CA2219208C - Aqueous dispersion of a peelable coating composition - Google Patents
Aqueous dispersion of a peelable coating composition Download PDFInfo
- Publication number
- CA2219208C CA2219208C CA 2219208 CA2219208A CA2219208C CA 2219208 C CA2219208 C CA 2219208C CA 2219208 CA2219208 CA 2219208 CA 2219208 A CA2219208 A CA 2219208A CA 2219208 C CA2219208 C CA 2219208C
- Authority
- CA
- Canada
- Prior art keywords
- acrylic copolymer
- emulsion
- weight
- emulsions
- coating composition
- 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.)
- Expired - Fee Related
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 25
- 239000006185 dispersion Substances 0.000 title claims abstract description 18
- 239000000839 emulsion Substances 0.000 claims abstract description 92
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 239000002253 acid Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 13
- 230000009477 glass transition Effects 0.000 claims abstract description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 238000012360 testing method Methods 0.000 description 23
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000003002 pH adjusting agent Substances 0.000 description 13
- 239000002518 antifoaming agent Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 230000002265 prevention Effects 0.000 description 12
- 239000006254 rheological additive Substances 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- -1 alkalis Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- 238000003912 environmental pollution Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- IHTCZSNKQINGDD-UHFFFAOYSA-M trimethyl-[(5-methylfuran-2-yl)methyl]azanium;iodide Chemical compound [I-].CC1=CC=C(C[N+](C)(C)C)O1 IHTCZSNKQINGDD-UHFFFAOYSA-M 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HILUWRPVFKJTAD-ZGHMGGRHSA-N GA21 Chemical compound O=C(O)[C@H]1[C@@H]2[C@]3(C(=O)O)C(=O)O[C@@]2([C@H]2[C@]41CC(=C)[C@@](O)(C4)CC2)CCC3 HILUWRPVFKJTAD-ZGHMGGRHSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 239000008157 edible vegetable oil Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical class C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-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
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- AEPWOCLBLLCOGZ-UHFFFAOYSA-N 2-cyanoethyl prop-2-enoate Chemical class C=CC(=O)OCCC#N AEPWOCLBLLCOGZ-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- DRMYLINAGHHBNG-UHFFFAOYSA-N 2-oxo-3h-furan-4-carboxylic acid Chemical compound OC(=O)C1=COC(=O)C1 DRMYLINAGHHBNG-UHFFFAOYSA-N 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
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- AIMDYNJRXHEXEL-UHFFFAOYSA-N 3-phenylprop-1-enylbenzene Chemical compound C=1C=CC=CC=1CC=CC1=CC=CC=C1 AIMDYNJRXHEXEL-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
- 102100026788 ATP synthase subunit C lysine N-methyltransferase Human genes 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical class [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 206010011416 Croup infectious Diseases 0.000 description 1
- 101100536354 Drosophila melanogaster tant gene Proteins 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 244000182067 Fraxinus ornus Species 0.000 description 1
- 101000833848 Homo sapiens ATP synthase subunit C lysine N-methyltransferase Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- DUFKCOQISQKSAV-UHFFFAOYSA-N Polypropylene glycol (m w 1,200-3,000) Chemical compound CC(O)COC(C)CO DUFKCOQISQKSAV-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 101150024767 arnT gene Proteins 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 201000010549 croup Diseases 0.000 description 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012948 isocyanate Chemical class 0.000 description 1
- 150000002513 isocyanates Chemical class 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
- 239000002480 mineral oil Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- 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
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31645—Next to addition polymer from unsaturated monomers
- Y10T428/31649—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
- Y10T428/31699—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31928—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Abstract
The aqueous dispersion of a peelable coating composition of the present invention is (a) a mixture containing 5-40% by weight of an emulsion of an acrylic copolymer having a glass transition temperature (hereinafter referred to as "Tg") of not lower than 40 °C , and 95-60% by weight of an emulsion of another acrylic copolymer having a Tg ranging from -20 °C through 5°C . The acrylic copolymer emulsion mixture (b) contains ethylenically unsaturated vinyl monomers having acid value in a total amount of 0.5-1.0% by weight, and (c) at least one of the acrylic copolymer emulsions is an acrylic copolymer which has been polymerized by use of a reactive surfactant, and (d) the particle size of the acrylic copolymer emulsions is not more than 200 nm.
Description
Aqueous Dispersion of a Peelable Coating Composition BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to an aqueous dispersion of a peelable coating composition which is intended to be used for temporary protection of articles and is effective in temporary storage of articles during distribution, where articles may be temporarily stored in the open air or exposed to the open air during distribution.
' Description of the Related Art In more and more cases, articles such as automobiles and other vehicles, machine parts, metallic household articles and other ferrous and non-ferrous articles, wooden articles, glass articles, rubber articles, and coated rubber articles (hereinafter collectively referred to as "articles") reach the hands of consumers after being transported from the manufacturer and stored temporarily in the open air. In such cases, during the period before these articles are in,hands of consumers (generally this period is 2-12 months in duration), the surfaces of these goods are prone to becoming scratched, stained, discolored, or contaminated due to, for example, deposits such as sandy dust, iron powder, salts, alkalis, acids, soot and smoke, dead bodies or body fluids of insects, and excrement of birds and insects; sunlight; and wind and rain. Moreover, the material may come to have marks due to physical forces.
These deposits, etc. must be removed as soon as possible, as they may reduce the value of goods. However, removal of deposits requires elaborate work, which is accompanied by additional costs.
Thus, in order to temporarily protect surfaces of an article from being damaged by the aforementioned deposits, sunlight, elements, or scratches, and to eliminate the elaborate work and accompanying costs, there have been proposed a number of strippable coating compositions which areapplied to surfaces of an article when the article is shipped, and which, after a predetermined period of custody ' is over, can be easily stripped off.
For example, two types of strippable coating compositions are used for outer panels of automobiles: one is a so-calledoily wax type in which paraffin wax is dispersed in a petroleum-based solvent, and the other is a type in which a mixture of calcium carbonate powder in paraffin wax is dispersed in a petroleum-based solvent.
These strippable coating compositions call for use of a petroleum-based solvent for removal, and in addition, they may raise the fear of environmental problems such as air pollution. Compositions of a type in which an alkali-soluble resin is the primary component are also used, and these require an alkali detergent for removal, and therefore involve the problem of environmental pollution such as water contamination.
Accordingly, in order to eliminate the aforementioned problems, there have been proposed emulsion-type coating compositions which form a coating film capable of being peeled off by hand after they have carried out their function of protection (see, for example, Japanese Patent Publication (kokoku) Nos. 50-39685 and 44-29583).
However, the above-described conventional coating compositions of the emulsion type have the following drawbacks.
1) The coating compositions disclosed in Japanese Patent Publication (kokoku) No. 50-39685 are made from a single starting material. Therefore, their peeling property is not satisfactory under environmental conditions in which ' they are usually used. For example, they cannot be satisfactorily peeled off in a wide temperature range from low temperatures around 5 °~ to high temperatures around 40°~ : at low temperatures the formed film breaks during the peeling operation, whereas at high temperatures it stretches and thus is not quickly peeled off.
2) Japanese Patent Publication No. 44-29593 discloses a coating composition obtained through emulsion polymerization in water of acrylonitrile and an acrylic acid ester of an lower alkyl.
Aqueous dispersions of an acrylic resin which contains acrylonitrile as an essential component raise a problem that harmful nitrogen oxides are produced during incineration of waste films that have been peeled and cause environmental pollution.
In the meantime, regarding peelable coating compositions for use with automobile outer panels, there exists need for compositions capable of forming a protective film that exerts contrasting functions simultaneously in terms of adhesion; i.e., proper adhesiveness and holding power that does not permit release of the film with ease during water-resistance tests or that never permits release during transportation of vehicles under protection by the film, and ease in peeling of the film with fingers after the period of protection by the film is over.
SUMMARY OF THE INVENTION
To solve the above-described problems and meet the ' above-stated need, the present inventors have carried out careful studies on dispersion compositions that do not contain a nitrogen-containing vinyl monomer, and have found that an aqueous dispersion of a peelable coating composition having excellent peelability can be obtained by forming an a mulsion having the following characteristics: 1) the emulsion is an acrylic copolymer emulsion which is a mixture of two acrylic copolymer emulsions, wherein the acrylic copolymers have different predetermined glass transition temperatures, 2) the amount of ethylenically unsaturated monomers having acid value contained in the mixture is not higher than a predetermined level, and 3) the emulsion does not make use of a nitrogen-containing monomer. The present invention has been accomplished based on this finding.
Moreover, the present inventors have found that, in addition to the above-mentioned features 1) through 3), when 4) polymerization is performed under conditions in which at least one of the emulsions contains a reactive surfactant and 5) the particle size of the emulsions is controlled to fall within a predetermined range, there can be obtained an aqueous dispersion of a peelable coating composition having further improved water resistance and excellent adhesiveness, leading to completion of the present invention.
