
Timken the foJ.lowing subsr_ances mare lidded, i.n succession:
magnes~.um alc~aniraum silicate 0.8 fz~drcx~~et kxyl aelluloee a . 5 ~reserviry agent 0.1 5~?~ eclution of y-aminopx~pyltriethoxy silane D.2 3U p~~ui.n, vigorous st2-~ri:~g was carried out, until a ~:crncge.nEnus pxoduct vras foamed.
*) 'i"Yae polymer dispersion uved toad a solids content of 4S
a~zd an acwci value ref 73, caxculated on the go7.ids content.
sS The polymer in Lhe L~indel had kaeen for ned excltrsa.vely Lrom acr~,~s~ate moriorr~exs .
viscosity of end product at 20°C
2fl Fa.sey tBroc;kfield 0.5 z~pm, spindle 5) vise~sity of dilution of use at 20°~ (~. pant by weight of ' product c3~.~,uted with 1.5 paxts by weight of water) ~D mFa.sea tHxookfield G.9 rpan, spindle 1) Fxamp~e 2: Precaratir~n of a remo~rine~aq~nt In a react.-ion vessel, the following substar~cee were added 1~ to each oth$r in the prder specifzsd:
wt.~
_ . w~tex ' 73 ;~anthan gum 0.5 i6 "3~e ~ri~cLUre obtained wa:. sti:rred at a mcdexate speed, ux~tzl a t:~ickening tied occurred.
Then the following were added, in succession:
:~0 sodium hyetroacide splut~.on 33% 6.~
solLtzon of trisadium n tri,lotriacetate 40% 20 30°s so:~utior. of an amphoteric surfactant 0.5 Stirxir_g was carxied out until a homcgeneous product was ~5 faxwed_ Viscosity of ez~d prc:duct 20°C:
30 Fa.sec t8xoakfi.eld 0.5 rpm, spindle 5) Vzscvsity of da.luti.an c~f use at 2n°~ (Z part by weight ~f 30 groduct diluted with fi-ve parts by weight of watex):
4D mpa.sec tisxoakfield ~.5 xpcn, spindle 1) 1e 3 , cYtr ~ t~ r6tec ~.v atiri The pxntective agent of Example 1 was diluted wi'h ~5 1.a paz-ts by weagh'C of watex and applied to a glass horticultural greenhouse by spraying in the early spxing.
After six months, ~:he px~ctt~aiwe coating formed was etil~.
fu3ly int ~AcIG .
~~a ~ 4: ~er.~a~,ri a x'c~tectatre natm .~.~,:..~,.,._.~,._.m......~p . ~~'C xen~oring agent of ~xumple 2 was dilur.ed, for use, with fire parts by weaght of water and applied to the yrotective coaGinsg of Example 3 by spraying in the autumn. After a few ahc~we:rs of ra~.n, which h;ad came down by the end of a few days, the protecGa.~re coat;a.a-~g was found to have been 1,0 con;p~.~ae~.y washed off 3~y the rain.
~.~:amt~le 5: ~arat3cn of a oro ecCive agewt In a,xea.ctian vess~:~, the following subs:ances were added earl: othex irz the order specified:
wt.~
water 6.0 Sex-AD FA 6a?~' ~~i~.ls AG) ~ 0.3 alkyl wGhox~~lats (txr~n-ie~nic ~;urfactant) 0.3 polymex dispersion *1 3.0 antif pam agent 0.5 titanium white The ~raixt~:re abta~.nec~ was disrsed with e~ hi.gr shear dissc:~.~~er untie the desired fineness was achieved.
~"!teri t7ve rolxowing wexe added, i.n sucCessian:
water 31.3 tvy~3xo:xyetMyl cel~.u~.ase 0.90 :30 St3rxiryg was pexfcxmed until a ha:nr>ger~eous mixture was ebrained. i:~er. the foT7_cwing were added, zn succession:
am.-noria solution 25~ 3.4 poi. ymer dz seers Lcrt~ * ) 34 preserving ngent 0.~
~G~ soluta~on of y°a~ninc;propyltrie~:hoxy silane a.2 xs ~,'gc~zour~ st.rxing a=mss pm:fo::med ~:rxtil a horna~ene~oua praduc~
~r~xs fo~~d.
*) ~°he pcalymex~ disgersio~a used had ~ solic)e content c~~ ~#5%
and an acid value of ~3, ~a~cu~.atec~ on the solids aotxt~at.
T)-~e polymer in tree binder had Seri farmed exclusively from acr~raate mc~.u;~amers.
Vis~:~aity at er~d pxoduct rrt ~0°Cs ~.0 10 pa.sec taxoakfie3ld 0.5 rpm. spindxe S) t~iacouity of dilutic~~. of use at 2G°C (1 part by ~reigbt of pxoduet daluted with fdtvr pax-ta by weight of water) _ x5 mpa.sec (Bx~ookfield 0.5 rpm, spindle 7.) I5 ~xa le~~ ~'Y'E~J~XutlOf: c5f a xemav~fr~a ~caent Tn d reaction vessel, tl~e fc7.l.owix~g suhetances were added to each other in the oraex specified:
wt.#
grater 5~ . s5 2a Xanthan gum ~ 0.5 ml~~e mxxtur~e obtained was stir°ed at a moderate speed, unxil a thickening was achieved.
',hen thexe were added, ~.n succession:
25 ~odecyLhenxenesulfanic acid sodium hydrox.de salutao» 3~% ~~Z
soiutinn of. trisodiurn ~:iCri~.atr:.acetate 90~ 10 t%er~2~,~1 a~.cahol 25 dine vii 0.5 0 5ti.~cring spas pex~ormed unta.l a homogeneous product was farmed.
visco;~ity of end pxocuct 20°C:
Pa . sec (~srookf ieZd_ ~7 . S r-pm, spind~ a 5 ) 1 ~6 Visccasity csf dilution o: use at ~:fl°C (1 part by weight of proc9uct dxlmted with five parts by we~.ght of water) a , 2o rnPa.sec ;8~oakfield ~.5 rpm, spindle ~.~
~'xam~l a '~ L r~.rmi ns~ a nratect~rv colt t xnq The pr~tecteve ag~r_t of E°~cample 5 was diluted with four part by waight ct water arid ,app~.:~ed to a plastic . horticultural tuiused by spxaying, in the early spring.
