CA2482599A1 - Coating compositions containing polyurethane dispersions and highly crosslinked polymer particles - Google Patents
Coating compositions containing polyurethane dispersions and highly crosslinked polymer particles Download PDFInfo
- Publication number
- CA2482599A1 CA2482599A1 CA 2482599 CA2482599A CA2482599A1 CA 2482599 A1 CA2482599 A1 CA 2482599A1 CA 2482599 CA2482599 CA 2482599 CA 2482599 A CA2482599 A CA 2482599A CA 2482599 A1 CA2482599 A1 CA 2482599A1
- Authority
- CA
- Canada
- Prior art keywords
- meth
- acrylate
- group
- ethylenically unsaturated
- polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract 48
- 229920003009 polyurethane dispersion Polymers 0.000 title claims abstract 31
- 239000008199 coating composition Substances 0.000 title claims 43
- 229920006037 cross link polymer Polymers 0.000 title 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract 246
- 239000000178 monomer Substances 0.000 claims abstract 135
- 239000000203 mixture Substances 0.000 claims abstract 64
- 239000007795 chemical reaction product Substances 0.000 claims abstract 52
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract 40
- 238000004132 cross linking Methods 0.000 claims abstract 39
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract 38
- 229920005862 polyol Polymers 0.000 claims abstract 38
- 229920002635 polyurethane Polymers 0.000 claims abstract 36
- 239000004814 polyurethane Substances 0.000 claims abstract 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract 32
- 239000001257 hydrogen Substances 0.000 claims abstract 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract 32
- 150000003077 polyols Chemical class 0.000 claims abstract 32
- 239000005056 polyisocyanate Substances 0.000 claims abstract 29
- 229920001228 polyisocyanate Polymers 0.000 claims abstract 29
- 150000001875 compounds Chemical class 0.000 claims abstract 20
- 230000002209 hydrophobic effect Effects 0.000 claims abstract 20
- 239000012736 aqueous medium Substances 0.000 claims abstract 13
- 239000000839 emulsion Substances 0.000 claims abstract 13
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract 7
- -1 acrylic polyols Chemical class 0.000 claims 68
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 36
- 125000000524 functional group Chemical group 0.000 claims 35
- 239000010410 layer Substances 0.000 claims 34
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 30
- 239000000758 substrate Substances 0.000 claims 30
- 239000011248 coating agent Substances 0.000 claims 27
- 238000000576 coating method Methods 0.000 claims 27
- 239000002131 composite material Substances 0.000 claims 27
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims 24
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 24
- 238000000034 method Methods 0.000 claims 23
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 22
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 claims 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 18
- 150000002334 glycols Chemical class 0.000 claims 18
- 239000000376 reactant Substances 0.000 claims 17
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 14
- 239000011859 microparticle Substances 0.000 claims 14
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 12
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 12
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims 12
- 150000002148 esters Chemical class 0.000 claims 12
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims 12
- 229920001223 polyethylene glycol Polymers 0.000 claims 12
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims 12
- 238000006116 polymerization reaction Methods 0.000 claims 11
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims 10
- 239000003795 chemical substances by application Substances 0.000 claims 10
- 239000000049 pigment Substances 0.000 claims 10
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims 8
- 125000003282 alkyl amino group Chemical group 0.000 claims 8
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims 7
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims 6
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims 6
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims 6
- 229940058015 1,3-butylene glycol Drugs 0.000 claims 6
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 claims 6
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 claims 6
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims 6
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims 6
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims 6
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims 6
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims 6
- 239000004641 Diallyl-phthalate Substances 0.000 claims 6
- 239000004593 Epoxy Substances 0.000 claims 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 6
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 claims 6
- 239000002202 Polyethylene glycol Substances 0.000 claims 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 6
- 125000001931 aliphatic group Chemical group 0.000 claims 6
- 125000003118 aryl group Chemical group 0.000 claims 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 6
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims 6
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 claims 6
- 235000019437 butane-1,3-diol Nutrition 0.000 claims 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 6
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims 6
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 6
- 230000000694 effects Effects 0.000 claims 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims 6
- 239000012948 isocyanate Substances 0.000 claims 6
- 150000002513 isocyanates Chemical class 0.000 claims 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims 6
- 229920005906 polyester polyol Polymers 0.000 claims 6
- 229920001451 polypropylene glycol Polymers 0.000 claims 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 6
- 239000000600 sorbitol Substances 0.000 claims 6
- 125000001424 substituent group Chemical group 0.000 claims 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 6
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims 6
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims 6
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 claims 6
- 229940114072 12-hydroxystearic acid Drugs 0.000 claims 5
- 239000004816 latex Substances 0.000 claims 5
- 229920000126 latex Polymers 0.000 claims 5
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims 4
- 239000011247 coating layer Substances 0.000 claims 4
- 239000000084 colloidal system Substances 0.000 claims 4
- 239000003995 emulsifying agent Substances 0.000 claims 4
- 230000001681 protective effect Effects 0.000 claims 4
- QIGWKXJECZQOGX-UHFFFAOYSA-N 1-amino-1-(1-amino-1,2-dihydroxyethoxy)ethane-1,2-diol Chemical compound C(O)C(O)(N)OC(O)(CO)N QIGWKXJECZQOGX-UHFFFAOYSA-N 0.000 claims 3
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims 3
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 claims 3
- 150000001412 amines Chemical class 0.000 claims 3
- 229920003180 amino resin Polymers 0.000 claims 3
- 239000003431 cross linking reagent Substances 0.000 claims 3
- ARZLUCYKIWYSHR-UHFFFAOYSA-N hydroxymethoxymethanol Chemical compound OCOCO ARZLUCYKIWYSHR-UHFFFAOYSA-N 0.000 claims 3
- 239000000463 material Substances 0.000 claims 3
- VGPBPWRBXBKGRE-UHFFFAOYSA-N n-(oxomethylidene)hydroxylamine Chemical compound ON=C=O VGPBPWRBXBKGRE-UHFFFAOYSA-N 0.000 claims 3
- 229920000768 polyamine Polymers 0.000 claims 3
- 229920000642 polymer Polymers 0.000 claims 3
- 229920005989 resin Polymers 0.000 claims 3
- 239000011347 resin Substances 0.000 claims 3
- 239000000843 powder Substances 0.000 claims 2
- AZKSXXWROJGHGN-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O.CCCCCCC(O)CCCCCCCCCCC(O)=O AZKSXXWROJGHGN-UHFFFAOYSA-N 0.000 claims 1
- 239000011258 core-shell material Substances 0.000 claims 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
- C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
- C08G18/765—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
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- 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.]
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- 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.]
- Y10T428/31554—Next to second layer of polyamidoester
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- 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.]