Accordingly, a first aqueous dispersion of a peelable coating composition of the present invention is characterized by comprising (a) a mixture containing 5-40% by weight of an emulsion of an acrylic copolymer having a glass transition temperature (hereinafter referred to as "Tg") of not lower than 40 °C , and 95-60o by weight of an emulsion of another acrylic copolymer having a Tg ranging from -20°C through °C ; wherein (b') the acrylic copolymer emulsion mixture (a) contains ethylenically unsaturated vinyl monomers having acid value in a total amount of less than 2.0o by weight; and (c) the acrylic copolymer emulsion mixture (a) contains no nitrogen-containing vinyl monomers in the form of a monomer.
A second aqueous dispersion of a peelable coating composition of the present invention is characterized by, in addition to the aforementioned requirements (a), (b), and (c).
(d) at least one of the acrylic copolymer emulsions to be incorporated into the mixture is an acrylic copolymer which has been polymerized by use of a reactive surfactant, and (e) the particle size of the acrylic copolymer emulsions is not more than 200 nm.
MODES FOR CARRYING OUT THE INVENTION
Next will be described modes for carrying out the present invention.
A first mode of the present invention is drawn to the first aqueous dispersion of a peelable coating composition characterized by an acrylic copolymer emulsion having the ' below-described features (a) through (c). Synergism of these features afford, as demonstrated in Examples hereinbelow, not only excellent physicochemical properties including water resistance, adhesive strength, protective power, and weatherability during the period of protection, but also excellent peelability in a wide temperature range from low temperatures (about 5°C ) to high temperatures (about 40 °C ) after the protection period is over, and in addition, when the after-use waste film is incinerated, the film does not generate nitrogen oxides and thus eliminates adverse effects of environmental pollution, etc.
(a) The acrylic copolymer emulsion mixture of the present invention contains 5-40% by weight of an emulsion of an acrylic copolymer having a glass transition temperature o f not lower than 40 °C and 95-60o by weight of an emulsion of another acrylic copolymer having a Tg ranging from -20 °C
through 5 °C .
(b) The acrylic copolymer emulsion mixture (a) contains g ethylenically unsaturated vinyl monomers having acid value in a total amount of less than 2.0o by weight.
(c) The acrylic copolymer emulsion mixture (a) contains no nitrogen source such as acrylonitrile in the form of a monomer.
A second mode of the present invention is drawn to the second aqueous dispersion of a peelable coating composition of the present invention characterized by, in addition to the aforementioned requirements (a), (b), and (c), the following features (d) and (e). Synergism of all these ' features afford, as demonstrated in Examples hereinbelow, excellent physicochemical properties including water resistance, adhesive strength, and so on.
(d) At least one of the acrylic copolymer emulsions to be incorporated into the mixture is an acrylic copolymer which has been polymerized by use of a reactive surfactant.
(e) The particle size of the acrylic copolymer emulsions is not more than 200 nm.
Examples of the acrylic copolymer emulsion of the present invention include, but are not limited to, copolymer emulsions of one or more acrylic acid alkyl esters and/or methacrylic acid alkyl esters and one or more vinyl monomers which are capable of being polymerized with the acrylic alkyl esters and/or methacrylic alkyl esters, wherein the vinyl monomers include vinyl acetate, hydroxyl-group-containing vinyl monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and allyl alcohol, epoxy-group-containing vinyl monomers such as glycidyl acrylate and glycidyl methacrylate, and aromatic vinyl monomers such as styrene, methylstyrene, dimethylstyrene, ethylstyrene, butylstyrene, and benzylstyrene; and copolymer emulsions of a carboxyl-group-containing vinyl monomer such as acrylic acid, methacrylic acid, itaconic acid, citraconic acid, and crotonic acid and the aforementioned one or more vinyl monomers which are capable of being polymerized with the acrylic alkyl esters and/or methacrylic alkyl esters.
It should, however, be noted that nitrogen-containing ' monomers including acrylonitrile, aminoalkyl acrylates such as diethylaminoethyl acrylate and aminodimethyl acrylate, cyanoethyl acrylate, and isocyanate adducts are excluded from constituent monomers of the aforementioned acrylic copolymer emulsions.
With this exclusion, the waste coating film does not generate nitrogen oxides when incinerated, thus eliminating the fear of environmental pollution.
According to the present invention, two acrylic copolymer emulsions having different Tg ranges are mixed.
Specifically, the Tg range of a first acrylic copolymer is equal to or greater than 40 °C , and that of a second acrylic copolymer is from -20 °C to 5 °C .
The proportions of these two emulsions are preferably such that the acrylic copolymer emulsion having a Tg of not lower than 40 °C is between 5o by weight and 40o by weight inclusive and the acrylic copolymer emulsion having a Tg from -20°C to 5 °C is between 95o by weight and 60o by weight g _ inclusive.
More preferably, tha:~ proportions of these two emulsions are such t~rnat. t:he ac:ry7_i.c ~~:apo7_ymer emulsion having a Tg c>f not: ~_c:~wer tharu ~) (.~ "C i,> between 10 o by weight and 35% by weight inclusive and the acrylic copolymer emulsion tiavinca a 'f ca from -::'C ~C t=o 5 "C is between 90o by weight and 65'o by weigtnt inclusive.
Also, the prop~.>rt.ior of the ettyy i.enica_Lly unsaturated vinyl monomers having aci=: value in the acrylic copolymer emulsion mi.xt=ure sy~~tem is not. more than 2 . 0 o by weight:, more preferab.7...y ) . 2-0 . f3 o by weight, with respect to the weight of the entirety of the mixture.
If ethylenicall_y unsaturated vin~..~l monomers having acid value are contc~i.nf:d in amounts ire excess of 2 . 0 o by weight, water resistance of trie resu:l~ ant coating film becomes poor, and i.ru addition, adhes:i~,re strE:ngth increases to render' the film e~~cessivc>ly heat- and weather- resistant and therefore the 'vilm may not be easily peeled off, which is r~.c;t prefet-red.
The ethylenical.ly unsaturated v:i:uyl monomers having acid value may be --w arnon:~ t~ho~>e wh:icra .~onstil~ute the aforementioned acrylic copolymer emu_L.,ion - carboxy-containing vinyl rnonomE~r; suc:r: <-~s <~c.:r~,~lic acid, methacrylic acid, it~.aconic acid, citv~iconicacid, and crotonic acid. How ever, the ethyleni,~ally unsaturated vinyl monomers having acid value <:cre r ct limited only to these compounds.
In the preservt invertion, examples of t:he reactive surfactants include AQLJALON* RN" serifs (Dai-ichi *Trade-mark Kogyo Seiyaku K. K. ) which are s~~rf_act~~rvts o F the polyoxyethylene alkylpheryl ether typo in which a radical-polymerizable prapenyl. croup teas been introduced into the hydrophobic. groi.;p; aruionic s:.irfactants, AQUALON
HS series (Dai-icrui Kogyc Sei.yaku K. _~. ) which are based on the sulfuric ester salts c>f AQUALc»J RN; acrylic anion surfactants, ELEMINC>1* RS30 and ELEM:IP~C>L JS-2 (both by Sanyo Chemical Tndu~>t.rie., Lt:d. ) and .%'~DEKA REASOAP*
series (Asahi Denka Kogyo K.K.).
When reactive ~urfac~tant:s are adc:led upon synthesis of acrylic copolymer emulsions, water resistance of the coating film is improved, film streng=:h i.s enhanced, and peelability of them fa..lm s s prc>mc;ted.
The particle size of the acrylic copolymer emulsions is preferably not mc7re tr,an 2(.i~:) nm, m,:~re preferably not more than 100 nm. When tree particle s~.ze is in excess of 200 nm, a suff.iciF:n;:. contact area canr;ct be obtained between the composi.t.i.on and t:Y.<~ surfaa:::e of t:he object to be coated, which leads tc: poar water Tesistance.
The aforement.ic_~ned mixtLarfv may :ir:corpox-ate, as desired, small amouras of additives wtich may be useful in the manufactures of peelabl.e-c:oatinci compositions. Such additives include plast~icizers (e. g., phthalate esters and fatty acid est.ers), wax emulsions (including polyethylene-based emulsions and pol.y;~ropy:lE>ne-based emulsions), defoamir_g agents (e.g., mineral oils and silicone oils) , Rheoloc~y mod.i.f: ier (.ins ludinq inorganic type and organic type), UV ak.~sorbents (e. g., benzotriazoles and *Trade-mark benzophenones), pH modifiers (e.g., organic alkalis and ethanolamines), preservatives (e.g., benzoisothiazolines and triazines), coalescing agents (e. g., alkyl ethers of mono-or di-ethylene glycol and alkyl ethers of mono- or di-propylene glycol), anti-freezing agents (e. g., polyhydric alcohols), peelability-improving agents (e. g., silicone emulsions and alkylphosphoric esters), drying accelerators (e. g., lower alcohols such as ethyl alcohol).