1.0 After sxx months, the px-ratective ooating formet~ was still fully ir~taGt .
scar. 1e ~ : ~~movirc~ a r~tective cn,~tina 15 Tree r~mavirig agent df E~:ampl.e 6 was diluted with tiv~ parts by ws_~ght c~f water and «pplied by spraying onto the protective coating of Ea:ample 7, in the autuatn,. After a, short :.irne of actiotr, tt~e pxoteGtive ccatiag was removed completely with a water jet.
xhis invex~tiaxt relates Go a remvvab3.e protective acating, and to a protective agent and a method for forming such coating.
In horticulture, many .plants are grown in ~ greenhouses. ~ltusr they ~:an benefit from optimized conc~it~.ons, such as temperature, nmaunt of light, humidity and the like. However. a problem here is that the plants being grown axe exposed. under waxen, sunny weather condi.tacnsr to a Lax-ga art~nunt of radiation, which might 1.0 disturb the living caxzditions and grtawth of the plants, algid might even reuse them to burn. To obviate this problem, it~
is customary in horticulture to protect the planGS during the spring and the summ~:r against they adverse effect of uz.due radiation cy providing the transparent surfaces of la tYie greezzhc~use with a protective coating.
one of the chief requirements to ba met Jay such a prratective casting ~.s that sufficient prvteCtion #rom light.
anti heat is achieved. Ta meet this requi.remerit, the prcreGtive coating, should contain a pigment, such as cha~.k 20 or titanium oxide. A further important requirement is that the protective agent from which the protective coating is fozmed exhihits suffic:3ent adhesion to the surface of a greer,'zouse~ When its adhesive str~eragth is too Sow, the , coa~:ing wall not be resistant to weather influences and it 2S will be necessary tc~ restore the coating sevezal times per season .ox to rPplaaa~ it. When adhesion i.s too strong., it requires much effort to remove the coating at the end of the seasax~, In European patent apgla.cation 0 428 X37, it is 3c3 pzcpc~sed to use a prat.Prtive agent based on a polymeric binder anc3 pigments, >suc:h as aluminum pigments, titanium pig;~~r~ts or calcium c~~rbc~r_ate. No particular requirement$
are set with regard to the nature o~ the pc~lymexic binder.
In practice, it has be~ea f.~und that many palymera.c 35 binders impart too high an adhesive strength to the °
'-"~"'--'-""'~°' " ~'CA 02561429 2005-03-15'-' "' z prcteotive agent. This ma.l:es it particularly labor-irstensi.ve tca remove the pa:c~tective coating; at ttze end of the r~easori ardjoz~ ret~xixes the use of aggressive chemicals; , which is undesira.tle on trxe ground of health and envir'cnmertal corasidsratiar~.
EuxopepatenC appli.catioz~ 0 478 OG'7 disclase~ a methac~ fc~r app~.ying a pxatecti.ve ccaating to a greenhouse, which casting provides pxoteGtion against sa~.ar radiation.
~ thin layer of a gxatective agent is applied to a suri~ace, ' ie arid after a rhernical c;~nversioa, a stab~.e caatir~g is ckaained. 2'~s t'emove txse c:aar:;.ng at the end of the seast~n, the coating :~s treated w:vth a szr:ipping agent, which .. . xeiv,es 't~:e stability and the water-resistance of the ~:oata.r~g. ~'he surface can subsequently be easily c3.eaned by rinsing with water.
The protective a~~~nt ezsed according to this European patent appl~.catxon is based an an inorganic pigment sad a ~:ol.ymer~ c bznr~~:r. fhe single example shown the use of cale:iz:~:~ c:arJ~oraate as pigment and a partially esterified 2a atrpc?lrmew Gf styxer~e and maJ.eic acid anhydride as binder.
A pxraec2.ive coati.rrg fox-med from the agent described in ~P~~.-G ~'~B ~~'7 p~:cwzcs to be ixisuffi.ci~eatly reaa.atant to weat~ser ~.nf2uencea. Such a er~at~.ng must be fre~taentJ.y res;:oa:ed or even be re-apgJ.ied several times i.n the course ~5 of are seascan. It is assumed that the instability of the cs:aeing is due Lc 8e~xac~ataon of the polymer chains of the hinder by, fox irzsLance. UV radiation, 1'h:is degradat~.c~n shorter~s the chaa_ns of the binder, thereby reducing tha adhesive stze:ae~th of the,proteative coating. The adverse 3D effect of degradation of the polymer cha~.ns of the binder a a~.l the grater in r_he above~mentioned capoly;raar of at;jx'ene arid ma~.eic acid anhydride because the, chains c~f "hat polymer are aa.teady chart as it ie.
E~uxopean patent application b 5~3 3~? diacJ.oses ~
3S coat ing bases oat a c.apc~iymex of an a, ~-et'h~rlenically ;.~.r~eaturated caxbc~xyla.r- aClC~r another a,~~ezh~~~.enical~.y wv W ;~.:~o ur~sat~:rated raonrarrex and ~.n arrphiphil,»c monorsier. Tn the e~caanpl~a of the app3.icat:.ari, the Coating descr~bed was tented o.n steel pSates. '.Che prope~-tlea that are deemed to a pe re:Levant are drying t~ima, resistance to a~c~.d rain and to r~,xst rxs metallic powders, and xemr7:=abi~.ity by an aqueous.
k~as»c solution.