- Y10T428/31605—Next to free metal
Abstract
An aqueous polyurethane dispersion and thermosetting compositions containing them. The aqueous polyurethane dispersion includes an aqueous medium with dispersed polyurethane-acrylate particles, which include the reaction product obtained by polymerizing a pre-emulsion formed from hydrophobic polymerizable ethylenically unsaturated monomers, a crosslinking monomer, and an active hydrogen-containing polyurethane acrylate prepolymer, which is a reaction product obtained by reacting a polyol, a polymerizable, ethylenically unsaturated monomer containing at least one hydroxyl group, a compound that includes an alkyl group having at least one hydroxyl group and optionally a carboxylic acid group, and a polyisocyanate. The prepolymer includes at least 30 percent by weight of polyurethane acrylate prepolymers with at least one terminal ethylenic unsaturation at one end of the molecule, and at least one active hydrogen-containing group at the opposite end; and at least 10 percent by weight of prepolymers having at least one terminal ethylenic unsaturation at each end of the molecule.
Claims (129)
1. A thermosetting composition comprising:
(I) a first reactant comprising reactive functional groups;
(II) a curing agent having functional groups reactive with the functional groups of the first reactant in (I);
(III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprised of:
(a) at least 20 weight percent of a crosslinking monomer having two or more groups of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 2 weight percent of one or more polymerizable ethylenically unsaturated monomers having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from -NR1R2, -OR3 and -SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and , -CH2CH2-(OC(CH3)HCH3)m-OH
where m is 0 to 30, D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) optionally, the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other; and (IV) an aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium, said particles comprising the reaction product obtained by polymerizing the components of a pre-emulsion formed from:
(A) an active hydrogen-containing polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable, ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1-C30 alkyl group having at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group; and (iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers; and (C) a crosslinking monomer;
wherein the active hydrogen functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation, at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule; and at least 10 percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end of the molecule.
(I) a first reactant comprising reactive functional groups;
(II) a curing agent having functional groups reactive with the functional groups of the first reactant in (I);
(III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprised of:
(a) at least 20 weight percent of a crosslinking monomer having two or more groups of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 2 weight percent of one or more polymerizable ethylenically unsaturated monomers having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from -NR1R2, -OR3 and -SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and , -CH2CH2-(OC(CH3)HCH3)m-OH
where m is 0 to 30, D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) optionally, the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other; and (IV) an aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium, said particles comprising the reaction product obtained by polymerizing the components of a pre-emulsion formed from:
(A) an active hydrogen-containing polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable, ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1-C30 alkyl group having at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group; and (iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers; and (C) a crosslinking monomer;
wherein the active hydrogen functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation, at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule; and at least 10 percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end of the molecule.
2. The thermosetting composition of claim 1, wherein the polyol is one or more polyols selected from the group consisting of polyetherpolyols, polyesterpolyols and acrylic polyols.
3. The thermosetting composition of claim 2, wherein the polyol is one or more polyetherpolyols comprising the following formula (I):
wherein R1 is H or C1-C5 alkyl including mixed substituents, n is from 1 to and m is from 1 to 5.
wherein R1 is H or C1-C5 alkyl including mixed substituents, n is from 1 to and m is from 1 to 5.
4. The thermosetting composition of claim 2, wherein the polyol is one or more polyetherpolyol selected from the group consisting of poly(oxytetramethylene) glycols, poly(oxyethylene) glycols, poly(oxy-1,2-propylene) glycols, the reaction products of ethylene glycol with a mixture of 1,2-propylene oxide and ethylene oxide, poly(tetrahydrofuran), the reaction products obtained by the polymerization of ethylene oxide, propylene oxide and tetrahydrofuran, 1,6-hexanediol, trimethylolpropane, sorbitol and pentaerythritol.
5. The thermosetting composition of claim 1, wherein the polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group is one or more monomers comprising the formula where R2 is H or C1-C4 alkyl and R3 is selected from -(CHR4)p-OH, -CH2CH2-(O- CH2-CHR4)p-OH, -CH2-CHOH-CH2-O-CO-CR5R6R7, and -CH2-CHR4-O-CH2-CHOH-CH2-O-CO-CR5R6R7 where R4 is H or C1-C4 alkyl, R5, R6, and R7 are H or C1-C20 linear or branched alkyl and p is an integer from 0 to 20.
6. The thermosetting composition of claim 1, wherein the polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group (ii) comprises one or more monomers selected from the group consisting of hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, polyethyleneglycol ester of (meth)acrylic acid, polypropyleneglycol ester of (meth)acrylic acid, the reaction product of (meth)acrylic acid and the glycidyl ester of versatic acid, the reaction product of hydroxyethyl(meth)acrylate and the glycidyl ester of versatic acid, and the reaction product of hydroxypropyl(meth)acrylate and the glycidyl ester of versatic acid.
7. The thermosetting composition of claim 1, wherein the compound (iii) comprises a compound selected from the group consisting of dimethylol proprionic acid and 12-hydroxystearic acid 12-hydroxystearic acid.
8. The thermosetting composition of claim 1, wherein the polyisocyanate (iv) comprises one or more of an aliphatic and an aromatic polyisocyanate.
9. The thermosetting composition of claim 1, wherein the polyisocyanate (iv) comprises one or more selected from the group consisting of isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, alpha, alpha-xylylene diisocyanate, 4,4'-methylene-bis(cyclohexyl isocyanate), 1,2,4-benzene triisocyanate, and polymethylene polyphenyl isocyanate.
10. The thermosetting composition of claim 1, wherein the polyurethane-acrylate dispersed particles of the polyurethane dispersion has an ordered structure wherein greater than 50 percent by weight of an outer portion of the dispersed particle near the aqueous medium comprises residues from the active hydrogen functional polyurethane acrylate prepolymer comprising prepolymers with a polymerizable double bond at one end of the prepolymer and an active hydrogen containing group at the other end of the prepolymer and an interior portion of the particle comprises greater than 50 percent by weight of the reaction product of the one or more hydrophobic polymerizable ethylenically unsaturated monomers (B); and crosslinking monomer (C).
11. The thermosetting composition of claim 1, wherein each of the crosslinking monomer (a) and the crosslinking monomer (C) have two or more sites of polymerizable ethylenic unsaturation.
12. The thermosetting composition of claim 1, wherein each of the crosslinking monomer (a) and the crosslinking monomer (C) comprises one or more monomers selected from the group consisting of ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, glycerol allyloxy di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane tri(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane tri(meth)acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl phthalate, diallyl terephthalate, divinyl benzene, methylol (meth)acrylamide, triallylamine, and methylenebis (meth) acrylamide.
13. The thermosetting composition of claim 1, wherein each of the polymerizable ethylenically unsaturated monomer (c) and the one or more hydrophobic polymerizable ethylenically unsaturated monomers (B) comprises one or more monomers selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, N-butyl(meth)acrylate, t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, N-butoxy methyl (meth)acrylamide, styrene, (meth)acrylonitrile, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate.