The peelable coating composition of the present invention is intended to be applied onto surfaces of ' articles such as automobiles and other vehicles, machine parts, metallic household articles and other ferrous and non-ferrous articles, wooden articles, glass articles, rubber articles, and coated rubber articles, to thereby protect the surfaces of the articles in the open air or indoors. Needless to say, the composition of the present invention may be used for protecting surfaces of objects other than the above articles.
Specifically, the aqueous dispersion of peelable coating composition of the present invention is advantageously used, for example, for the following purposes.
1) Prevention of stains and scratches, or degradation due to UV rays, etc. of panel coatings and resin portions of automobiles.
2) Prevention of rust stains of machine parts.
3) Prevention of stains of edible oil and dirt from hands, when applied to ventilation fans and kitchen devices and utensils, 4) Prevention of stains and scratches of aluminum fences .
5) Prevention of stains and scratches of indoor floors.
Field of the Invention The present invention relates to an aqueous dispersion of a peelable coating composition which is intended to be used for temporary protection of articles and is effective in temporary storage of articles during distribution, where articles may be temporarily stored in the open air or exposed to the open air during distribution.
' Description of the Related Art In more and more cases, articles such as automobiles and other vehicles, machine parts, metallic household articles and other ferrous and non-ferrous articles, wooden articles, glass articles, rubber articles, and coated rubber articles (hereinafter collectively referred to as "articles") reach the hands of consumers after being transported from the manufacturer and stored temporarily in the open air. In such cases, during the period before these articles are in,hands of consumers (generally this period is 2-12 months in duration), the surfaces of these goods are prone to becoming scratched, stained, discolored, or contaminated due to, for example, deposits such as sandy dust, iron powder, salts, alkalis, acids, soot and smoke, dead bodies or body fluids of insects, and excrement of birds and insects; sunlight; and wind and rain. Moreover, the material may come to have marks due to physical forces.
These deposits, etc. must be removed as soon as possible, as they may reduce the value of goods. However, removal of deposits requires elaborate work, which is accompanied by additional costs.
Thus, in order to temporarily protect surfaces of an article from being damaged by the aforementioned deposits, sunlight, elements, or scratches, and to eliminate the elaborate work and accompanying costs, there have been proposed a number of strippable coating compositions which areapplied to surfaces of an article when the article is shipped, and which, after a predetermined period of custody ' is over, can be easily stripped off.
For example, two types of strippable coating compositions are used for outer panels of automobiles: one is a so-calledoily wax type in which paraffin wax is dispersed in a petroleum-based solvent, and the other is a type in which a mixture of calcium carbonate powder in paraffin wax is dispersed in a petroleum-based solvent.
These strippable coating compositions call for use of a petroleum-based solvent for removal, and in addition, they may raise the fear of environmental problems such as air pollution. Compositions of a type in which an alkali-soluble resin is the primary component are also used, and these require an alkali detergent for removal, and therefore involve the problem of environmental pollution such as water contamination.
Accordingly, in order to eliminate the aforementioned problems, there have been proposed emulsion-type coating compositions which form a coating film capable of being peeled off by hand after they have carried out their function of protection (see, for example, Japanese Patent Publication (kokoku) Nos. 50-39685 and 44-29583).
However, the above-described conventional coating compositions of the emulsion type have the following drawbacks.
1) The coating compositions disclosed in Japanese Patent Publication (kokoku) No. 50-39685 are made from a single starting material. Therefore, their peeling property is not satisfactory under environmental conditions in which ' they are usually used. For example, they cannot be satisfactorily peeled off in a wide temperature range from low temperatures around 5 °~ to high temperatures around 40°~ : at low temperatures the formed film breaks during the peeling operation, whereas at high temperatures it stretches and thus is not quickly peeled off.
2) Japanese Patent Publication No. 44-29593 discloses a coating composition obtained through emulsion polymerization in water of acrylonitrile and an acrylic acid ester of an lower alkyl.
Aqueous dispersions of an acrylic resin which contains acrylonitrile as an essential component raise a problem that harmful nitrogen oxides are produced during incineration of waste films that have been peeled and cause environmental pollution.
In the meantime, regarding peelable coating compositions for use with automobile outer panels, there exists need for compositions capable of forming a protective film that exerts contrasting functions simultaneously in terms of adhesion; i.e., proper adhesiveness and holding power that does not permit release of the film with ease during water-resistance tests or that never permits release during transportation of vehicles under protection by the film, and ease in peeling of the film with fingers after the period of protection by the film is over.
SUMMARY OF THE INVENTION
To solve the above-described problems and meet the ' above-stated need, the present inventors have carried out careful studies on dispersion compositions that do not contain a nitrogen-containing vinyl monomer, and have found that an aqueous dispersion of a peelable coating composition having excellent peelability can be obtained by forming an a mulsion having the following characteristics: 1) the emulsion is an acrylic copolymer emulsion which is a mixture of two acrylic copolymer emulsions, wherein the acrylic copolymers have different predetermined glass transition temperatures, 2) the amount of ethylenically unsaturated monomers having acid value contained in the mixture is not higher than a predetermined level, and 3) the emulsion does not make use of a nitrogen-containing monomer. The present invention has been accomplished based on this finding.
Moreover, the present inventors have found that, in addition to the above-mentioned features 1) through 3), when 4) polymerization is performed under conditions in which at least one of the emulsions contains a reactive surfactant and 5) the particle size of the emulsions is controlled to fall within a predetermined range, there can be obtained an aqueous dispersion of a peelable coating composition having further improved water resistance and excellent adhesiveness, leading to completion of the present invention.
Accordingly, a first aqueous dispersion of a peelable coating composition of the present invention is characterized by comprising (a) a mixture containing 5-40% by weight of an emulsion of an acrylic copolymer having a glass transition temperature (hereinafter referred to as "Tg") of not lower than 40 °C , and 95-60o by weight of an emulsion of another acrylic copolymer having a Tg ranging from -20°C through °C ; wherein (b') the acrylic copolymer emulsion mixture (a) contains ethylenically unsaturated vinyl monomers having acid value in a total amount of less than 2.0o by weight; and (c) the acrylic copolymer emulsion mixture (a) contains no nitrogen-containing vinyl monomers in the form of a monomer.
A second aqueous dispersion of a peelable coating composition of the present invention is characterized by, in addition to the aforementioned requirements (a), (b), and (c).
(d) at least one of the acrylic copolymer emulsions to be incorporated into the mixture is an acrylic copolymer which has been polymerized by use of a reactive surfactant, and (e) the particle size of the acrylic copolymer emulsions is not more than 200 nm.
MODES FOR CARRYING OUT THE INVENTION
Next will be described modes for carrying out the present invention.
A first mode of the present invention is drawn to the first aqueous dispersion of a peelable coating composition characterized by an acrylic copolymer emulsion having the ' below-described features (a) through (c). Synergism of these features afford, as demonstrated in Examples hereinbelow, not only excellent physicochemical properties including water resistance, adhesive strength, protective power, and weatherability during the period of protection, but also excellent peelability in a wide temperature range from low temperatures (about 5°C ) to high temperatures (about 40 °C ) after the protection period is over, and in addition, when the after-use waste film is incinerated, the film does not generate nitrogen oxides and thus eliminates adverse effects of environmental pollution, etc.
(a) The acrylic copolymer emulsion mixture of the present invention contains 5-40% by weight of an emulsion of an acrylic copolymer having a glass transition temperature o f not lower than 40 °C and 95-60o by weight of an emulsion of another acrylic copolymer having a Tg ranging from -20 °C
through 5 °C .
(b) The acrylic copolymer emulsion mixture (a) contains g ethylenically unsaturated vinyl monomers having acid value in a total amount of less than 2.0o by weight.
(c) The acrylic copolymer emulsion mixture (a) contains no nitrogen source such as acrylonitrile in the form of a monomer.
A second mode of the present invention is drawn to the second aqueous dispersion of a peelable coating composition of the present invention characterized by, in addition to the aforementioned requirements (a), (b), and (c), the following features (d) and (e). Synergism of all these ' features afford, as demonstrated in Examples hereinbelow, excellent physicochemical properties including water resistance, adhesive strength, and so on.
(d) At least one of the acrylic copolymer emulsions to be incorporated into the mixture is an acrylic copolymer which has been polymerized by use of a reactive surfactant.
(e) The particle size of the acrylic copolymer emulsions is not more than 200 nm.