European paterst appl~.catiar~ D 578 498 xelate~r to a speci.fxc acrylic pc3ymex~ of improved heat resistance and pxrsaessabf.i»ty. xhe p~al~m~e:x has a number-average molecular '.0 wea.g~3t of 3" 30~ to 1, God, C~QS, s~ g~,ass tranaitiorx temperature of ~ 84°C or hic~h~r, and a molecular wea.ght c~la.strxbut~.on of 5 ox leN~. The intended uses of ~ the -- . p.oi~~mca are ir~tcr alza :acr.~lac xu3~ber~s, pressure-serisitiva adiaes~.ves, dispersants, adr~itzves to asphalt, coatings,.
z5 fiber procees~.ng agents, and impra~~ers for r_esirla and water ~.nlcs ' 7;t i~t an abject of the pxespnt invention to pzcwide a pr.otccti~=e er~ai:inc~ wr~ich affords prc~tec.taon against (solar) x°adiatzon and has an adhesive strength such that 20 tre a3~ave-descritaed disadvantages from the prior art do not ~arcuw. What i.s furthr~r contemplated is that the protective wo~~tixag can be easily xe~mtwed at the moment when it is no ic~rtgex c9esi~~wdr Tt has been fou~~td that these objects are achxev~ed 23 ~rhen a paor.ect~.ve coating is formed from a protective agent wh.ch comprises a pigment and a specific bindr~r>
l-.Ycardixy3y, th~e~ ir:,rention reXates to a protective cca,t.ing ,al~xch i9 recne~vab~.e wat.h a,xemavir~g agent cdmpr~.sa.ng a etra-cng base and a ccm~alex former, whieh prote~;~tive. cc~atzrxg ~C~ camp?-a.ses a pigment and a binder, the ba.ndtrr being a pclo~t~r Having a we»ght-average molecular weight of 10,G~~-1~0,0~~ arid an acid value of 90-250.
SuxpYisin.ga~.~, a protective coating aGcordizzg the :i.rwentibn has been found to have excel~.ent adhesive pov~ex .
~5 The coating is sufficiently stable to afford prolax~ged pxotect~.on against, x.~dzatic~z~, withorat requiring irxterim CA 0256142 9 2005-03-15~' regair. Fux~Cher, the coat.i.ng is eminently xes3staz~t to various 'weather iafluencca, sa.ch as rain, frost and W
radiation. ~not.~ex gzeat advarxtage of a protective coating , acGOrdinc~ to the invention is that it can be removed in a 5 marsxzex~ that is nctf particularly ~.abor-intensive nor , res~uxras chemica9.s that affect the environment: unacceptabay ond/or Gnnstxtute health hazards.
The protective ccating according to the invention ca.n be applied to suxfat~es of different raaterials.
to Prefexablg, Ghe surface is a substantially transparent surface, such as axe outuide surface of a gxeenhauge, ft~x instazxce a hc~rticultura~. greer~t~ouse. Typica~.~.y, the surface ._ , w~.ll. be made of glass o;r plsst:i.c. Conver~tiotzal.ly used plasta~.s are, for ir~stamce, pokycarbor~ates, polyoiefins, 15 fsclyathy2~ne t~rephthaXate and polyesters.
,~s stated, the protective coating acaarding to the invention comprises a pigment and a bint3er. Preferably, the pigment is present in art amount of 30-95% by weight, more pxeyerably of 40-85~ by weigh~G, based ort the weight of the ~.o prafiective ccsatixrg. The: binder is preferably. present: in an atnau-ut of 4-60% by vreight, more preferab7.y of fi-45% by weight, based on the we:aght of the protective coating. It has hees~ found that, a )~rotecti~lE Coating containiF~g these coinpaner~ts in these am~~unts hag both rpti.mum protective 25 action and optimum adhesive strength.
As pa.r~ment, any substance can bs used that can ?~e suitably dispersed in a protective agent: from which the protective aoatzng according to the ~.nvent~.on is formed, and which impax'ts to L_he coating the desired protective 3~ acaiar~ against '(solar radiation. Preferably, a pigment a.s used wh::ah yields a white protective cs~ating. Suitable x~igmants are se~.ected fxvm the group of calcium cazbanate, titanium axid~a, a sixicate, such as magnesium or a~.uminuat silicate, gypsum, baryte, and combiaatiorrs thereof.
35 ~epend~.ng on the desired ~Sropezties of the pxot:ective coating, Ghe skilled person w~.ll be abJ.e to suitably select:
CA 02561429 2005-03-15'"""""
Yf V TW rr.7vu the pigmexxt. ~'itanium oxide has a ver~r high covering power, 5o that only s relatively small quantity thereof a.s needed.
As a consequence, the xati.a between binder and pigment is more favorable, when much binder with respect to the 5 pi~net~t can be used,, the weather resistance of Ghe pxot~e4tive coating is better. The advantage of the use of calcium carbo:tate ie that a proteatxve coating based chereor~ becomes slightly transparent in damp weather, so chat the light ~.nteasity within a greenhvuae xd~usts itself ? 0 to the weuthe.'~~~. 4"D1',ld5.C10iIa, further, calcium carbonate is aza cconorwir:al.ly attractive :natural product and ugon removal gives x~.ttle, if any, visual or other Gontaminaci:an of the _ . environment.
An important constituent of the protective coating ZS according to the invention as the polymeric binder. This cnr~stituent should be selected such that a suffica.ent adhesion of the coating to a.surface is obtainarl, while yet the coating ca.n be easi?y removed at any desired time.
According to the i.rwent,ion, as binder, a pa~.ymer as used 20 ~rhich has a weight-average molecular weight of 10, ood-laU,1700 and a.n aGid ve;.lue of 90-250.
'?'he weight-a~~erage molecular weight of the tinder shou~.d not he too low. A low weight-average molecular weic7ht is raoxmal.ly indicative of shore po~.ymex chains, 25 ~~rh.zch wia_1 entai ~, a poG~rex binding effect in the protective agent to be used. Mnzerver, the degzadatzon of ttxe binder under the influence of (W) radiation has mate effect when short cha:ir~~s axa broken than when long chains are broken.
Too high a weight-average molecular weight also entai~.s 34 d:a.sadvantagea. Often, the viscosity a,f the protective agent wili be ton high when, the ehai.ns of the binder are tvo lung. The agent is then difficu3.t to apply to a surface. ~t is preferred that the weight-average rnalecular weight of the poix~nexic binder lies between 15,004, preferab3.y 35 ~0,0~0, a~3d 75,oQc3, preferably 50,000. xhe weight-average molacular~ weight. can be suitably determined with gel.