14. The thermosetting composition of claim 1, wherein the ethylenically unsaturated monomer having hydrophilic functional groups (b) comprises one or more monomers selected from the group consisting of (meth)acrylamide, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate.
15. The thermosetting composition of claim 1, wherein the average particle size of the polymeric microparticles of (III) ranges from 0.01 to 1 microns.
16. The thermosetting composition of claim 1, wherein the average particle size of the polyurethane-acrylate particles of (IV) ranges from 50 nm to 500 nanometers.
17. The thermosetting composition of claim 1, wherein said thermosetting composition is a coating composition.
18. The thermosetting composition of claim 1, wherein the thermosetting composition is substantially free of polymeric emulsifiers and/or protective colloids.
19. The thermosetting composition of claim 1, wherein the functional groups of the first reactant (I) are selected from the group consisting of epoxy, carboxylic acid, hydroxy, amide, oxazoline, aceto acetate, isocyanate, methylol, amino, methylol ether, carbamate, and mixtures thereof.
20. The thermosetting composition of claim 1, wherein the functional groups of curing agent (II) are selected from the group consisting of epoxy, carboxylic acid, hydroxy, isocyanate, capped isocyanate, amine, methylol, methylol ether, beta-hydroxyalkylamide, and mixtures thereof.
21. The thermosetting composition of claim 1, wherein the functional groups of crosslinking agent (II) are different from and reactive with those of the first reactant (I).
22. The thermosetting composition of claim 1, wherein the first reactant (I) is a polymer containing hydroxyl functional groups, and the curing agent (II) comprises one or more materials selected from polyamines, aminoplast resins and polyisocyanates.
23. A coated substrate comprising:
(a) a substrate; and (b) the thermosetting composition of claim 1 over at least a portion of the substrate (a).
(a) a substrate; and (b) the thermosetting composition of claim 1 over at least a portion of the substrate (a).
24. The coated substrate of claim 23, wherein the thermosetting composition further comprises one or more effect pigments.
25. The coated substrate of claim 24, wherein the thermosetting composition when cured has a Flop Index of at least 10 and shortwave values of no more than 14.
26. A method of coating a substrate comprising:
(A) applying a thermosetting composition over at least a portion of the substrate;
(B) coalescing said thermosetting composition to form a substantially continuous film on the substrate; and (C) curing the thermosetting composition, wherein the thermosetting composition comprises:
(I) a first reactant comprising reactive functional groups;
(II) a curing agent having functional groups reactive with the functional groups of the first reactant in (I);
(III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprised of:
(a) at least 20 weight percent of a crosslinking monomer having two or more sites of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 2 weight percent of one or more polymerizable ethylenically unsaturated monomers having hydrophilic functional groups; and (c) optionally, the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other; and (IV) an aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium, said particles comprising the reaction product obtained by polymerizing the components of a pre-emulsion formed from:
(A) an active hydrogen-containing functional polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1-C30 alkyl group comprising at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group; and (iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers; and (C) a crosslinking monomer;
wherein the active hydrogen functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation, at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule; and at least 10 percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end of the molecule.
(A) applying a thermosetting composition over at least a portion of the substrate;
(B) coalescing said thermosetting composition to form a substantially continuous film on the substrate; and (C) curing the thermosetting composition, wherein the thermosetting composition comprises:
(I) a first reactant comprising reactive functional groups;
(II) a curing agent having functional groups reactive with the functional groups of the first reactant in (I);
(III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprised of:
(a) at least 20 weight percent of a crosslinking monomer having two or more sites of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 2 weight percent of one or more polymerizable ethylenically unsaturated monomers having hydrophilic functional groups; and (c) optionally, the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other; and (IV) an aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium, said particles comprising the reaction product obtained by polymerizing the components of a pre-emulsion formed from:
(A) an active hydrogen-containing functional polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1-C30 alkyl group comprising at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group; and (iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers; and (C) a crosslinking monomer;
wherein the active hydrogen functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation, at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule; and at least 10 percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end of the molecule.
27. The method of claim 26, wherein the polyol is one or more polyols selected from the group consisting of polyetherpolyols, polyesterpolyols and acrylic polyols.
28. The method of claim 26, wherein the polyol is one or more polyetherpolyols comprising the following formula (I):
wherein R1 is H or C1-C5 alkyl including mixed substituents, n is from 0 to and m is from 1 to 5.
wherein R1 is H or C1-C5 alkyl including mixed substituents, n is from 0 to and m is from 1 to 5.
29. The method of claim 26, wherein the polyol is one or more polyetherpolyol selected from the group consisting of poly(oxytetramethylene) glycols, poly(oxyethylene) glycols, poly(oxy-1,2-propylene) glycols, the reaction products of ethylene glycol with a mixture of 1,2-propylene oxide and ethylene oxide, poly(tetrahydrofuran), the reaction products obtained by the polymerization of ethylene oxide, propylene oxide and tetrahydrofuran, 1,6-hexanediol, trimethylolpropane, sorbitol and pentaerythritol.
30. The method of claim 26, wherein the polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group is one or more monomers comprising the formula where R2 is H or C1-C4 alkyl and R3 is selected from -(CHR4)p-OH, -CH2CH2-(OCH2-CHR4)p-OH, -CH2-CHOH-CH2-O-CO-CR5R6R7, and -CH2-CHR4-O-CH2-CHOH-CH2-O-CO-CR5R6R7 where R4 is H or C1-C4 alkyl, R5, R6, and R7 are H or C1-C20 linear or branched alkyl and p is an integer from 0 to 20.
31. The method of claim 26, wherein the polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group (ii) comprises one or more monomers selected from the group consisting of hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, polyethyleneglycol ester of (meth)acrylic acid, polypropyleneglycol ester of (meth)acrylic acid, the reaction product of (meth)acrylic acid and the glycidyl ester of versatic acid, the reaction product of hydroxyethyl(meth)acrylate and the glycidyl ester of versatic acid, and the reaction product of hydroxypropyl(meth)acrylate and the glycidyl ester of versatic acid.
32. The method of claim 26, wherein the compound (iii) comprises a compound selected from the group consisting of dimethylol proprionic acid and 12-hydroxystearic acid.
33. The method of claim 26, wherein the polyisocyanate (iv) comprises one or more of an aliphatic and an aromatic polyisocyanate.
34. The method of claim 26, wherein the polyisocyanate (iv) comprises one or more selected from the group consisting of isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, alpha, alpha-xylylene diisocyanate, 4,4'-methylene-bis(cyclohexyl isocyanate), 1,2,4-benzene triisocyanate, and polymethylene polyphenyl isocyanate.