Examples of the acrylic copolymer emulsion of the present invention include, but are not limited to, copolymer emulsions of one or more acrylic acid alkyl esters and/or methacrylic acid alkyl esters and one or more vinyl monomers which are capable of being polymerized with the acrylic alkyl esters and/or methacrylic alkyl esters, wherein the vinyl monomers include vinyl acetate, hydroxyl-group-containing vinyl monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and allyl alcohol, epoxy-group-containing vinyl monomers such as glycidyl acrylate and glycidyl methacrylate, and aromatic vinyl monomers such as styrene, methylstyrene, dimethylstyrene, ethylstyrene, butylstyrene, and benzylstyrene; and copolymer emulsions of a carboxyl-group-containing vinyl monomer such as acrylic acid, methacrylic acid, itaconic acid, citraconic acid, and crotonic acid and the aforementioned one or more vinyl monomers which are capable of being polymerized with the acrylic alkyl esters and/or methacrylic alkyl esters.
It should, however, be noted that nitrogen-containing ' monomers including acrylonitrile, aminoalkyl acrylates such as diethylaminoethyl acrylate and aminodimethyl acrylate, cyanoethyl acrylate, and isocyanate adducts are excluded from constituent monomers of the aforementioned acrylic copolymer emulsions.
With this exclusion, the waste coating film does not generate nitrogen oxides when incinerated, thus eliminating the fear of environmental pollution.
According to the present invention, two acrylic copolymer emulsions having different Tg ranges are mixed.
Specifically, the Tg range of a first acrylic copolymer is equal to or greater than 40 °C , and that of a second acrylic copolymer is from -20 °C to 5 °C .
The proportions of these two emulsions are preferably such that the acrylic copolymer emulsion having a Tg of not lower than 40 °C is between 5o by weight and 40o by weight inclusive and the acrylic copolymer emulsion having a Tg from -20°C to 5 °C is between 95o by weight and 60o by weight g _ inclusive.
More preferably, tha:~ proportions of these two emulsions are such t~rnat. t:he ac:ry7_i.c ~~:apo7_ymer emulsion having a Tg c>f not: ~_c:~wer tharu ~) (.~ "C i,> between 10 o by weight and 35% by weight inclusive and the acrylic copolymer emulsion tiavinca a 'f ca from -::'C ~C t=o 5 "C is between 90o by weight and 65'o by weigtnt inclusive.
Also, the prop~.>rt.ior of the ettyy i.enica_Lly unsaturated vinyl monomers having aci=: value in the acrylic copolymer emulsion mi.xt=ure sy~~tem is not. more than 2 . 0 o by weight:, more preferab.7...y ) . 2-0 . f3 o by weight, with respect to the weight of the entirety of the mixture.
If ethylenicall_y unsaturated vin~..~l monomers having acid value are contc~i.nf:d in amounts ire excess of 2 . 0 o by weight, water resistance of trie resu:l~ ant coating film becomes poor, and i.ru addition, adhes:i~,re strE:ngth increases to render' the film e~~cessivc>ly heat- and weather- resistant and therefore the 'vilm may not be easily peeled off, which is r~.c;t prefet-red.
The ethylenical.ly unsaturated v:i:uyl monomers having acid value may be --w arnon:~ t~ho~>e wh:icra .~onstil~ute the aforementioned acrylic copolymer emu_L.,ion - carboxy-containing vinyl rnonomE~r; suc:r: <-~s <~c.:r~,~lic acid, methacrylic acid, it~.aconic acid, citv~iconicacid, and crotonic acid. How ever, the ethyleni,~ally unsaturated vinyl monomers having acid value <:cre r ct limited only to these compounds.
In the preservt invertion, examples of t:he reactive surfactants include AQLJALON* RN" serifs (Dai-ichi *Trade-mark Kogyo Seiyaku K. K. ) which are s~~rf_act~~rvts o F the polyoxyethylene alkylpheryl ether typo in which a radical-polymerizable prapenyl. croup teas been introduced into the hydrophobic. groi.;p; aruionic s:.irfactants, AQUALON
HS series (Dai-icrui Kogyc Sei.yaku K. _~. ) which are based on the sulfuric ester salts c>f AQUALc»J RN; acrylic anion surfactants, ELEMINC>1* RS30 and ELEM:IP~C>L JS-2 (both by Sanyo Chemical Tndu~>t.rie., Lt:d. ) and .%'~DEKA REASOAP*
series (Asahi Denka Kogyo K.K.).
When reactive ~urfac~tant:s are adc:led upon synthesis of acrylic copolymer emulsions, water resistance of the coating film is improved, film streng=:h i.s enhanced, and peelability of them fa..lm s s prc>mc;ted.
The particle size of the acrylic copolymer emulsions is preferably not mc7re tr,an 2(.i~:) nm, m,:~re preferably not more than 100 nm. When tree particle s~.ze is in excess of 200 nm, a suff.iciF:n;:. contact area canr;ct be obtained between the composi.t.i.on and t:Y.<~ surfaa:::e of t:he object to be coated, which leads tc: poar water Tesistance.
The aforement.ic_~ned mixtLarfv may :ir:corpox-ate, as desired, small amouras of additives wtich may be useful in the manufactures of peelabl.e-c:oatinci compositions. Such additives include plast~icizers (e. g., phthalate esters and fatty acid est.ers), wax emulsions (including polyethylene-based emulsions and pol.y;~ropy:lE>ne-based emulsions), defoamir_g agents (e.g., mineral oils and silicone oils) , Rheoloc~y mod.i.f: ier (.ins ludinq inorganic type and organic type), UV ak.~sorbents (e. g., benzotriazoles and *Trade-mark benzophenones), pH modifiers (e.g., organic alkalis and ethanolamines), preservatives (e.g., benzoisothiazolines and triazines), coalescing agents (e. g., alkyl ethers of mono-or di-ethylene glycol and alkyl ethers of mono- or di-propylene glycol), anti-freezing agents (e. g., polyhydric alcohols), peelability-improving agents (e. g., silicone emulsions and alkylphosphoric esters), drying accelerators (e. g., lower alcohols such as ethyl alcohol).
The peelable coating composition of the present invention is intended to be applied onto surfaces of ' articles such as automobiles and other vehicles, machine parts, metallic household articles and other ferrous and non-ferrous articles, wooden articles, glass articles, rubber articles, and coated rubber articles, to thereby protect the surfaces of the articles in the open air or indoors. Needless to say, the composition of the present invention may be used for protecting surfaces of objects other than the above articles.
Specifically, the aqueous dispersion of peelable coating composition of the present invention is advantageously used, for example, for the following purposes.
1) Prevention of stains and scratches, or degradation due to UV rays, etc. of panel coatings and resin portions of automobiles.
2) Prevention of rust stains of machine parts.
3) Prevention of stains of edible oil and dirt from hands, when applied to ventilation fans and kitchen devices and utensils, 4) Prevention of stains and scratches of aluminum fences .
5) Prevention of stains and scratches of indoor floors.
6) Protection of the wall or floor materials in a paint booth against splashing of paints.
7) Prevention of scratches, or maintenance of good appearance when applied to skis made of an FRP resin.
Examples ' The present invention will next be described by way of Examples which demonstrate the effects of the invention as contrasted to Comparative Examples. However, the present invention should not be construed as being limited by the examples.
The emulsions having Tgs and particle sizes as shown in Tables 1 through 3 below were prepared, and subjected to the tests described hereinbelow.
The glass transition temperature (Tg) of each composition was measured in accordance with JIS K7121 "Testing Methods for Transition Temperatures of Plastics"
Table 1 1) Acrylic copolymer emulsion having a Tg of 40 °C or more Tg Particle Surfactant Ethylenically unsaturated (C size (nm) monomer having acid value (wto) ) A1 58 80 Reactive 0.6 A2 58 80 Non-reactive 0 B1 46 75 Reactive 0.8 B2 46 75 Reactive 5.0 C 46 250 Reactive 0.5 D 46 100 Non-reactive 0.1 Table 2 2) Acrylic copolymer emulsion having a Tg from -20°C to 5 °C
Tg Particle Surfactant Ethylenically unsaturated (C ) size (nm) monomer having acid value (wt%) F1 2 85 Reactive 0.4 F2 2 85 Reactive 0 G 2 300 ~ Reactive 0.5 H 2 250 Non-reacti ve 0.7 I -15 80 Reactive 0.7 Table 3 3) Acrylic copolymer emulsion having a Tg from 5°C to 40°C
Tg Particle Surfactant Ethylenically unsaturated (°C ) size (nm) monomer having acid value (wto) E 15 80 Reactive 0.5 4) Method for emulsion polymerization <Emulsion A1>
In a glass reactor equipped with a reflux condenser, a stirrer, a thermometer, a dropping funnel, and a gas-introduction tube were charged ammonium persulfate (1.25 parts), water (250 parts), a reactive surfactant "Aqualon RN-20" (trade name, Dai-ichi Kogyo Seiyaku K.K.) (1.8 parts), methyl methacrylate (MMA) (25 parts), butyl acrylate (BA) (23 parts), acrylic acid (AA) (2.3 parts), and t-dodecylmercaptane (0.9 parts). While the contents of the ' reactor were stirred, the air in the reactor was purged with nitrogen gas, and subsequently, the reactor was heated in a water bath (maintained at 60°C ).