CA-02561429 2005-03-15' ~'""
~~ y»«. .....,........_ pexmeaticsrs chrcamatograp~:y (CPC) . This techniques which is kryos~fn per se, cyan be c:a6ried out in this connect~.na in a manner lcno~m to these skilled in the art,. using. for ' iriatat~ce, tetrahvdxofuran as solvent and polystyrene se external standard.
Aa~,r~.ther rec~uaremez~t to he satisfied by the k~index a~~cording to the invez~ta on is that it have an acid vr~l.ue of 4th to 2~t~. 'the acid value is connected with the average nxmber of free said scoops per chain of the polymeric 1D binder. This value is ~xeferably 60-160. The ac~.d value can be dete~n~.r.ed key tit~~catiart with patass~.um hydrcxide, with the end poarat-.being det~:nni.ned potentiometrica.~.l~r. The acid - _ valm~: then corresponds co the number of milligrams of paGac~sium hydroxide use3 in the titration per gram o~ the 1~ polymeric b~.ader.
pc5lymer whwch, according t4 the invention, is suitaJ~le for xxse as b~,nder in a protective agent preferably has a p~alydi.spersity of a value of ~ to s, preferably of 3 to 5, Tha term 'polydiepexsity~ used herein means the ratio 2~ between *~he weight-average arid the number-average mo.leculax weight ' CM"li~,) . The number-average molecular weight, like the weight.-average molecular weight, aan be deterrna.ned using GF~C.
~:referabxy. the binder has a glass transition x~ c,em~7erature between 10 and 60°C, with a psrtacular preference far the range between. 20 and 50~C. It has teen fauxzd that a protective Coating based on a polymer satisfying this xeyuixement exhibits particularly suitable adhesion to a surface of a greerhause. It has also been 30 found that using, as a binder, a polymer haring a glass 4rans~.tion temperat~uxe within the range mentioned yields a protective age:~t that has good handling properties and 3s easy i:o apply to form t7:e protective coating.
As binder, both hornopalymers and copolymers can be ~.5 used. The nature of the manomeza in the binder as of ?ess impnrta:ce than tra parameters already mentioned.
CA 02561429 2005-03-15 ~~
The binder i.s preferably a vinyl, polymer. The use c~f a vir7yl.polymer as binder yields an exceptionally suitab~.e protective coating. ~uitahxe monomers arse, fox instance, vinyl aromatic monomers, such as a.~methylstyrene and ~ styrene, a~:rylonitrile, n~thacxyloniGrile, acrylamide3 vinyl acEtaC.e, via~yl chaoxa~de, phe»oxyethyl acxylaxe,.
a~ultitunctxona~. acryiates, such as hexanediol da.methyl acx~ylate, glycol dimethyl acrylate, divinyl benzene and esters of r~et~-~acrylic acid ax acrylic acid, or mixeux~es of 1~ these esters. Exae~les of suit~.ble esters comprise alkyl esz.ers, where the alkyl group can contain arora x to 24 carbon atoms, alk4xy alkyl esters, such as butoxy ethyl.
acxy? a.te and butoxy aak~yl. methaczylate, and hydroxy al3c~r3.
esters. An acrylic acid or methacrylic acid ester can 1~5 a~ccunt far up to °o% of the polymer. when acrylaniLxile or aerylamide is present in the vinyl polymer,, these monornere w~.ll typically be pxes4nt in the polymer in an apt of less than 10 to ~.5~ by weight. Styrene arzd vinyl acetate, x~e5pectively. ~Y acca~,rrt fc~r up to 30 and ~O~k by weight of ~t the pol~~mer. Other suitable monomers are acid mon~acnerr tech as acrylic acid. methacryTic acid, malefic acid, fumaric acid. cxvtonic acs,d, itaconic acid. aconitic acid and semi~esters ther~af, and c~al,eiC ae~.d anhydride and the like. These acid mano~nexs cars be prESerit in amounts of up ~~ to 5~~ by weight. ~arL.~.et~larly suitable monomers art methyl mett:acxyl ate, butyl acrylate, ~-ethy7.hexy7. aczylate, ethyl a~:rylate, styrene, meGhacrylic acid and acrylic acid.
Furtherr ~.t is possible that the polymer a.s wholly crr partly crossli.nkect. ~3.igzbls as crosslinking manamers 3~ axe methylolacry?amide, rnethyl.olmethacxylamide and the Nike. These exosslinkirxg tnc5nomers wiil typicalJ.y a.ccaunt Tc~x r:~at mare than 5~ by weight of the polymer.
In addition to a pigment, a weak base and a binder, a prc:tective coaCi~~g according to Che invention can further 35 comprise a few other components.
""~"wCA 02561429 2005-03-15 . .....,.:"....,.~...~.
Thus, it, is adva:~tageous to include an adhesion pramatex in the,,protective coating. The adhesaion of the , coating ro a surface will be improved by the pa~esence at an acihesi.on prt~mote.r, while tha Ease of removing the 5 protec~:ive casting is ha3-dly, if at all, affected.
~ependa.ng cry the rnateria:t of Ghe surface on which a projective caatirsg is to be provided, the skilled person Wihl ;oe able ~:o selec.G a suitable adhesion promoter_ Pre,fera~ly, the adrission prornt~ter must be water-salable axed 10 cantairr ass amino 5xoup.. ~'ox use on glass suxfaceg, it is recommended tc~ use a silane, such as y-aminopropyltriethoxy silarae, y-arninvpropyltririethoxy silarra, . °~- ta~~~r.3-,yl.smi.na)propyltx~i.methoxy silane, y-am~.ncpxopy~,nethyldiet!rc:xy sflane, y- (2--aminoeGhyl-3-1~ amyxapxopy~7.> triethc~xy silane and y- (2-ama.noethyl-3~-amv~opzopyl)methyldimeth,acy silarra. An adhesion prnrnoter will typically tie present iri the protective agent in an amount c~f O.CS to 1~ by weight, preferably from 0.l to Q.3~r by weight, based can the weight of the protective coating.