35. The method of claim 26, wherein the polyurethane-acrylate dispersed particles of the polyurethane dispersion have an ordered structure wherein greater than 50 percent by weight of an outer portion of the dispersed particle near the aqueous medium comprises residues from the active hydrogen functional polyurethane acrylate prepolymer comprising prepolymers with a polymerizable double bond at one end of the prepolymer and an active hydrogen containing group at the other end of the prepolymer and an interior portion of the particle comprises greater than 50 percent by weight of the reaction product of the one or more hydrophobic polymerizable ethylenically unsaturated monomers (B); and crosslinking monomer (C).
36. The method of claim 26, wherein each of the crosslinking monomer (a) and the crosslinking monomer (C) have two or more sites of polymerizable ethylenic unsaturation.
37. The method of claim 26, wherein each of the crosslinking monomer (a) and the crosslinking monomer (C) comprises one or more monomers selected from the group consisting of ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, glycerol allyloxy di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane tri(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane tri(meth)acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl phthalate, diallyl terephthalate, divinyl benzene, methylol (meth)acrylamide, triallylamine, and methylenebis (meth) acrylamide.
38. The method of claim 26, wherein each of the polymerizable ethylenically unsaturated monomer (c) and the one or more hydrophobic polymerizable ethylenically unsaturated monomers (B) comprises one or more monomers selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, N-butyl(meth)acrylate, t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, N-butoxy methyl (meth)acrylamide, styrene, (meth)acrylonitrile, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate.
39. The method of claim 26, wherein the ethylenically unsaturated monomer having hydrophilic functional groups (b) comprises one or more monomers selected from the group consisting of (meth)acrylamide, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate.
40. The method of claim 26, wherein the average particle size of the polymeric microparticles of (III) ranges from 0.01 to 1 microns.
41. The method of claim 26, wherein the average particle size of the polyurethane-acrylate particles of (IV) ranges from 50 nm to 500 nanometers.
42. The method of claim 269 wherein said thermosetting composition is a coating composition.
43. The method of claim 26, wherein the thermosetting composition is substantially free of polymeric emulsifiers and/or protective colloids.
44. The method of claim 26, wherein the functional groups of the first reactant (I) are selected from the group consisting of epoxy, carboxylic acid, hydroxy, amide, oxazoline, aceto acetate, isocyanate, methylol, amino, methylol ether, carbamate, and mixtures thereof.
45. The method of claim 26, wherein the functional groups of curing agent (II) are selected from the group consisting of epoxy, carboxylic acid, hydroxy, isocyanate, capped isocyanate, amine, methylol, methylol ether, beta-hydroxyalkylamide, and mixtures thereof.
46. The method of claim 26, wherein the functional groups of crosslinking agent (II) are different from and reactive with those of the first reactant (I).
47. The method of claim 26, wherein the first reactant (I) is a polymer containing hydroxyl functional groups, and the curing agent (II) comprises one or more materials selected from polyamines, aminoplast resins and polyisocyanates.
48. A substrate coated by the method of claim 26.
49. The coated substrate of claim 48, wherein the thermosetting composition further comprises one or more effect pigments.
50. The coated substrate of claim 49, wherein the thermosetting composition when cured has a Flop index of at least 10 and shortwave values of no more than 14.
51. A multi-layer composite coating comprising:
(A) a base coat layer deposited from an effect pigment-containing base coat composition, wherein said base coat composition comprises:
(I) a first reactant comprising reactive functional groups;
(II) a curing agent having functional groups reactive with the functional groups of the first reactant in (I);
(III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprised of:
(a) at least 20 weight. percent of a crosslinking monomer having two or more groups of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 2 weight percent of one or more polymerizable ethylenically unsaturated monomers having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from -NR1R2, -OR3 and -SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and , -CH2CH2-(OC(CH3)HCH2)m-OH
where m is 0 to 30, D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) optionally, the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other; and (IV) an aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium, said particles comprising the reaction product obtained by polymerizing the components of a pre-emulsion formed from:
(A) an active hydrogen-containing polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1-C30 alkyl group comprising at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group; and (iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers; and (C) a crosslinking monomer;
wherein the active hydrogen functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule; and at least 10 percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end of the molecule; and (B) a substantially pigment free top coat layer deposited over at least a portion of said base coat layer from a substantially pigment free top coat composition.
(A) a base coat layer deposited from an effect pigment-containing base coat composition, wherein said base coat composition comprises:
(I) a first reactant comprising reactive functional groups;
(II) a curing agent having functional groups reactive with the functional groups of the first reactant in (I);
(III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprised of:
(a) at least 20 weight. percent of a crosslinking monomer having two or more groups of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 2 weight percent of one or more polymerizable ethylenically unsaturated monomers having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from -NR1R2, -OR3 and -SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and , -CH2CH2-(OC(CH3)HCH2)m-OH
where m is 0 to 30, D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) optionally, the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other; and (IV) an aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium, said particles comprising the reaction product obtained by polymerizing the components of a pre-emulsion formed from:
(A) an active hydrogen-containing polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1-C30 alkyl group comprising at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group; and (iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers; and (C) a crosslinking monomer;
wherein the active hydrogen functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule; and at least 10 percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end of the molecule; and (B) a substantially pigment free top coat layer deposited over at least a portion of said base coat layer from a substantially pigment free top coat composition.
52. The multi-layer composite coating of claim 51, wherein the polyol is one or more polyols selected from the group consisting of polyetherpolyols, polyesterpolyols and acrylic polyols.
53. The multi-layer composite coating of claim 52, wherein the polyol is one or more polyetherpolyols comprising the following formula (I):
wherein R1 is H or C1-C5 alkyl including mixed substituents, n is from 0 to and m is from 1 to 5.
wherein R1 is H or C1-C5 alkyl including mixed substituents, n is from 0 to and m is from 1 to 5.
54. The multi-layer composite coating of claim 51, wherein the polyol is one or more polyetherpolyols selected from the group consisting of poly(oxytetramethylene) glycols, poly(oxyethylene) glycols, poly(oxy-1,2-propylene) glycols, the reaction products of ethylene glycol with a mixture of 1,2-propylene oxide and ethylene oxide, poly(tetrahydrofuran), the reaction products obtained by the polymerization of ethylene oxide, propylene oxide and tetrahydrofuran, 1,6-hexanediol, trimethylolpropane, sorbitol and pentaerythritol.
55. The multi-layer composite coating of claim 51, wherein the polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group is one or more monomers comprising the formula where R2 is H or C1-C4 alkyl and R3 is selected from -(CHR4)p-OH, -CH2CH2-(O- CH2-CHR4)p-OH, -CH2-CHOH-CH2-O-CO-CR5R6R7, and -CH2-CHR4-O-CH2-CHOH-CH2-O-CO-CR5R6R7 where R4 is H or C1-C4 alkyl, R5, R6, and R7 are H or C1-C20 linear or branched alkyl and p is an integer from 0 to 20.