When the temperature of the mixture in the reactor reached 60°C , a monomer mixture consisting of "Aqualon RN-20" (8.2 parts), methyl methacrylate (MMA) (112.5 parts), butyl acrylate (BA) (102 parts), acrylic acid (AA) (10.2 parts), and t-dodecylmercaptane (3.9 parts) and 2 wt.o aqueous sodium hydrogensulfite solution (32 parts) were added dropwise respectively for two hours.
After completion of addition, the system was stirred for 2 hours at 60 °C .
After completion of reaction,the mixture was cooled to obtain a thermoplastic resin emulsion containing 48o solids and having a pH of 3.2.
This system was neutralized with ammonia water to thereby obtain a stable emulsion A1. The Tg of this emulsion as measured in accordance with JIS K7121 was 58°C .
and the average particle size was 80 rurn.
<Emulsions Bl, B2, :, ~, fl, E'a, i~, I >
In a manner :~irni lar to that E:mpl;oyed for emulsion A1, Emulsions Bl, B~'., C, E, F1, F'~, ~~~ and T were prepared by changing the pro~)cr_ticlns ~~.f the monomers and changing the amourrt:r> of surfactants, ~.o thereby obtain emulsions Bl, B2, C, E~, F~'l, F2, G, an~ 1, having different particle ~>izes.
<Emulsions A2, D, and 1-~>
In the case of emul:ion:> A.'%, D, ,_:md H ~n whi_ch a nonreactive surfactmr=t was u~>c:,d, a surfactant (TRITON*
X-301, Rohm & Haas) , an initiator, arnt water werE: charged from the first, and when the t:.~urnpc:~ra~r_e of the mixture reached 60°C , a moruomer mixture and ai terminator were added to thereby obtain an emul:-;ion A::, D, or H.
Through use of emulsions A~. t:hro~..~gh I, the following compositions, i.e., representar_:i~res «i the present invention and the comparativEa exampl e.>, were obtained.
Example 1 Composition (unity parts) by weight) Emulsion D 3'.a Emulsion H ~,:3 Defoaming agents ') . 4 Rheology modifier ),1 pH modifier 1.5 MFT (minimum f:i lm--fc.rming t.erripera:~ture) - 12 ~C
Ethylenically i:.nsaturated znor~orne having acid va::lue . 0.490 by weight *Trade-mark _ 15 _ Example 2 Composition (unit: parts) by weight) Emulsion C 3'7 Emulsion G 59 Defoaming agent 0.5 Rheology modifier 0.1 Peelability-improving agent 1.0 pH modifier 1.4 Coalescing agent 1.0 ' MFT = 5 °C
Ethylenically unsaturated monomer having acid value . 0.500 by weight Example 3 Composition (unit: parts) by weight) Emulsion D 35 Emulsion F 63 Defoaming agent 0.4 Rheology modifier 0.1 pH modifier 1.5 MFT = 12°C
Ethylenically unsaturated monomer having acid value . 0.160 by weight Example 4 Composition (unit: parts) by weight) Emulsion A2 30 Emulsion F2 Defoaming agent 0.5 Rheology modifier 0.1 Peelability-improving agent 1.0 pH modifier 1.4 MFT = 12°C
Ethylenically unsaturated monomer having acid value . 0o by weight Example 5 ' Composition (unit: parts) by weight) Emulsion B2 3 Emulsion F2 60 Defoaming agent 0.4 Rheology modifier 0.1 pH modifier 1.5 Coalescing agent 1.0 MFT = 10°C
Ethylenically unsaturated monomer having acid value . 1.940 by weight Example 6 Composition (unit: parts) by weight) Emulsion A 30 Emulsion I 6g Defoaming agent 0.4 Rheology modifier 0.1 pH modifier 1.5 MFT < 0 °C
Ethylenically unsaturated monomer having acid value . 0.670 by weight Example 7 Composition (unit: parts) by weight) Emulsion B 37 Emulsion I 60 Defoaming agent 0.5 Rheology modifier 0.1 ' Peelability-improving agent 1.0 pH modifier 1.4 MFT < 0 °C
Ethylenically unsaturated monomer having acid value . 0.74% by weight Example 8 Composition (unit: parts) by weight) Emulsion B 25 Emulsion F 73 Defoaming agent 0.4 Rheology modifier 0.1 pH modifier 1.0 Peelability-improving agent 0.5 MFT = 7 °C
Ethylenically unsaturated monomer having acid value . 0.350 by weight Example 9 Composition (unit: parts) by weight) Emulsion D 20 Emulsion I
Defoaming agent 0,5 Rheology modifier 0.1 Peelability-improving agent 1.0 pH modifier 1.4 MFT < 0 °C
Ethylenically unsaturated monomer ' having acid value . 0.580 by weight Comparative Example 1 Composition (unit: parts) by weight) Emulsion A 4g Emulsion F 4g Defoaming agent 0.4 Rheology modifier 0.1 pH modifier 1.5 Coalescing agent 2.0 MFT (minimum film-forming temperature) - 10 °C
Ethylenically unsaturated monomer having acid value . 0.500 by weight Comparative Example 2 Composition (unit: parts) by weight) Emulsion B2 36 Emulsion F 59 Defoaming agent 0.4 Rheology modifier 0.1 pH modifier 1.5 Coalescing agent 2.0 MFT (minimum film-forming temperature) < 0°C
Ethylenically unsaturated monomer having acid value . 2.340 by weight Comparative Example 3 Composition (unit: parts) by weight) ' Emulsion E 98 (Tg . 15°C ) Defoaming agent 0.4 Rheology modifier 0.1 pH modifier 1.5 MFT (minimum film-forming temperature) - 12 °C
Ethylenically unsaturated monomer having acid value . 0.5o by weight (Test Items and Methods) <Preparation of test specimens>
The specimens used in the tests were coated plates prepared as follows. Electrodeposited mild steel plates were spray-coated with an aminoalkyd resin-base paint. When the surface drys to Touch, an acrylic resin-base clear paint was sprayed, and the plates were subsequently baked at 140 °C for 20 minutes. To the resultant painted plates were applied each of the compositions prepared in the above-described Examples and Comparative Examples so as to have a film thickness of 70,u m (dry). A diversified tests were performed in terms of the below-described properties by use of the thus-prepared coated plates as test specimens.
* Peelability: Peelability of test specimens placed at °C , 25°C , or 40 °C was checked.
* Acid resistance: A droplet of 40o sulfuric acid aq.soln was placed on each test specimen, and the specimen was allowed to stand for 15 minutes in a 60 °C thermostatic chamber.
After the specimen was cooled to room temperature, the film ' was peeled off, and changes of the paint were checked.
* Alkali resistance: A droplet of 0.1N sodium hydroxide aq.soln was placed on each test specimen, and the specimen was allowed to stand for 3 hours at 70°C . After the specimen was cooled to room temperature, the film was peeled off, andchanges of the paint were checked.
* water resistance: The film-coated test specimens were soaked in 25°C water for 24 hours, and the whitening degree was observed.
* Adhesive strength: The film-coated test specimens were soaked in 25°C water for 24 hours, and presence or absence of natural peeling-off was observed.
* Peelability after heated: The test specimens were left in a 80 °C thermostatic chamber for 500 hours and subsequently peelability was checked at room temperature.
* Accelerated weather resistance: The test specimens were placed in an SwOM tester for 500 hours so as to accelerate degradation of the film and subsequently peelability was checked.
* Cycle test: Each test specimen was subjected to a cycle test, in which each cycle consisted of heating at 80°~ for 24 hours and subsequent cooling at 0°~ for 24 hours. After the test specimen had undergone 10 cycles, peelability of the specimen was checked.
* External exposure: The test specimens were exposed to the open air in Okinawa prefecture. When six months (including 3 months in summer) had passed, peelability of the specimen was checked.
' *Combustion test: A small amount of film that had peeled off was collected and burned. Nitrogen oxides contained in the combustion gas were analyzed in accordance with JIS
K0104.
The test results are shown in Table 4.
The evaluation standards were as follows:
A: Very good, B: Good, C: Poor, and D: Very poor.
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As shown in Table 4, whereas specimens falling within the scope of the present invention were excellent with respect to all the test items, those of comparative examples were inferior to the specimens of the invention, proving the synergism achieved by the present invention.
As described hereinabove by way of examples, the aqueous dispersion of peelable coating composition of the present invention which is an acrylic copolymer emulsion exhibits excellent peelability due to the synergism of the following features: 1) The composition comprises a mixture of two acrylic copolymer emulsions, wherein the acrylic copolymers have different predetermined glass transition temperatures, 2) the amount of ethylenically unsaturated monomers having acid value in the mixture is not higher than a predetermined level, and 3) the emulsion does not make use of a nitrogen- containing monomer.
Moreover, in addition to the above-mentioned features 1) through 3), when 4) polymerization is performed under conditions in which at least one of the emulsions contains a reactive surfactant and 5) the particle size of the emulsions is controlled to fall within a predetermined range, there can be obtained, as a result of further synergism, an aqueous dispersion of a peelable coating composition having further improved water resistance, adhesiveness, and peelability.