~.lnoiPher constituent yielding advantages is a pigment di~~i.der. ~'he presence of such a substance pxavents aggregwtion c-f p5gment upon drying of the protective agenC
~~hich has been applied in diluted foam fvx forming thc~
protective coating. A p~.grnent dzvidex can be present ire 25 amc~urats of fxcrn o.1 to U.5# by weight, based on. the weight of the _t~ratecaive ct~atimg. The nature of the pxgmezlt dzwider dgpsnds on the a;ature of the pagme:~t present in the protective coating. Thus, sodium hexametaphosphate is higl-~l~,r s~.zitalaae wren calcium carbonate ie used as pigment.
30 '~r:en t~.tanium dioxide is used as pigment, for instance a po4yrr;erac mu~.t'_fexnc~ionaT surfactant, such as set-Ad FA
E;oi~ (m-ai?able ~'rom the firan of HMIs AG) can be used excellei.tly as a pigment divider.
Ta optit~ti~e t:~e viscosity of the protective agent 35 f~sr fcrmiag a p:rcwective coating according to the invention, a tjhickener can be included. The optimum 'y'"-~-'""~-~--"' """'CA 02561429 2005-03-15--~~
visca$i.ty c~f t:"xe prcstecti°ae agen t. depends on the method by which the ccsatng is applied to a suxfacs.. I~ a suxface is br~.~shed with a ;protective agent, n highex viscosity wi31 b~
desi.xable t?:an ~ahan a surface is sprayed with a protective agent. ~'uxtner, the viscosity must be sufficient ts~ obtaia~
a thx~:k caati:~g. on the basis of his corn.rnon profeasiona3 kr~nwlc~dge, the a.killed ~~:raon wilt be able to deCexmine which viscosity i~ most ~~u~-table in any given case.
~x~a;rples of thickeners c~;mprise organic arid inorganic 14 thickeners, such as hydroxyethyl cellulose, magneeiu~n all~ma.rtum siaic.ate and oombixzations thereof . The amouxrt of the thi-ckezser will be tuned to the desired viscosity and t~~ip.~',:ca~.ly be batweerx 1 Qnd 5~ by we~.ght, based on the weight ref the pratecti~re coating.
l~ '~v k~e c:~ntioned as othex add~.ti,c~na7. cc~z~stituents of the protective coating axe dispexsants, detergents, an;.ifoam agents, yreserv°ing agents and Che like.
~t wii~. be clear that the invention also xelates to a protective agent for Forming a ~rrotective coating as ZD descxibed shave. Tree protective agent w~.ll conraa,n watex, in addition to Lhe g~ratective coaxing constituents already mE:ntiozxed. zf the protective agent coratains~ calcium cax-t:ondte as pigment, iC will contain such an amot;nt of .
water Chat ~he above-mentioned cons~:ituc~nts of the 25 pxctect=°~re cr_.atir~g in the ratios specified, axe diluted 1,~-~ t.imeb. If titaniL~m oxide is used as pigment, that dzlllt~.orl is a factax of 5-1~ times. It is are advantage of tae vr:~renLiori that no vc~3atil~e axgani.c sr~lventg need tc~ b~:
~.aed .
3d '~refexably, there is also a weak ~aase present in the protects: ve ~:gant accordizig to the znventian. It provides fax neutzG7ization of fYee acid groups pxesent in one or r~c~xe cc~pf~r~er~ts of the agent . Tt has alga been found that the pxes~:nas oaf trze w~:ak base leads to impxc~ve~3 f~ 3m 35 foz-~ration of t:ae protective agesnt upon d~,~zng, when a pror.eLzi.ve coating ~.s being formed. Preferably, the ~ueak "'~~CA 02561429 2005-03-15 1 ~D
base is selected from the group of ammonia. monoy di- and trxall~ylarnines, with the alkyl ~3ro9ap captaining from 1 tra a cax;~-on atoms. Particularly preferred ig ammonia. .
The weak base zs pr~af~rably present in an amount of 0.2-5%. by weight, mare preferably c~f t~.~-3% by wea-ght, based cn the weight of the protective agent.
As stated, the application of the protective age»t tv fcnr a prcteGtive ccati.ng can occur in different ways.
Fc~ssib;le Ways include spraying, brushing and the like. The pratective aet~ion of the coating will be hardly, if at a21, affected by the rnanner of appliCatian.
When an the course of time, for instance at the end _ of the eeason, the protective cvatxng is to be removed, the casting aceordi.r~g to the ino~entinn is treated with a .
xwmaving agent;, ::cmprising a stror=.g base and a complex fcz~mer. The wemaving agent renders the binder in the protQCtwve coating water-soluble.
~'he strong k~ase ig preferably preserxt in the z~movirxc~ agent r n an amourti: df from 2 to 1U% by weight, zQ more preferably of frcm 2 to ~% by weight, based on the weight of the xemaving agent. Suitable strong bases axe, fc~r instance, alkali metal hydroxides Such as sodium hydraa.icie, potassium hydr«xide and lithium hydroxide.
PreferabJ.y, sodium hydroxide is used.
Preferably p~'esent, in addition to the strong base, ' is a oomplex far~eer, pref_rably in an amount of 2 to 10% ~by weight, based ors the weight of the rEmoving agent. Tt hat ;peen found that e:~pecaally the use of the Grisodiurn salt of nitrilo-triacetic acid or the tetrasodium salt of ethylene 30 diamine tetrsacetc a;:id grea'~ly promotes the protective casting becoming soiuble. The use of Crisodium salt of nitrila-trla~e~:ic ar;ad is preferred. .'this substance is , ~.~operly an~~ rapidly biodegradable.
EspECia:Lly when a protecti~re coating provided on a 35 plastic is to be removed, it is found to be of great adwntac;e to tae a removing agent that furzhex comprises «;n az organic solvent. 1t is also possible to use an organic solveist separately, in additions to tha removing agent. The latter oFtion is adiantageous in that the axga.ttic solvent used does not necessarily need to be a?ka~.~:-reBisLant. A
great many solvents are eligible for use as a separate compaz~ent. ~xamgles include benxyl alcohol, tet.xahydrofuran, 1, 4-di.r~xane,~ dimethyl sulfaxide, higher alcohols, such as butanoJ, pentanal, hexanol, cyalahexanol and isomers thereof, and cyclahexanc~ne. Tha orga-ni.c solvent 1o effects a still easier; removal of the protective coating.