56. The multi-layer composite coating of claim 51, wherein the polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group (ii) comprises one or more monomers selected from the group consisting of hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, polyethyleneglycol ester of (meth)acrylic acid, polypropyleneglycol ester of (meth)acrylic acid, the reaction product of (meth)acrylic acid and the glycidyl ester of versatic acid, the reaction product of hydroxyethyl(meth)acrylate and the glycidyl ester of versatic acid, and the reaction product of hydroxypropyl(meth)acrylate and the glycidyl ester of versatic acid.
57. The multi-layer composite coating of claim 51, wherein the compound (iii) comprises a compound selected from the group consisting of dimethylol proprionic acid and 12-hydroxystearic acid.
58. The multi-layer composite coating of claim 51, wherein the polyisocyanate (iv) comprises one or more of an aliphatic and an aromatic polyisocyanate.
59. The multi-layer composite coating of claim 51, wherein the polyisocyanate (iv) comprises one or more selected from the group consisting of isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, alpha, alpha-xylylene diisocyanate, 4,4'-methylene-bis(cyclohexyl isocyanate), 1,2,4-benzene triisocyanate, and polymethylene polyphenyl isocyanate.
60. The multi-layer composite coating of claim 51, wherein the polyurethane-acrylate dispersed particles of the polyurethane dispersion have an ordered structure wherein greater than 50 percent by weight of an outer portion of the dispersed particle near the aqueous medium comprises residues from the active hydrogen functional polyurethane acrylate prepolymer comprising prepolymers with a polymerizable double bond at one end of the prepolymer and an active hydrogen containing group at the other end of the prepolymer and an interior portion of the particle comprises greater than 50 percent by weight of the reaction product of the one or more hydrophobic polymerizable ethylenically unsaturated monomers (B); and crosslinking monomer (C).
61. The multi-layer composite coating of claim 51, wherein each of the crosslinking monomer (a) and the crosslinking monomer (C) each have two or more sites of polymerizable ethylenic unsaturation.
62. The multi-layer composite coating of claim 51, wherein each of the crosslinking monomer (a) and the crosslinking monomer (C) comprises one or more monomers selected from the group consisting of ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, glycerol allyloxy di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane tri(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane tri(meth)acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl phthalate, diallyl terephthalate, divinyl benzene, methylol (meth)acrylamide, triallylamine, and methylenebis (meth) acrylamide.
63. The multi-layer composite coating of claim 51, wherein each of the polymerizable ethylenically unsaturated monomer (c) and the one or more hydrophobic polymerizable ethylenically unsaturated monomers (B) comprises one or more monomers selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, N-butyl(meth)acrylate, t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, N-butoxy methyl (meth)acrylamide, styrene, (meth)acrylonitrile, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate.
64. The multi-layer composite coating of claim 51, wherein the ethylenically unsaturated monomer having hydrophilic functional groups (b) comprises one or more monomers selected from the group consisting of (meth)acrylamide, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate.
65. The multi-layer composite coating of claim 51, wherein the average particle size of the polymeric microparticles of (III) ranges from 0.01 to 1 microns.
66. The multi-layer composite coating of claim 51, wherein the average particle size of the polyurethane-acrylate particles of (IV) ranges from 50 nm to 500 nanometers.
67. The multi-layer composite coating of claim 51, wherein said thermosetting composition is a coating composition.
68. The multi-layer composite coating of claim 51, wherein the thermosetting composition is substantially free of polymeric emulsifiers and/or protective colloids.
69. The multi-layer composite coating of claim 51, wherein the functional groups of the first reactant (I) are selected from the group consisting of epoxy, carboxylic acid, hydroxy, amide, oxazoline, aceto acetate, isocyanate, methylol, amino, methylol ether, carbamate, and mixtures thereof.
70. The multi-layer composite coating of claim 51, wherein the functional groups of curing agent (II) are selected from the group consisting of epoxy, carboxylic acid, hydroxy, isocyanate, capped isocyanate, amine, methylol, methylol ether, beta-hydroxyalkylamide, and mixtures thereof.
71. The multi-layer composite coating of claim 51, wherein the functional groups of crosslinking agent (II) are different from and reactive with those of the first reactant (I).
72. The multi-layer composite coating of claim 51, wherein the first reactant (I) is a polymer containing hydroxyl functional groups, and the curing agent (II) comprises one or more materials selected from polyamines, aminoplast resins and polyisocyanates.
73. A coated substrate comprising:
(A) a substrate, and (B) the multi-layer composite coating composition of claim 51 over at least a portion of the substrate (A).
(A) a substrate, and (B) the multi-layer composite coating composition of claim 51 over at least a portion of the substrate (A).
74. The coated substrate of claim 73, wherein the thermosetting composition further comprises one or more effect pigments.
75. The coated substrate of claim 73, wherein the substrate is selected from a metallic substrate, an elastomeric substrate, and combinations thereof.
76. The coated substrate of claim 74, wherein the thermosetting composition when cured has a Flop index of at least 10 and shortwave values of no more than 14.
77. A coating composition comprising:
(I) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprised of:
(a) at least 20 weight percent of a crosslinking monomer having two or more groups of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 2 weight percent of one or more polymerizable ethylenically unsaturated monomers having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from ~NR1R2, -OR3 and ~SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and , -CH2CH2-(OC(CH3)HCH2)m-OH
where m is 0 to 30, D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) optionally, the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other; and (II) an aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium, said particles comprising the reaction product obtained by polymerizing the components of a pre-emulsion formed from:
(A) an active hydrogen-containing polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1-C30 alkyl group having at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group; and (iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers; and (C) a crosslinking monomer;
wherein the acid-functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation, at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule; and at least percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end the molecule.
(I) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprised of:
(a) at least 20 weight percent of a crosslinking monomer having two or more groups of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 2 weight percent of one or more polymerizable ethylenically unsaturated monomers having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from ~NR1R2, -OR3 and ~SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and , -CH2CH2-(OC(CH3)HCH2)m-OH
where m is 0 to 30, D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) optionally, the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other; and (II) an aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium, said particles comprising the reaction product obtained by polymerizing the components of a pre-emulsion formed from:
(A) an active hydrogen-containing polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1-C30 alkyl group having at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group; and (iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers; and (C) a crosslinking monomer;
wherein the acid-functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation, at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule; and at least percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end the molecule.
78. The coating composition of claim 77, wherein the polyol is one or more polyols selected from the group consisting of polyetherpolyols, polyesterpolyols and acrylic polyols.
79. The coating composition of claim 78, wherein the polyol is one or more polyetherpolyols comprising the following formula (I):
wherein R1 is H or C1-C5 alkyl including mixed substituents, n is from 0 to and m is from 1 to 5.
wherein R1 is H or C1-C5 alkyl including mixed substituents, n is from 0 to and m is from 1 to 5.