Furthermore, since no nitrogen-containing monomers such as acrylonitrile are contained in the acrylic emulsions, when the film is peeled off after the protection period is over and the waste film is burned and disposed of, gases containing nitrogen oxides are not generated and thus there is no fear of environmental pollution.
Accordingly, the aqueous dispersion of peelable coating composition of the present invention enables to achieve protective effects superior to those obtained from previous products when used, for example, for the following purposes.
1) Prevention of stains and scratches, or degradation due to UV rays, etc. of panel coatings and resin portions of automobiles.
2) Prevention of rust stains of machine parts.
3) Prevention of stains of edible oil and dirt from hands, through application to ventilation fans and kitchen devices and utensils, 4) Prevention of stains and scratches of aluminum fences .
5) Prevention of stains and scratches of indoor floors.
6) Protection of the wall or floor materials in a paint booth against splashing of paints.
7) Prevention of scratches, or maintenance of good appearance when applied to skis made of an FRP resin.
Examples ' The present invention will next be described by way of Examples which demonstrate the effects of the invention as contrasted to Comparative Examples. However, the present invention should not be construed as being limited by the examples.
The emulsions having Tgs and particle sizes as shown in Tables 1 through 3 below were prepared, and subjected to the tests described hereinbelow.
The glass transition temperature (Tg) of each composition was measured in accordance with JIS K7121 "Testing Methods for Transition Temperatures of Plastics"
Table 1 1) Acrylic copolymer emulsion having a Tg of 40 °C or more Tg Particle Surfactant Ethylenically unsaturated (C size (nm) monomer having acid value (wto) ) A1 58 80 Reactive 0.6 A2 58 80 Non-reactive 0 B1 46 75 Reactive 0.8 B2 46 75 Reactive 5.0 C 46 250 Reactive 0.5 D 46 100 Non-reactive 0.1 Table 2 2) Acrylic copolymer emulsion having a Tg from -20°C to 5 °C
Tg Particle Surfactant Ethylenically unsaturated (C ) size (nm) monomer having acid value (wt%) F1 2 85 Reactive 0.4 F2 2 85 Reactive 0 G 2 300 ~ Reactive 0.5 H 2 250 Non-reacti ve 0.7 I -15 80 Reactive 0.7 Table 3 3) Acrylic copolymer emulsion having a Tg from 5°C to 40°C
Tg Particle Surfactant Ethylenically unsaturated (°C ) size (nm) monomer having acid value (wto) E 15 80 Reactive 0.5 4) Method for emulsion polymerization <Emulsion A1>
In a glass reactor equipped with a reflux condenser, a stirrer, a thermometer, a dropping funnel, and a gas-introduction tube were charged ammonium persulfate (1.25 parts), water (250 parts), a reactive surfactant "Aqualon RN-20" (trade name, Dai-ichi Kogyo Seiyaku K.K.) (1.8 parts), methyl methacrylate (MMA) (25 parts), butyl acrylate (BA) (23 parts), acrylic acid (AA) (2.3 parts), and t-dodecylmercaptane (0.9 parts). While the contents of the ' reactor were stirred, the air in the reactor was purged with nitrogen gas, and subsequently, the reactor was heated in a water bath (maintained at 60°C ).
When the temperature of the mixture in the reactor reached 60°C , a monomer mixture consisting of "Aqualon RN-20" (8.2 parts), methyl methacrylate (MMA) (112.5 parts), butyl acrylate (BA) (102 parts), acrylic acid (AA) (10.2 parts), and t-dodecylmercaptane (3.9 parts) and 2 wt.o aqueous sodium hydrogensulfite solution (32 parts) were added dropwise respectively for two hours.
After completion of addition, the system was stirred for 2 hours at 60 °C .
After completion of reaction,the mixture was cooled to obtain a thermoplastic resin emulsion containing 48o solids and having a pH of 3.2.
This system was neutralized with ammonia water to thereby obtain a stable emulsion A1. The Tg of this emulsion as measured in accordance with JIS K7121 was 58°C .
and the average particle size was 80 rurn.
<Emulsions Bl, B2, :, ~, fl, E'a, i~, I >
In a manner :~irni lar to that E:mpl;oyed for emulsion A1, Emulsions Bl, B~'., C, E, F1, F'~, ~~~ and T were prepared by changing the pro~)cr_ticlns ~~.f the monomers and changing the amourrt:r> of surfactants, ~.o thereby obtain emulsions Bl, B2, C, E~, F~'l, F2, G, an~ 1, having different particle ~>izes.
<Emulsions A2, D, and 1-~>
In the case of emul:ion:> A.'%, D, ,_:md H ~n whi_ch a nonreactive surfactmr=t was u~>c:,d, a surfactant (TRITON*
X-301, Rohm & Haas) , an initiator, arnt water werE: charged from the first, and when the t:.~urnpc:~ra~r_e of the mixture reached 60°C , a moruomer mixture and ai terminator were added to thereby obtain an emul:-;ion A::, D, or H.
Through use of emulsions A~. t:hro~..~gh I, the following compositions, i.e., representar_:i~res «i the present invention and the comparativEa exampl e.>, were obtained.
Example 1 Composition (unity parts) by weight) Emulsion D 3'.a Emulsion H ~,:3 Defoaming agents ') . 4 Rheology modifier ),1 pH modifier 1.5 MFT (minimum f:i lm--fc.rming t.erripera:~ture) - 12 ~C
Ethylenically i:.nsaturated znor~orne having acid va::lue . 0.490 by weight *Trade-mark _ 15 _ Example 2 Composition (unit: parts) by weight) Emulsion C 3'7 Emulsion G 59 Defoaming agent 0.5 Rheology modifier 0.1 Peelability-improving agent 1.0 pH modifier 1.4 Coalescing agent 1.0 ' MFT = 5 °C
Ethylenically unsaturated monomer having acid value . 0.500 by weight Example 3 Composition (unit: parts) by weight) Emulsion D 35 Emulsion F 63 Defoaming agent 0.4 Rheology modifier 0.1 pH modifier 1.5 MFT = 12°C
Ethylenically unsaturated monomer having acid value . 0.160 by weight Example 4 Composition (unit: parts) by weight) Emulsion A2 30 Emulsion F2 Defoaming agent 0.5 Rheology modifier 0.1 Peelability-improving agent 1.0 pH modifier 1.4 MFT = 12°C
Ethylenically unsaturated monomer having acid value . 0o by weight Example 5 ' Composition (unit: parts) by weight) Emulsion B2 3 Emulsion F2 60 Defoaming agent 0.4 Rheology modifier 0.1 pH modifier 1.5 Coalescing agent 1.0 MFT = 10°C
Ethylenically unsaturated monomer having acid value . 1.940 by weight Example 6 Composition (unit: parts) by weight) Emulsion A 30 Emulsion I 6g Defoaming agent 0.4 Rheology modifier 0.1 pH modifier 1.5 MFT < 0 °C
Ethylenically unsaturated monomer having acid value . 0.670 by weight Example 7 Composition (unit: parts) by weight) Emulsion B 37 Emulsion I 60 Defoaming agent 0.5 Rheology modifier 0.1 ' Peelability-improving agent 1.0 pH modifier 1.4 MFT < 0 °C
Ethylenically unsaturated monomer having acid value . 0.74% by weight Example 8 Composition (unit: parts) by weight) Emulsion B 25 Emulsion F 73 Defoaming agent 0.4 Rheology modifier 0.1 pH modifier 1.0 Peelability-improving agent 0.5 MFT = 7 °C
Ethylenically unsaturated monomer having acid value . 0.350 by weight Example 9 Composition (unit: parts) by weight) Emulsion D 20 Emulsion I
Defoaming agent 0,5 Rheology modifier 0.1 Peelability-improving agent 1.0 pH modifier 1.4 MFT < 0 °C
Ethylenically unsaturated monomer ' having acid value . 0.580 by weight Comparative Example 1 Composition (unit: parts) by weight) Emulsion A 4g Emulsion F 4g Defoaming agent 0.4 Rheology modifier 0.1 pH modifier 1.5 Coalescing agent 2.0 MFT (minimum film-forming temperature) - 10 °C
Ethylenically unsaturated monomer having acid value . 0.500 by weight Comparative Example 2 Composition (unit: parts) by weight) Emulsion B2 36 Emulsion F 59 Defoaming agent 0.4 Rheology modifier 0.1 pH modifier 1.5 Coalescing agent 2.0 MFT (minimum film-forming temperature) < 0°C
Ethylenically unsaturated monomer having acid value . 2.340 by weight Comparative Example 3 Composition (unit: parts) by weight) ' Emulsion E 98 (Tg . 15°C ) Defoaming agent 0.4 Rheology modifier 0.1 pH modifier 1.5 MFT (minimum film-forming temperature) - 12 °C
Ethylenically unsaturated monomer having acid value . 0.5o by weight (Test Items and Methods) <Preparation of test specimens>
The specimens used in the tests were coated plates prepared as follows. Electrodeposited mild steel plates were spray-coated with an aminoalkyd resin-base paint. When the surface drys to Touch, an acrylic resin-base clear paint was sprayed, and the plates were subsequently baked at 140 °C for 20 minutes. To the resultant painted plates were applied each of the compositions prepared in the above-described Examples and Comparative Examples so as to have a film thickness of 70,u m (dry). A diversified tests were performed in terms of the below-described properties by use of the thus-prepared coated plates as test specimens.