It is preferred to use the organic solvent in the removing agent. This is Z~ene~icial an particular to the s~mp3.icity of the procedure of removing the protective orating. In that case, an alkali-resistant organic solvent shr~uld be used. The amaun.t of arcranic solvent i8 preferably ~0-:30~ by weight, more preferabJ-y 1~-Z5~ by weight, based on the weight of the removing agent. particularly preferred is the use of benzyl alcoh~al, Ben~y1 alcohol is little vr~latiZe, little toxic to ~nan and an.imaXs and hardly 2~! camlauscib7-e, so that the health of hose working with the re~ntwing agent. is not put at xi&k. When benryl aycohol ends up in the envarQrment after the removal of the protective coz~t.~.rig, this dons n,ot yield unacr_egcsble coneamination.
In addition to the eonstatuesats mentioned, the removing agent may fuxtlzex contain a thickener, such as xanthan gum. Xanthan gun xcnders the removing agent highly pseudop3astic, so that ~.t i,s thin when being applied and tha,ck after being applied. Thin prdpr~xty p, rEVents r~he agent from f,'.owing off the surface too fast. Further, the 3D re-.r~cving agent may contain a substance reducing the s~uw-face eens:~na, ox an ec:~ulsif~er. For inatane~e, the sodium slit of ~:,decylk;erazenasuifo:u.c acis3 is suitable.
To xemave the pz.-catective coating, the coGtina is treated with the a'acve-described removing agent. yh-.a treatment comprises aui.tabl.y applying, a9 by spraying an pouring, the removing agent oneo the coating Gm he removed.
'T°ical?y, the removing agent is zsed in a S to ZO-fold c3ilutinn. After app~.icatian rf the removing agent, the surf~sce ran be rinsed with water. Tt is also possible tr ~ , allow the rain to wash things ofd. Thereafter, virtually all txacss of tfie protective coating will be.gone.
The irw~ention w~,l:l. presently be further e1 ucidated ire anci by the following e~samples.
E'xar~,n7.e 1,_Pr~~aration of a ~arotec~.ivp agex~t 1G~ Tn a reaction vessel, ,the follovair~g substaneess were added to each other in the order apecifa.ed~
wt . %
_, . w~ttex' 3~.9 alJ.yl ethc~xylate (non-ionic surfaet.arW) a.z '' S unt i foam ac~enC Q . 3 3Cr'6 salutiQn of sodium hexametaphos~rhate 0.6 ommc~na.a s~oluCiolx '~,'S% 1.5 polymer dispersion ~) 19.~
~vnelv divi~3ed calcium carbonate 4~3 'D
Ttze mi,x~ture obtained was stirxed °or 20 minutes under high.
sk:raar canditic~ns .
Timken the foJ.lowing subsr_ances mare lidded, i.n succession:
magnes~.um alc~aniraum silicate 0.8 fz~drcx~~et kxyl aelluloee a . 5 ~reserviry agent 0.1 5~?~ eclution of y-aminopx~pyltriethoxy silane D.2 3U p~~ui.n, vigorous st2-~ri:~g was carried out, until a ~:crncge.nEnus pxoduct vras foamed.
*) 'i"Yae polymer dispersion uved toad a solids content of 4S
a~zd an acwci value ref 73, caxculated on the go7.ids content.
sS The polymer in Lhe L~indel had kaeen for ned excltrsa.vely Lrom acr~,~s~ate moriorr~exs .
viscosity of end product at 20°C
2fl Fa.sey tBroc;kfield 0.5 z~pm, spindle 5) vise~sity of dilution of use at 20°~ (~. pant by weight of ' product c3~.~,uted with 1.5 paxts by weight of water) ~D mFa.sea tHxookfield G.9 rpan, spindle 1) Fxamp~e 2: Precaratir~n of a remo~rine~aq~nt In a react.-ion vessel, the following substar~cee were added 1~ to each oth$r in the prder specifzsd:
wt.~
_ . w~tex ' 73 ;~anthan gum 0.5 i6 "3~e ~ri~cLUre obtained wa:. sti:rred at a mcdexate speed, ux~tzl a t:~ickening tied occurred.
Then the following were added, in succession:
:~0 sodium hyetroacide splut~.on 33% 6.~
solLtzon of trisadium n tri,lotriacetate 40% 20 30°s so:~utior. of an amphoteric surfactant 0.5 Stirxir_g was carxied out until a homcgeneous product was ~5 faxwed_ Viscosity of ez~d prc:duct 20°C:
30 Fa.sec t8xoakfi.eld 0.5 rpm, spindle 5) Vzscvsity of da.luti.an c~f use at 2n°~ (Z part by weight ~f 30 groduct diluted with fi-ve parts by weight of watex):
4D mpa.sec tisxoakfield ~.5 xpcn, spindle 1) 1e 3 , cYtr ~ t~ r6tec ~.v atiri The pxntective agent of Example 1 was diluted wi'h ~5 1.a paz-ts by weagh'C of watex and applied to a glass horticultural greenhouse by spraying in the early spxing.
After six months, ~:he px~ctt~aiwe coating formed was etil~.
fu3ly int ~AcIG .
~~a ~ 4: ~er.~a~,ri a x'c~tectatre natm .~.~,:..~,.,._.~,._.m......~p . ~~'C xen~oring agent of ~xumple 2 was dilur.ed, for use, with fire parts by weaght of water and applied to the yrotective coaGinsg of Example 3 by spraying in the autumn. After a few ahc~we:rs of ra~.n, which h;ad came down by the end of a few days, the protecGa.~re coat;a.a-~g was found to have been 1,0 con;p~.~ae~.y washed off 3~y the rain.