80. The coating composition of claim 78, wherein the polyol is one or more polyetherpolyol selected from the group consisting of poly(oxytetramethylene) glycols, poly(oxyethylene) glycols, poly(oxy-1,2-propylene) glycols, the reaction products of ethylene glycol with a mixture of 1,2-propylene oxide and ethylene oxide, poly(tetrahydrofuran), the reaction products obtained by the polymerization of ethylene oxide, propylene oxide and tetrahydrofuran, 1,6-hexanediol, trimethylolpropane, sorbitol and pentaerythritol.
81. The coating composition of claim 77, wherein the polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group is one or more monomers comprising the formula where R2 is H or C1-C4 alkyl and R3 is selected from ~(CHR4)p-OH, -CH2CH2~
(O-CH2-CHR4)p-OH, -CH2-CHOH-CH2-O-CO-CR5R6R7, and -CH2-CHR4-O-CH2-CHOH-CH2-O-CO-CR5R6R7 where R4 is H or C1-C4 alkyl, R5, R6, and R7 are H or C1-C20 linear or branched alkyl and p is an integer from 0 to 20.
(O-CH2-CHR4)p-OH, -CH2-CHOH-CH2-O-CO-CR5R6R7, and -CH2-CHR4-O-CH2-CHOH-CH2-O-CO-CR5R6R7 where R4 is H or C1-C4 alkyl, R5, R6, and R7 are H or C1-C20 linear or branched alkyl and p is an integer from 0 to 20.
82. The coating composition of claim 77, wherein the polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group (ii) comprises one or more monomers selected from the group consisting of hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, polyethyleneglycol ester of (meth)acrylic acid, polypropyleneglycol ester of (meth)acrylic acid, the reaction product of (meth)acrylic acid and the glycidyl ester of versatic acid, the reaction product of hydroxyethyl(meth)acrylate and the glycidyl ester of versatic acid, and the reaction product of hydroxypropyl(meth)acrylate and the glycidyl ester of versatic acid.
83. The coating composition of claim 77, wherein the compound (iii) comprises a compound selected from the group consisting of dimethylol proprionic acid and 12-hydroxystearic acid.
84. The coating composition of claim 77, wherein the polyisocyanate (iv) comprises one or more of an aliphatic and an aromatic polyisocyanate.
85. The coating composition of claim 77, wherein the polyisocyanate (iv) comprises one or more selected from the group consisting of isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, alpha, alpha-xylylene diisocyanate, 4,4'-methylene-bis(cyclohexyl isocyanate), 1,2,4-benzene triisocyanate, and polymethylene polyphenyl isocyanate.
86. The coating composition of claim 77, wherein the polyurethane-acrylate dispersed particles of the polyurethane dispersion have an ordered structure wherein greater than 50 percent by weight of an outer portion of the dispersed particle near the aqueous medium comprises residues from the active hydrogen functional polyurethane acrylate prepolymer comprising prepolymers with a polymerizable double bond at one end of the prepolymer and an active hydrogen containing group at the other end of the prepolymer and an interior portion of the particle comprises greater than 50 percent by weight of the reaction product of the one or more hydrophobic polymerizable ethylenically unsaturated monomers (B); and crosslinking monomer (C).
87. The coating composition of claim 77, wherein each of the crosslinking monomer (a) and the crosslinking monomer (C) have two or more sites of polymerizable ethylenic unsaturation.
88. The coating composition of claim 77, wherein each of the crosslinking monomer (a) and the crosslinking monomer (C) comprises one or more monomers selected from the group consisting of ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, glycerol allyloxy di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane tri(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane tri(meth)acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl phthalate, diallyl terephthalate, divinyl benzene, methylol (meth)acrylamide, triallylamine, and methylenebis (meth) acrylamide.
89. The coating composition of claim 77, wherein each of the polymerizable ethylenically unsaturated monomer (c) and the one or more hydrophobic polymerizable ethylenically unsaturated monomers (B) comprises one or more monomers selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, N-butyl(meth)acrylate, t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, N-butoxy methyl (meth)acrylamide, styrene, (meth)acrylonitrile, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate.
90. The coating composition of claim 77, wherein the ethylenically unsaturated monomer having hydrophilic functional groups (b) comprises one or more monomers selected from the group consisting of (meth)acrylamide, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate.
91. The coating composition of claim 77, wherein the average particle size of the polymeric microparticles of (III) ranges from 0.01 to 1 microns.
92. The coating composition of claim 77, wherein the average particle size of the polyurethane-acrylate particles of (IV) ranges from 50 nm to 500 nanometers.
93. The coating composition of claim 77, wherein the coating composition is substantially free of polymeric emulsifiers and/or protective colloids.
94. A coated substrate comprising:
(a) a substrate; and (b) a coating layer derived from the coating composition of claim 77 over at least a portion of the substrate (a).
(a) a substrate; and (b) a coating layer derived from the coating composition of claim 77 over at least a portion of the substrate (a).
95. The coated substrate of claim 94, wherein the coating composition further comprises one or more effect pigments.
96. The coated substrate of claim 95, wherein the coating layer has a Flop Index of at least 10 and shortwave values of no more than 14.
97. A coating composition comprising an aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium, said particles comprising the reaction product obtained by polymerizing the components of a pre-emulsion formed from:
(A) an active hydrogen-containing polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1-C30 alkyl group having at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group; and (iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers; and (C) a crosslinking monomer;
wherein the acid-functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation, at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule; and at least percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end the molecule.
(A) an active hydrogen-containing polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1-C30 alkyl group having at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group; and (iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers; and (C) a crosslinking monomer;
wherein the acid-functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation, at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule; and at least percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end the molecule.
98. The coating composition of claim 97, wherein the polyol is one or more polyols selected from the group consisting of polyetherpolyols, polyesterpolyols and acrylic polyols.
99. The coating composition of claim 98, wherein the polyol is one or more polyetherpolyols comprising the following formula (I):
wherein R1 is H or C1-C5 alkyl including mixed substituents, n is from 0 to and m is from 1 to 5.
wherein R1 is H or C1-C5 alkyl including mixed substituents, n is from 0 to and m is from 1 to 5.
100. The coating composition of claim 98, wherein the polyol is one or more polyetherpolyol selected from the group consisting of poly(oxytetramethylene) glycols, poly(oxyethylene) glycols, poly(oxy-1,2-propylene) glycols, the reaction products of ethylene glycol with a mixture of 1,2-propylene oxide and ethylene oxide, poly(tetrahydrofuran), the reaction products obtained by the polymerization of ethylene oxide, propylene oxide and tetrahydrofuran, 1,6-hexanediol, trimethylolpropane, sorbitol and pentaerythritol.