* Peelability: Peelability of test specimens placed at °C , 25°C , or 40 °C was checked.
* Acid resistance: A droplet of 40o sulfuric acid aq.soln was placed on each test specimen, and the specimen was allowed to stand for 15 minutes in a 60 °C thermostatic chamber.
After the specimen was cooled to room temperature, the film ' was peeled off, and changes of the paint were checked.
* Alkali resistance: A droplet of 0.1N sodium hydroxide aq.soln was placed on each test specimen, and the specimen was allowed to stand for 3 hours at 70°C . After the specimen was cooled to room temperature, the film was peeled off, andchanges of the paint were checked.
* water resistance: The film-coated test specimens were soaked in 25°C water for 24 hours, and the whitening degree was observed.
* Adhesive strength: The film-coated test specimens were soaked in 25°C water for 24 hours, and presence or absence of natural peeling-off was observed.
* Peelability after heated: The test specimens were left in a 80 °C thermostatic chamber for 500 hours and subsequently peelability was checked at room temperature.
* Accelerated weather resistance: The test specimens were placed in an SwOM tester for 500 hours so as to accelerate degradation of the film and subsequently peelability was checked.
* Cycle test: Each test specimen was subjected to a cycle test, in which each cycle consisted of heating at 80°~ for 24 hours and subsequent cooling at 0°~ for 24 hours. After the test specimen had undergone 10 cycles, peelability of the specimen was checked.
* External exposure: The test specimens were exposed to the open air in Okinawa prefecture. When six months (including 3 months in summer) had passed, peelability of the specimen was checked.
' *Combustion test: A small amount of film that had peeled off was collected and burned. Nitrogen oxides contained in the combustion gas were analyzed in accordance with JIS
K0104.
The test results are shown in Table 4.
The evaluation standards were as follows:
A: Very good, B: Good, C: Poor, and D: Very poor.
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As shown in Table 4, whereas specimens falling within the scope of the present invention were excellent with respect to all the test items, those of comparative examples were inferior to the specimens of the invention, proving the synergism achieved by the present invention.
As described hereinabove by way of examples, the aqueous dispersion of peelable coating composition of the present invention which is an acrylic copolymer emulsion exhibits excellent peelability due to the synergism of the following features: 1) The composition comprises a mixture of two acrylic copolymer emulsions, wherein the acrylic copolymers have different predetermined glass transition temperatures, 2) the amount of ethylenically unsaturated monomers having acid value in the mixture is not higher than a predetermined level, and 3) the emulsion does not make use of a nitrogen- containing monomer.
Moreover, in addition to the above-mentioned features 1) through 3), when 4) polymerization is performed under conditions in which at least one of the emulsions contains a reactive surfactant and 5) the particle size of the emulsions is controlled to fall within a predetermined range, there can be obtained, as a result of further synergism, an aqueous dispersion of a peelable coating composition having further improved water resistance, adhesiveness, and peelability.
Furthermore, since no nitrogen-containing monomers such as acrylonitrile are contained in the acrylic emulsions, when the film is peeled off after the protection period is over and the waste film is burned and disposed of, gases containing nitrogen oxides are not generated and thus there is no fear of environmental pollution.
Accordingly, the aqueous dispersion of peelable coating composition of the present invention enables to achieve protective effects superior to those obtained from previous products when used, for example, for the following purposes.
1) Prevention of stains and scratches, or degradation due to UV rays, etc. of panel coatings and resin portions of automobiles.
2) Prevention of rust stains of machine parts.
3) Prevention of stains of edible oil and dirt from hands, through application to ventilation fans and kitchen devices and utensils, 4) Prevention of stains and scratches of aluminum fences .
5) Prevention of stains and scratches of indoor floors.
6) Protection of the wall or floor materials in a paint booth against splashing of paints.
7) Prevention of scratches, or maintenance of good appearance when applied to skis made of an FRP resin.
Claims (2)
1. An aqueous dispersion of a peelable coating composition comprising a mixture containing 5-40% by weight of an emulsion of a first acrylic copolymer having a glass transition temperature of not lower than 40 °C, and 95-60% by weight of an emulsion of a second acrylic copolymer having a glass transition temperature ranging from -20°C through 5 °C; wherein the mixture of the acrylic copolymer emulsions contains ethylenically unsaturated vinyl monomers having acid value in a total amount of less than 2.0% by weight, and wherein the mixture of acrylic copolymer emulsions is free of nitrogen-containing vinyl monomers.
2. An aqueous dispersion of a peelable coating composition according to claim 1, wherein at least one of said first and second acrylic copolymers is an acrylic copolymer which has been polymerized by use of a reactive surfactant, and the acrylic copolymer emulsions have a particle size of not more than 200 nm.
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10098696A JP3486050B2 (en) | 1996-04-23 | 1996-04-23 | Peelable coating agent water dispersion |
| US08/953,090 US6211282B1 (en) | 1996-04-23 | 1997-10-17 | Aqueous dispersion of a peelable coating composition |
| ES97118159T ES2191799T3 (en) | 1996-04-23 | 1997-10-20 | WATERPROOF DISPERSION OF A DISPOSABLE COATING COMPOSITION. |
| PT97118159T PT911375E (en) | 1996-04-23 | 1997-10-20 | AQUEOUS DISPERSION OF A STRENGTHY COATING COMPOSITION |
| DE1997620724 DE69720724T2 (en) | 1996-04-23 | 1997-10-20 | Aqueous dispersion of a peelable coating composition |
| DK97118159T DK0911375T3 (en) | 1996-04-23 | 1997-10-20 | Aqueous dispersion of a peelable coating composition |
| EP97118159A EP0911375B1 (en) | 1996-04-23 | 1997-10-20 | Aqueous dispersion of a peelable coating composition |
| AT97118159T ATE236961T1 (en) | 1996-04-23 | 1997-10-20 | AQUEOUS DISPERSION OF A REMOVABLE COATING COMPOSITION |
| AU42735/97A AU747352B2 (en) | 1996-04-23 | 1997-10-21 | Aqueous dispersion of a peelable coating composition |
| TW86115594A TW428015B (en) | 1996-04-23 | 1997-10-22 | Aqueous dispersion of a peelable coating composition |
| CNB971228663A CN1177900C (en) | 1996-04-23 | 1997-10-22 | Strippable coating water dispersion material |
| CA 2219208 CA2219208C (en) | 1996-04-23 | 1997-10-23 | Aqueous dispersion of a peelable coating composition |
| US09/775,776 US6344236B2 (en) | 1996-04-23 | 2001-02-02 | Aqueous dispersion of a peelable coating composition |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10098696A JP3486050B2 (en) | 1996-04-23 | 1996-04-23 | Peelable coating agent water dispersion |
| US08/953,090 US6211282B1 (en) | 1996-04-23 | 1997-10-17 | Aqueous dispersion of a peelable coating composition |
| EP97118159A EP0911375B1 (en) | 1996-04-23 | 1997-10-20 | Aqueous dispersion of a peelable coating composition |
| AU42735/97A AU747352B2 (en) | 1996-04-23 | 1997-10-21 | Aqueous dispersion of a peelable coating composition |
| CNB971228663A CN1177900C (en) | 1996-04-23 | 1997-10-22 | Strippable coating water dispersion material |
| CA 2219208 CA2219208C (en) | 1996-04-23 | 1997-10-23 | Aqueous dispersion of a peelable coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2219208A1 CA2219208A1 (en) | 1999-04-23 |