~.~:amt~le 5: ~arat3cn of a oro ecCive agewt In a,xea.ctian vess~:~, the following subs:ances were added earl: othex irz the order specified:
wt.~
water 6.0 Sex-AD FA 6a?~' ~~i~.ls AG) ~ 0.3 alkyl wGhox~~lats (txr~n-ie~nic ~;urfactant) 0.3 polymex dispersion *1 3.0 antif pam agent 0.5 titanium white The ~raixt~:re abta~.nec~ was disrsed with e~ hi.gr shear dissc:~.~~er untie the desired fineness was achieved.
~"!teri t7ve rolxowing wexe added, i.n sucCessian:
water 31.3 tvy~3xo:xyetMyl cel~.u~.ase 0.90 :30 St3rxiryg was pexfcxmed until a ha:nr>ger~eous mixture was ebrained. i:~er. the foT7_cwing were added, zn succession:
am.-noria solution 25~ 3.4 poi. ymer dz seers Lcrt~ * ) 34 preserving ngent 0.~
~G~ soluta~on of y°a~ninc;propyltrie~:hoxy silane a.2 xs ~,'gc~zour~ st.rxing a=mss pm:fo::med ~:rxtil a horna~ene~oua praduc~
~r~xs fo~~d.
*) ~°he pcalymex~ disgersio~a used had ~ solic)e content c~~ ~#5%
and an acid value of ~3, ~a~cu~.atec~ on the solids aotxt~at.
T)-~e polymer in tree binder had Seri farmed exclusively from acr~raate mc~.u;~amers.
Vis~:~aity at er~d pxoduct rrt ~0°Cs ~.0 10 pa.sec taxoakfie3ld 0.5 rpm. spindxe S) t~iacouity of dilutic~~. of use at 2G°C (1 part by ~reigbt of pxoduet daluted with fdtvr pax-ta by weight of water) _ x5 mpa.sec (Bx~ookfield 0.5 rpm, spindle 7.) I5 ~xa le~~ ~'Y'E~J~XutlOf: c5f a xemav~fr~a ~caent Tn d reaction vessel, tl~e fc7.l.owix~g suhetances were added to each other in the oraex specified:
wt.#
grater 5~ . s5 2a Xanthan gum ~ 0.5 ml~~e mxxtur~e obtained was stir°ed at a moderate speed, unxil a thickening was achieved.
',hen thexe were added, ~.n succession:
25 ~odecyLhenxenesulfanic acid sodium hydrox.de salutao» 3~% ~~Z
soiutinn of. trisodiurn ~:iCri~.atr:.acetate 90~ 10 t%er~2~,~1 a~.cahol 25 dine vii 0.5 0 5ti.~cring spas pex~ormed unta.l a homogeneous product was farmed.
visco;~ity of end pxocuct 20°C:
Pa . sec (~srookf ieZd_ ~7 . S r-pm, spind~ a 5 ) 1 ~6 Visccasity csf dilution o: use at ~:fl°C (1 part by weight of proc9uct dxlmted with five parts by we~.ght of water) a , 2o rnPa.sec ;8~oakfield ~.5 rpm, spindle ~.~
~'xam~l a '~ L r~.rmi ns~ a nratect~rv colt t xnq The pr~tecteve ag~r_t of E°~cample 5 was diluted with four part by waight ct water arid ,app~.:~ed to a plastic . horticultural tuiused by spxaying, in the early spring.
1.0 After sxx months, the px-ratective ooating formet~ was still fully ir~taGt .
scar. 1e ~ : ~~movirc~ a r~tective cn,~tina 15 Tree r~mavirig agent df E~:ampl.e 6 was diluted with tiv~ parts by ws_~ght c~f water and «pplied by spraying onto the protective coating of Ea:ample 7, in the autuatn,. After a, short :.irne of actiotr, tt~e pxoteGtive ccatiag was removed completely with a water jet.
Claims (53)
1. A protective coating removable with a removing agent comprising a strong base and a complex former, which protective, coating comprises a pigment end a binder, the binder being a polymer having a weight-average molecular weight of 10,000-100,000 an acid value of 40-250.
2. A protective coating according to claim 1, wherein the binder has a weight-average molecular weight of 15,000-75,000, preferably of 20,000-50,000.
3. A protective coating according to claim 1 or 2, wherein the acid value of the binder is between 60 and 160.
4. A protective coating according to any one of claims 1 to 3, wherein the binder has a polydispersity of 2 to 6.
5. A protective coating according to any one of claims 1 to 4, wherein the glass transition temperature of the binder is between 10 and 60°C, preferably between 20 and 50°C.
6. A protective coating according to any one of claims 1 to 5, wherein the binder is a vinyl polymer.
7. A protective coating according to claim 6, wherein the vinyl polymer is based on one or more monomers selected from the group of methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, styrene, methacrylic acid, and acrylic acid.
8. A protective coating according to any one of claims 1 to 7, wherein the binder is present in an amount of 4-60% by weight, based on the weight of the protective coating.
9. A protective coating according to any one of claims 1 to 8, wherein the pigment is selected from the group of calcium carbonate, titanium oxide, a silicate, such as magnesium or aluminum silicate, gypsum, barite, and combinations thereof.
10. A protective coating according to any one of claims 1 to 9, wherein the pigment is present in an amount of 30-95% by weight, based on the weight of the protective coating.
11. A protective coating according to any one of claims 1 to 10, wherein the protective coating further comprises an adhesion promoter.
12. A protective coating according to claim 11, wherein the adhesion promoter is selected from the group of silanes.
13. A protective coating according to any one of claims 1 to 12, wherein the protective coating further comprises a pigment divider.
14. A protective coating according to any one of claims 1 to 13, wherein the protective coating further comprises a thickener.
15. A protective agent comprising a pigment and a water-carried binder, wherein the binder is a polymer having a weight-average molecular weight of 10,000-100,000 and an acid value of 40-250, for forming a removable protective coating according to any one of claims 1 to 14.
16. A protective agent according to claim 15, wherein the protective agent further comprises a weak base selected from the group of ammonia, mono-, di- and trialkylamines, with the alkyl group containing from to 1 8 carbon atoms.
17. A protective agent according to claim 16, wherein the weak base is present in an amount of 0.2-5% by weight, based on the weight of the protective agent.