101. The coating composition of claim 97, wherein the polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group is one or more monomers comprising the formula where R2 is H or C1-C4 alkyl and R3 is selected from ~(CHR4)p-OH, -CH2CH2~
(O-CH2-CHR4)p-OH, -CH2-CHOH-CH2-O-CO-CR5R6R7, and -CH2-CHR4-O-CH2-CHOH-CH2-O-CO-CR5R6R7 where R4 is H or C1-C4 alkyl, R5, R6, and R7 are H or C1-C20 linear or branched alkyl and p is an integer from 0 to 20.
(O-CH2-CHR4)p-OH, -CH2-CHOH-CH2-O-CO-CR5R6R7, and -CH2-CHR4-O-CH2-CHOH-CH2-O-CO-CR5R6R7 where R4 is H or C1-C4 alkyl, R5, R6, and R7 are H or C1-C20 linear or branched alkyl and p is an integer from 0 to 20.
102. The coating composition of claim 97, wherein the polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group (ii) comprises one or more monomers selected from the group consisting of hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, polyethyleneglycol ester of (meth)acrylic acid, polypropyleneglycol ester of (meth)acrylic acid, the reaction product of (meth)acrylic acid and the glycidyl ester of versatic acid, the reaction product of hydroxyethyl(meth)acrylate and the glycidyl ester of versatic acid, and the reaction product of hydroxypropyl(meth)acrylate and the glycidyl ester of versatic acid.
103. The coating composition of claim 97, wherein the compound (iii) comprises a compound selected from the group consisting of dimethylol proprionic acid and 12-hydroxystearic acid.
104. The coating composition of claim 97, wherein the polyisocyanate (iv) comprises one or more of an aliphatic and an aromatic polyisocyanate.
105. The coating composition of claim 97, wherein the polyisocyanate (iv) comprises one or more selected from the group consisting of isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, alpha, alpha-xylylene diisocyanate, 4,4'-methylene-bis(cyclohexyl isocyanate), 1,2,4-benzene triisocyanate, and polymethylene polyphenyl isocyanate.
106. The coating composition of claim 97, wherein the polyurethane-acrylate dispersed particles of the polyurethane dispersion have an an ordered structure wherein greater than 50 percent by weight of an outer portion of the dispersed particle near the aqueous medium comprises residues from the active hydrogen functional polyurethane acrylate prepolymer comprising prepolymers with a polymerizable double bond at one end of the prepolymer and an active hydrogen containing group at the other end of the prepolymer and an interior portion of the particle comprises greater than 50 percent by weight of the reaction product of the one or more hydrophobic polymerizable ethylenically unsaturated monomers (B); and crosslinking monomer (C).
107. The coating composition of claim 97, wherein the crosslinking monomer (C) has two or more sites of polymerizable ethylenic unsaturation.
108. The coating composition of claim 97, wherein the crosslinking monomer (C) comprises one or more monomers selected from the group consisting of ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, glycerol allyloxy di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane tri(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane tri(meth)acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl phthalate, diallyl terephthalate, divinyl benzene, methylol (meth)acrylamide, triallylamine, and methylenebis (meth) acrylamide.
109. The coating composition of claim 97, wherein the one or more hydrophobic polymerizable ethylenically unsaturated monomers (B) comprises one or more monomers selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, N-butyl(meth)acrylate, t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, N-butoxy methyl (meth)acrylamide, styrene, (meth)acrylonitrile, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate.
110. The coating composition of claim 97, wherein the average particle size of the polyurethane-acrylate particles of (IV) ranges from 50 nm to 500 nanometers.
111. A coated substrate comprising:
(a) a substrate; and (b) a coating layer derived from the coating composition of claim 97 over at least a portion of the substrate (a).
(a) a substrate; and (b) a coating layer derived from the coating composition of claim 97 over at least a portion of the substrate (a).
112. The coated substrate of claim 97, wherein the coating composition further comprises one or more effect pigments.
113. The coated substrate of claim 112, wherein the coating layer has a Flop Index of at least 10 and shortwave values of no more than 14.
114. An aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium, said particles comprising the reaction product obtained by polymerizing the components of a pre-emulsion formed from:
(A) an active hydrogen-containing polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1-C30 alkyl group having at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group; and (iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers; and (C) a crosslinking monomer;
wherein the acid-functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation, at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule; and at least percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers aqueous having at least one terminal polymerizable site of ethylenic unsaturation at each end the molecule.
(A) an active hydrogen-containing polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1-C30 alkyl group having at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group; and (iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers; and (C) a crosslinking monomer;
wherein the acid-functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation, at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule; and at least percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers aqueous having at least one terminal polymerizable site of ethylenic unsaturation at each end the molecule.
115. The aqueous polyurethane dispersion of claim 114, wherein the polyol is one or more polyols selected from the group consisting of polyetherpolyols, polyesterpolyols and acrylic polyols.
116. The aqueous polyurethane dispersion of claim 115, wherein the polyol is one or more polyetherpolyols comprising the following formula (I):
wherein R1 is H or C1-C5 alkyl including mixed substituents, n is from 0 to and m is from 1 to 5.
wherein R1 is H or C1-C5 alkyl including mixed substituents, n is from 0 to and m is from 1 to 5.
117. The aqueous polyurethane dispersion of claim 115, wherein the polyol is one or more polyetherpolyol selected from the group consisting of poly(oxytetramethylene) glycols, poly(oxyethylene) glycols, poly(oxy-1,2-propylene) glycols, the reaction products of ethylene glycol with a mixture of 1,2-propylene oxide and ethylene oxide, poly(tetrahydrofuran), the reaction products obtained by the polymerization of ethylene oxide, propylene oxide and tetrahydrofuran, 1,6-hexanediol, trimethylolpropane, sorbitol and pentaerythritol.
118. The aqueous polyurethane dispersion of claim 114, wherein the polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group is one or more monomers comprising the formula where R2 is H or C1-C4 alkyl and R3 is selected from -(CHR4)p-OH, -CH2CH2-(O- CH2-CHR4)p-OH, -CH2-CHOH-CH2-O-CO-CR5R6R7, and -CH2-CHR4-O-CH2-CHOH-CH2-O-CO-CR5R6R7 where R4 is H or C1-C4 alkyl, R5, R6, and R7 are H or C1-C20 linear or branched alkyl and p is an integer from 0 to 20.
119. The aqueous polyurethane dispersion of claim 114, wherein the polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group (ii) comprises one or more monomers selected from the group consisting of hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, polyethyleneglycol ester of (meth)acrylic acid, polypropyleneglycol ester of (meth)acrylic acid, the reaction product of (meth)acrylic acid and the glycidyl ester of versatic acid, the reaction product of hydroxyethyl(meth)acrylate and the glycidyl ester of versatic acid, and the reaction product of hydroxypropyl(meth)acrylate and the glycidyl ester of versatic acid.