| CA2219208C true CA2219208C (en) | 2004-04-20 |
Family
ID=27542699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2219208 Expired - Fee Related CA2219208C (en) | 1996-04-23 | 1997-10-23 | Aqueous dispersion of a peelable coating composition |
Country Status (12)
| Country | Link |
|---|---|
| US (2) | US6211282B1 (en) |
| EP (1) | EP0911375B1 (en) |
| JP (1) | JP3486050B2 (en) |
| CN (1) | CN1177900C (en) |
| AT (1) | ATE236961T1 (en) |
| AU (1) | AU747352B2 (en) |
| CA (1) | CA2219208C (en) |
| DE (1) | DE69720724T2 (en) |
| DK (1) | DK0911375T3 (en) |
| ES (1) | ES2191799T3 (en) |
| PT (1) | PT911375E (en) |
| TW (1) | TW428015B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6767579B1 (en) * | 1998-11-24 | 2004-07-27 | Corning Incorporated | Methods for protecting silica-containing article in optical fiber manufacturing |
| JP3538574B2 (en) * | 1999-09-27 | 2004-06-14 | 株式会社リンレイ | Peelable coating composition |
| AU775470B2 (en) | 2000-03-03 | 2004-08-05 | Rohm And Haas Company | Removable coating composition and preparative method |
| EP1642940B1 (en) * | 2000-03-03 | 2010-06-09 | Rohm and Haas Company | Removable coating composition and preparative method |
| WO2003002674A1 (en) * | 2001-06-27 | 2003-01-09 | Pennzoil-Quaker State Company | Coating composition |
| DE10155184A1 (en) * | 2001-11-12 | 2003-05-22 | Bayer Ag | Emulsion polymers as a peelable varnish |
| US6645554B1 (en) * | 2002-07-30 | 2003-11-11 | Lepage Joseph R. | Method of using a multi-purpose flexible coating compound |
| US7030175B2 (en) * | 2003-02-06 | 2006-04-18 | Hewlett-Packard Development Company, L.P. | Ink jet latex having reactive surfactant stabilization |
| EP1602682A1 (en) * | 2004-05-31 | 2005-12-07 | Nippon Shokubai Co.,Ltd. | Dispersion, production method thereof and use thereof |
| EP1634921A1 (en) * | 2004-09-10 | 2006-03-15 | hanse chemie GmbH | Polymer resin composition |
| GB0424878D0 (en) * | 2004-11-10 | 2004-12-15 | Innovia Films Ltd | Innovia films case A100 |
| WO2007112294A1 (en) | 2006-03-24 | 2007-10-04 | Henkel Corporation | Sprayable water-based adhesive |
| US20070259029A1 (en) * | 2006-05-08 | 2007-11-08 | Mcentire Edward Enns | Water-dispersible patch containing an active agent for dermal delivery |
| US20070258935A1 (en) * | 2006-05-08 | 2007-11-08 | Mcentire Edward Enns | Water dispersible films for delivery of active agents to the epidermis |
| US20080057090A1 (en) * | 2006-09-01 | 2008-03-06 | Mcentire Edward Enns | Wrinkle masking film composition for skin |
| US7879942B2 (en) * | 2006-10-05 | 2011-02-01 | Eastman Chemical Company | Switchable adhesive article for attachment to skin and method of using the same |
| BRPI0811171A2 (en) * | 2007-05-17 | 2014-12-23 | Johnson Diversey Inc | SURFACE COATING SYSTEM AND METHOD |
| US20090068456A1 (en) * | 2007-09-06 | 2009-03-12 | Dai Nippon Printing Co., Ltd. | Protective layer transfer sheet |
| EP2714820A4 (en) | 2011-05-25 | 2014-11-05 | Diversey Inc | Surface coating system and method of using surface coating system |
| US20140087156A1 (en) * | 2011-05-25 | 2014-03-27 | Diversey, Inc. | Surface coating system and method of making and using same |
| GB2499787B (en) | 2012-02-23 | 2015-05-20 | Liberty Vaults Ltd | Mobile phone |
| TWI473863B (en) * | 2012-12-19 | 2015-02-21 | Nanya Plastics Corp | Peelable protective film and its composition thereof |
| GB2517732A (en) | 2013-08-29 | 2015-03-04 | Sim & Pin Ltd | System for accessing data from multiple devices |
| CN103467890B (en) * | 2013-09-18 | 2016-04-20 | 南亚塑胶工业股份有限公司 | A kind of peelable protective film and composite formula thereof |
| CN103555128B (en) * | 2013-10-25 | 2015-11-11 | 巫溪县迪纳木业有限公司 | Be convenient to the face glue of the template demoulding |
| JP2015232099A (en) * | 2014-06-10 | 2015-12-24 | 太洋塗料株式会社 | Color masking paint, building materials and building materials stack |
| US20170114244A1 (en) | 2014-06-18 | 2017-04-27 | Lubrizol Advanced Materials, Inc. | Peelable composition |
| US20160015178A1 (en) * | 2014-07-21 | 2016-01-21 | Mohammed Abdullah ALSHADY | Spray for kitchens and restrooms |
| WO2018073234A1 (en) | 2016-10-17 | 2018-04-26 | Dsm Ip Assets B.V. | Aqueous dispersion and uses thereof |
| JP2022130782A (en) * | 2021-02-26 | 2022-09-07 | バッセル化学株式会社 | Water-based antifouling paint composition, antifouling coating formed using the same, and fishing net, ship, and underwater structure having the coating on surface |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1536277A (en) | 1967-05-31 | 1968-08-16 | Ct Tech Du Cuir | Process and product for the protection against stains, scratches or the like, of the surfaces of articles of leather or other similar materials, during their manufacture |
| JPS5232757B2 (en) | 1973-08-14 | 1977-08-23 | ||
| JPS59215365A (en) | 1983-05-23 | 1984-12-05 | Nippon Akuriru Kagaku Kk | Strippable coating composition |
| DE3842796A1 (en) * | 1988-12-20 | 1990-06-21 | Roehm Gmbh | CLEAR IMPACT IMPACT ACRYLATE |
| JPH04318074A (en) | 1991-04-17 | 1992-11-09 | Shinto Paint Co Ltd | Temporarily protecting coating film composition |
| CA2079926A1 (en) | 1991-10-30 | 1993-05-01 | David C. Fistner, Sr. | Gloss acrylic paint |
| JPH06184469A (en) | 1992-12-16 | 1994-07-05 | Shinto Paint Co Ltd | Temporary protective film composition |
| ZA947537B (en) * | 1993-09-29 | 1995-05-26 | Ici Australia Operations | Water-borne soil resistant coatings |
| JP3751649B2 (en) | 1994-12-01 | 2006-03-01 | 関西ペイント株式会社 | Temporary protection method for automotive skin coating |
| US5712346A (en) * | 1995-02-14 | 1998-01-27 | Avery Dennison Corporation | Acrylic emulsion coatings |
| GB2300193B (en) * | 1995-04-05 | 1998-12-09 | Cray Valley Ltd | Aqueous polymer dispersions |
| WO1996036671A1 (en) | 1995-05-19 | 1996-11-21 | Kansai Paint Co., Ltd. | Peelable aqueous coating composition and method of temporarily protecting automobile outside-plate coating therewith |
| AUPO216396A0 (en) | 1996-09-06 | 1996-10-03 | Ici Australia Operations Proprietary Limited | Stain resistant water-borne paint |
-
1996
- 1996-04-23 JP JP10098696A patent/JP3486050B2/en not_active Expired - Lifetime
-
1997
- 1997-10-17 US US08/953,090 patent/US6211282B1/en not_active Expired - Fee Related
- 1997-10-20 EP EP97118159A patent/EP0911375B1/en not_active Expired - Lifetime
- 1997-10-20 PT PT97118159T patent/PT911375E/en unknown
- 1997-10-20 ES ES97118159T patent/ES2191799T3/en not_active Expired - Lifetime
- 1997-10-20 DK DK97118159T patent/DK0911375T3/en active
- 1997-10-20 AT AT97118159T patent/ATE236961T1/en not_active IP Right Cessation
- 1997-10-20 DE DE1997620724 patent/DE69720724T2/en not_active Expired - Fee Related
- 1997-10-21 AU AU42735/97A patent/AU747352B2/en not_active Ceased
- 1997-10-22 CN CNB971228663A patent/CN1177900C/en not_active Expired - Fee Related
- 1997-10-22 TW TW86115594A patent/TW428015B/en not_active IP Right Cessation
- 1997-10-23 CA CA 2219208 patent/CA2219208C/en not_active Expired - Fee Related
-
2001
- 2001-02-02 US US09/775,776 patent/US6344236B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US6344236B2 (en) | 2002-02-05 |
| DE69720724T2 (en) | 2004-03-04 |
| JPH09286934A (en) | 1997-11-04 |
| US6211282B1 (en) | 2001-04-03 |
| CN1215073A (en) | 1999-04-28 |
| EP0911375A1 (en) | 1999-04-28 |
| PT911375E (en) | 2003-06-30 |
| AU4273597A (en) | 1999-05-13 |
| US20010005733A1 (en) | 2001-06-28 |
| TW428015B (en) | 2001-04-01 |
| AU747352B2 (en) | 2002-05-16 |
| CA2219208A1 (en) | 1999-04-23 |
| DE69720724D1 (en) | 2003-05-15 |
| ATE236961T1 (en) | 2003-04-15 |
| JP3486050B2 (en) | 2004-01-13 |
| DK0911375T3 (en) | 2003-05-05 |
| EP0911375B1 (en) | 2003-04-09 |
| CN1177900C (en) | 2004-12-01 |
| ES2191799T3 (en) | 2003-09-16 |
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