18. A method for forming a protective coating which is removable with a removing agent comprising a strong base and a complex former, wherein a protective agent according to any one of claims 15 to 17 is applied to a substantially transparent surface, which protective agent, after drying, forms the protective coating.
19. A method according to claim 18, wherein the substantially transparent surface is an outside wall surface of a greenhouse.
20. A method for removing a protective coating according to any one of claims 1 to 14, by treating the protective coating with a removing agent which comprises a strong base and a complex former, the strong base being present in an amount of 1-10% by weight, based on the weight of the removing agent.
21. A method according to claim 20, wherein the complex former is present in an amount of 2-10% by weight, based on the weight of the removing agent.
22. A method according to claims 20 or 21, wherein the removing agent further comprises an organic solvent.
23. A method according to claim 22, wherein the organic solvent is selected from the group of tetrahydrofuran, benzyl alcohol, and higher alcohols.
24. A method according to claim 23, wherein the removing agent comprises 10-30% by weight, based on the weight of the removing agent, of benzyl alcohol.
25. A kit comprising a protective agent according to any one of claims 15 to 17 and a removing agent, which removing agent is suitable for use in a method according to claims 20 to 24.
26. A protective coating removable with a removing agent for application to and removal from a light transmissive material comprising a strong base and a complex former, which protective coating comprises a pigment and a binder, the binder being a polymer having a weight-average molecular weight of 10,000-100,000 and an acid value of 40-250.
27. A protective coating according to claim 26, wherein the binder has a weight-average molecular weight of 15,000-75,000, preferably of 20,000-50,000.
28. A protective coating according to claim 26 or 27, wherein the acid value of the binder is between 60 and 160.
29. A protective coating according to any one of claims 26 to 28, wherein the binder has a polydispersity of 2 to 6.
30. A protective coating according to any one of claims 26 to 29, wherein the glass transition temperature of the binder is between 10 and 60°C, preferably between 20 and 50°C.
31. A protective coating according to any one of claims 26 to 30, wherein the binder is a vinyl polymer.
32. A protective coating according to claim 31, wherein the vinyl polymer is based on one or more monomers selected from the group of methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, styrene, methacrylic acid, and acrylic acid.
33. A protective coating according to any one of claims 26 to 32, wherein the binder is present in an amount of 4-60% by weight, based on the weight of the protective coating.
34. A protective coating according to any one of claims 26 to 33, wherein the pigment is selected from the group of calcium carbonate, titanium oxide, a silicate, such as magnesium or aluminum silicate, gypsum, barite, and combinations thereof.
35. A protective coating according to any one of claims 26 to 34, wherein the pigment is present in an amount of 30-95% by weight, based on the weight of the protective coating.
36. A protective coating according to any one of claims 26 to 35, wherein the protective coating further comprises an adhesion promoter.
37. A protective coating according to claim 36, wherein the adhesion promoter is selected from the group of silanes.
38. A protective coating according to any one of claims 26 to 37, wherein the protective coating further comprises a pigment divider.
39. A protective coating according to any one of claims 26 to 38, wherein the protective coating further comprises a thickener.
40. A protective agent comprising a pigment and a water-carried binder, wherein the binder is a polymer having a weight-average molecular weight of 10,000-100,000 and an acid value of 40-250, for forming a removable protective coating according to any one of claims 26 to 39.
41. A protective agent according to claim 40, wherein the protective agent further comprises a weak base selected from the group of ammonia, mono-, di- and trialkylamines, with the alkyl group containing from to 1 8 carbon atoms.
42. A protective agent according to claim 41, wherein the weak base is present in an amount of 0.2-5% by weight, based on the weight of the protective agent.
43. A protective coating according to any one of claims 26 to 42 wherein the light transmissive material is selected from the group consisting of glass, polycarbonates, polyolefins, polyethylene terephthalate and polyesters.
44. A method for forming a protective coating which is removable with a removing agent comprising a strong base and a complex former, wherein a protective agent according to any one of claims 40 to 43 is applied to a substantially transparent surface, which protective agent, after drying, forms the protective coating.
45. A method according to claim 44, wherein the substantially transparent surface is an outside wall surface of a greenhouse.
46. A method for removing a protective coating according to any one of claims 26 to 39, by treating the protective coating with a removing agent which comprises a strong base and a complex former, the strong base being present in an amount of 1-10% by weight, based on the weight of the removing agent.
47. A method according to claim 46, wherein the complex former is present in an amount of 2-10% by weight, based on the weight of the removing agent.
48. A method according to claims 46 or 47, wherein the removing agent further comprises an organic solvent.
49. A method according to claim 48, wherein the organic solvent is selected from the group of tetrahydrofuran, benzyl alcohol, and higher alcohols.
50. A method according to claim 49, wherein the removing agent comprises 10-30% by weight, based on the weight of the removing agent, of benzyl alcohol.
51. A kit comprising a protective agent according to any one of claims 40 to 42 and a removing agent, which removing agent is suitable for use in a method according to claims 46 to 50.
52. The product substantially as described or referred to herein.
53. A method substantially as described or referred to herein.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1007433 | 1997-11-03 | ||
| NL1007433A NL1007433C2 (en) | 1997-11-03 | 1997-11-03 | Removable screen layer. |
| CA 2302738 CA2302738C (en) | 1997-11-03 | 1998-11-03 | Removable protective coating |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2302738 Division CA2302738C (en) | 1997-11-03 | 1998-11-03 | Removable protective coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2561429A1 true CA2561429A1 (en) | 1999-05-14 |
Family
ID=39343623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002561429A Abandoned CA2561429A1 (en) | 1997-11-03 | 1998-11-03 | Removable protective coating |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2561429A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114768793A (en) * | 2013-10-30 | 2022-07-22 | 巴斯夫公司 | Catalyst coating for pollution control |
-
1998
- 1998-11-03 CA CA002561429A patent/CA2561429A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114768793A (en) * | 2013-10-30 | 2022-07-22 | 巴斯夫公司 | Catalyst coating for pollution control |
| CN114768793B (en) * | 2013-10-30 | 2024-05-28 | 巴斯夫公司 | Catalyst coating for pollution control |
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| EEER | Examination request | ||
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