120. The aqueous polyurethane dispersion of claim 114, wherein the compound (iii) comprises a compound selected from the group consisting of dimethylol proprionic acid and 12-hydroxystearic acid.
121. The aqueous polyurethane dispersion of claim 114, wherein the polyisocyanate (iv) comprises one or more of an aliphatic and an aromatic polyisocyanate.
122. The aqueous polyurethane dispersion of claim 114, wherein the polyisocyanate (iv) comprises one or more selected from the group consisting of isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, alpha, alpha-xylylene diisocyanate, 4,4'-methylene-bis(cyclohexyl isocyanate), 1,2,4-benzene triisocyanate, and polymethylene polyphenyl isocyanate.
123. The aqueous polyurethane dispersion of claim 114, wherein the polyurethane-acrylate dispersed particles of the polyurethane dispersion have a core-shell architecture wherein greater than 50 percent by weight of the shell comprises residues from the active hydrogen functional polyurethane acrylate prepolymer comprising prepolymers with a polymerizable double bond at one end of the prepolymer and an active hydrogen containing group at the other end of the prepolymer and the core comprises greater than 50 percent by weight of the reaction product of the one or more hydrophobic polymerizable ethylenically unsaturated monomers (B); and crosslinking monomer (C).
124. The aqueous polyurethane dispersion of claim 114, wherein the crosslinking monomer (C) has two or more sites of polymerizable ethylenic unsaturation.
125. The aqueous polyurethane dispersion of claim 114, wherein the crosslinking monomer (C) comprises one or more monomers selected from the group consisting of ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, glycerol allyloxy di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane tri(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane tri(meth)acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl phthalate, diallyl terephthalate, divinyl benzene, methylol (meth)acrylamide, triallylamine, and methylenebis (meth) acrylamide.
126. The aqueous polyurethane dispersion of claim 114, wherein the one or more hydrophobic polymerizable ethylenically unsaturated monomers (B) comprises one or more monomers selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, N-butyl(meth)acrylate, t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, N-butoxy methyl (meth)acrylamide, styrene, (meth)acrylonitrile, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate.
127. The aqueous polyurethane dispersion of claim 114, wherein the average particle size of the polyurethane-acrylate particles of (IV) ranges from 50 nm to 500 nanometers.
128. A multi-layer composite coating comprising:
(A) a base coat layer deposited from a base coat composition, wherein said base coat composition comprises:
(I) a first reactant comprising reactive functional groups;
(II) a curing agent having functional groups reactive with the functional groups of the first reactant in (I);
(III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprised of:
(a) at least 20 weight percent of a crosslinking monomer having two or more groups of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 2 weight percent of one or more polymerizable ethylenically unsaturated monomers having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from -NR1R2, -OR3 and -SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and, -CH2CH2-(OC(CH3)HCH2)m-OH
where m is 0 to 30, D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) optionally, the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other; and (IV) an aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium, said particles comprising the reaction product obtained by polymerizing the components of a pre-emulsion formed from:
(A) an active hydrogen-containing polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1-C30 alkyl group comprising at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group; and (iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers; and (C) a crosslinking monomer;
wherein the active hydrogen functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule; and at least 10 percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end of the molecule; and (B) a substantially pigment free top coat layer wherein said top coat layer comprises a substantially pigment free powder coating composition deposited over at least a portion of said base coat layer from the powder coating composition.
(A) a base coat layer deposited from a base coat composition, wherein said base coat composition comprises:
(I) a first reactant comprising reactive functional groups;
(II) a curing agent having functional groups reactive with the functional groups of the first reactant in (I);
(III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprised of:
(a) at least 20 weight percent of a crosslinking monomer having two or more groups of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 2 weight percent of one or more polymerizable ethylenically unsaturated monomers having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from -NR1R2, -OR3 and -SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and, -CH2CH2-(OC(CH3)HCH2)m-OH
where m is 0 to 30, D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) optionally, the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other; and (IV) an aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium, said particles comprising the reaction product obtained by polymerizing the components of a pre-emulsion formed from:
(A) an active hydrogen-containing polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1-C30 alkyl group comprising at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group; and (iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers; and (C) a crosslinking monomer;
wherein the active hydrogen functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule; and at least 10 percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end of the molecule; and (B) a substantially pigment free top coat layer wherein said top coat layer comprises a substantially pigment free powder coating composition deposited over at least a portion of said base coat layer from the powder coating composition.
129. The multi-layer composite coating of claim 128, wherein the aqueous polyurethane dispersion (iv) is present in the base coat composition of (A) in an amount sufficient to provide a multi-layer composite coating having a b value, as measured according to the L*a*b color space theory, which is at least 0.2 less than the b value of a multi-layer composite coating in which the base coat composition does not contain the aqueous polyurethane dispersion (iv).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/126,903 | 2002-04-19 | ||
| US10/126,903 US7001952B2 (en) | 2002-04-19 | 2002-04-19 | Coating compositions containing polyurethane dispersions and highly crosslinked polymer particles |
| PCT/US2003/011890 WO2003089487A1 (en) | 2002-04-19 | 2003-04-17 | Coating compositions containing polyurethane dispersions and highly crosslinked polymer particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2482599A1 true CA2482599A1 (en) | 2003-10-30 |
| CA2482599C CA2482599C (en) | 2010-02-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2482599 Expired - Fee Related CA2482599C (en) | 2002-04-19 | 2003-04-17 | Coating compositions containing polyurethane dispersions and highly crosslinked polymer particles |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US7001952B2 (en) |
| EP (1) | EP1497349B1 (en) |
| JP (2) | JP4411407B2 (en) |
| KR (1) | KR20040103982A (en) |
| CN (1) | CN100335519C (en) |
| AU (1) | AU2003234123B2 (en) |
| BR (2) | BR0309378A (en) |
| CA (1) | CA2482599C (en) |
| ES (1) | ES2767930T3 (en) |
| WO (1) | WO2003089487A1 (en) |
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2002
- 2002-04-19 US US10/126,903 patent/US7001952B2/en not_active Expired - Lifetime
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2003
- 2003-04-17 JP JP2003586206A patent/JP4411407B2/en not_active Expired - Fee Related
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- 2003-04-17 WO PCT/US2003/011890 patent/WO2003089487A1/en active Application Filing
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| US7001952B2 (en) | 2006-02-21 |
| AU2003234123A1 (en) | 2003-11-03 |
| EP1497349B1 (en) | 2019-12-04 |
| CA2482599C (en) | 2010-02-02 |
| BR0309378A (en) | 2005-02-22 |
| CN100335519C (en) | 2007-09-05 |
| JP4411407B2 (en) | 2010-02-10 |
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